Environmental Isotopes in

the Hydrological Cycle
Principles and Applications

Vol. 1
Water Resources Programme

Atoms for Peace

International Atomic Energy Agency

and United Nations Educational, Scientific and Cultural Organization
Atoms for Peace

(reprinted with minor corrections)

 Environmental Isotopes
in the Hydrological Cycle
Principles and Applications

International Atomic Energy Agency

and United Nations Educational, Scientific and Cultural Organization
(reprinted with minor corrections)
FOREWORD
The increasing demand for water in many regions
of the world has been generally translated into
intensive and too often unsustainable, exploita-
tion of water resources. In many instances, natu-
ral and man-made changes have profoundly af-
fected the local hydrological cycle. Under these
circumstances, more detailed information is often
required for a more precise assessment of wa-
ter resources and for the adoption of sustainable
management practices.
Environmental isotopes have been extensively
used during the last decades to address key as-
pects of the water cycle, such as the study of
the origin, dynamics and interconnections of for
example, groundwater, surface water and the at-
mosphere. The use of environmental isotopes as
tracers of the water molecule has been extend-
ed beyond the classical applications of Isotope
Hydrology and today, a growing number of other
scientific disciplines, ranging from atmospheric
circulation to palaeoclimatology or ecology have
incorporated isotopes as powerful tracers to bet-
ter characterize systems and processes.
Expanding the use of isotope hydrology tools
to conduct hydrological studies relies on the ad-
equate training of scientists and technicians in
Member States and access to information. The
IAEA has played a key role over the years in
capacity building, especially with regard to con-
ducting individualized and group trainings on
how to use isotopes to improve water resources
management.
This publication is a reprint of a six-volume joint
IAEA-UNESCO document released in 2001 as
part of the IHP-V International Hydrological
Programme (Technical Documents in Hydrology,
No. 39). This document was originally edited by
W.G Mook and has been extensively used dur-
ing the last decade in training courses, seminars
and workshops, by the IAEA and others, deal-
ing with teaching the basic principles on the use
of environmental isotopes in hydrology and re-
lated fields. The publication has been a success-
ful technical reference as a training tool, and has
been translated into French and Spanish. It has
been distributed as hard copy and electronic files
in training packages and through the IAEA web
page. Now it is made available in the form of
IAEA Training Course Series in a single volume.
The IAEA officer responsible for this publication
is Pradeep Aggarwal of the Division of Physical
and Chemical Sciences.
PrEface

The availability of freshwater is one of the great Hydrology’ was realised in 1983 through the activ-
issues facing mankind today — in some ways ity of the joint IAEA/UNESCO Working Group on
the greatest, because problems associated with it Nuclear Techniques established within the frame-
affect the lives of many millions of people. It has work of IHP, and it has been widely used as practi-
consequently attracted a wide scale international cal guidance material in this specific field.
attention of UN Agencies and related internation-
In view of the fact that the IHP’s objectives in-
al/regional governmental and non-governmental
clude also a multi-disciplinary approach to the as-
organisations. The rapid growth of population
sessment and rational management of water re-
coupled to steady increase in water requirements
sources and taking note of the advances made in
for agricultural and industrial development have
isotope hydrology, the IAEA and UNESCO have
imposed severe stress on the available freshwater
initiated a joint activity in preparation of a series of
resources in terms of both the quantity and qual-
six up-to-date textbooks, covering the entire field
ity, requiring consistent and careful assessment
of hydrological applications of natural isotopes
and management of water resources for their sus-
(environmental isotopes) to the overall domain of
tainable development.
water resources and related environmental studies.
More and better water can not be acquired with-
The main aim of this series is to provide a com-
out the continuation and extension of hydrologi-
prehensive review of basic theoretical concepts
cal research. In this respect has the development
and principles of isotope hydrology methodolo-
and practical implementation of isotope method-
gies and their practical applications with some
ologies in water resources assessment and man-
illustrative examples. The volumes are designed
agement been part of the IAEA’s programme in
to be self-sufficient reference material for scien-
nuclear applications over the last four decades.
tists and engineers involved in research and/or
Isotope studies applied to a wide spectrum of hy-
practical applications of isotope hydrology as an
drological problems related to both surface and
integral part of the investigations related to wa-
groundwater resources as well as environmental
ter resources assessment, development and man-
studies in hydro-ecological systems are presently
agement. Furthermore, they are also expected to
an established scientific discipline, often referred
serve as ‘Teaching Material’ or text books to be
to as ‘Isotope Hydrology’. The IAEA contributed
used in universities and teaching institutions for
to this development through direct support to re-
incorporating the study of ‘isotopes in water’ in
search and training, and to the verification of iso-
general into the curriculum of the earth sciences.
tope methodologies through field projects imple-
Additionally the  contents can fulfil the  need for
mented in Member States.
basic knowledge in other disciplines of the Earth
The world-wide programme of the International Sciences dealing with water in general.
Hydrological Decade (1965–1974) and the sub-
These six volumes have been prepared through
sequent long-term International Hydrological
efforts and contributions of a number of scien-
Programme (IHP) of UNESCO have been an
tists involved in this specific field as cited in each
essential part of the well recognised interna-
volume, under the guidance and co-ordination of
tional frameworks for scientific research, edu-
the main author/co-ordinating editor designated
cation and training in the  field of hydrology.
for each volume. W. G. Mook (Netherlands),
The International Atomic Energy Agency (IAEA)
J. Gat (Israel), K. Rozanski (Poland), W. Stichler
and UNESCO have established a close co-opera-
(Germany), M.Geyh (Germany), K. P. Seiler
tion within the framework of both the earlier IHD
(Germany) and Y. Yurtsever (IAEA, Vienna) were
and the ongoing IHP in the specific aspects of sci-
involved as the main author/co-ordinating editors
entific and methodological developments related
in preparation of these six volumes, respectively.
to water resources that are of mutual interest to
Final editorial work on all volumes aiming to
the programmes of both organisations.
achieve consistency in the contents and layout
The first benchmark publication on isotope hydrol- throughout the whole series was undertaken by
ogy entitled ‘Guidebook on Nuclear Techniques in W. G. Mook (Netherlands).
Mr.Y. Yurtsever, Staff Member of the
Isotope Hydrology Section of the IAEA; and
Ms. A. Aureli, Programme Specialist, Division
of Water Sciences of UNESCO, were the Scientific
Officers in charge of co-ordination and provid-
ing scientific secretariat to the  various meetings
and activities that were undertaken throughout
the preparation of these publications.
The IAEA and UNESCO thank all those who
have contributed to the preparation of these vol-
umes and fully acknowledge the efforts and
achievements of the main authors and co-ordinat-
ing editors.
It is hoped that these six volumes will contribute
to wider scale applications of isotope methodolo-
gies for improved assessment and management
of water resources, facilitate incorporation of iso-
tope hydrology into the curricula of teaching and
education in water sciences and also foster fur-
ther developments in this specific field.
Paris / Vienna, March 2000
TABLE OF CONTENTS

VOLUME I: INTRODUCTION — Theory, methods, review

The Global Cycle of water...................................................................................................... 1

ATOMIC SYSTEMATICS AND NUCLEAR STRUCTURe............................................................... 19

Abundance and fractionation of stable isotopes .................................................. 23

ABUNDANCE VARIATIONS by NATURAL PROCESSEs............................................................. 33

rADIOnuclide DECAY and production............................................................................... 43

EQUATIONS OF RADIOACTIVE DECAY AND GROWTH............................................................. 49

natural abundance of the stable isotopes of C, O and H..................................... 55

NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H...................................... 75

CHEMISTRY OF CARBONIC ACID IN WATER............................................................................... 87

Water sampling and laboratory treatment............................................................... 99

measuring techniques............................................................................................................ 107

natural isotopes of elements other than h, c, o.................................................... 127

errors, means and fits............................................................................................................ 145

VOLUME II: Atmospheric water

The Atmosphere........................................................................................................................... 171

ISOTOPE METHODOLOGY............................................................................................................. 175

Stable isotope processes in the water cycle............................................................ 181

Observed isotope effects in precipitation................................................................... 197

TRITIUM IN the atmosphere.................................................................................................... 209

Isotopes De CO2 et O2 Atmospheriques.............................................................................. 217

VOLUME III: Surface Water

BASIC CONCEPTS AND MODELS.................................................................................................. 243

Rivers................................................................................................................................................ 249

Estuaries and the Sea.............................................................................................................. 273

LAKES AND RESERVOIRS.............................................................................................................. 279

RESPONSE OF SURFACE WATER SYSTEMS TO CLIMATIC CHANGES.................................. 299

VOLUME IV: groundwater — saturated and unsaturated zone

Hydrogeology and aquifer characteristics........................................................... 317

Tracers and transport.......................................................................................................... 327

Geohydraulic aspects............................................................................................................ 333

Water–Rock interactions..................................................................................................... 343

Applications to low-Temperature systems................................................................. 349

Applications tO high-Temperature systems................................................................ 389

Planning and performance of multiple isotope studies.................................... 409

References..................................................................................................................................... 413

VOLUME V: Man’s impact on groundwater systems

pOLLUTION SUSCEPTIBILITY OF AQUIFERS and pollution assessment................. 431

GROUNDWATER EXPLOITATION AND OVEREXPLOITATION................................................ 443

irrigation and the impact on groundwater quality............................................ 455

IMPACT OF URBANISATION ON GROUNDWATER.................................................................... 463

IMPACT OF LAND USE ON GROUNDWATER QUALITY........................................................... 469

SAMPLING OF WATER — QUANTITIES, METHODS, points of ATTENTION .................... 477

Outlook to further applications.................................................................................... 483

VOLUME VI: modelling

modelling INTRODUCTION....................................................................................................... 495

LUMPED PARAMETER MODELS................................................................................................... 497

COMPARTMENTAL MODEL APPROACHES TO GROUNDWATER FLOW SIMULATION...... 517

USE OF NUMERICAL MODELS TO SIMULATE GROUNDWATER FLOW AND

TRANSPORT............................................................................................................................... 541
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VOLUME I

INTRODUCTION
Theory, methods, review

Willem G. Mook
Centre for Isotope Research,
Groningen
Contribution de
J.J.de Vries, Free University, Amsterdam
Titre original en Anglais:
Environmental Isotopes in the hydrological cycle. Principles and applications
IHP-V Technical Documents in Hydrology, Nº 39. UNESCO – IAEA 2001
Preface to volume I
The  first volume in the  series of textbooks on
the environmental isotopes in the hydrologi-
cal cycle is the result of a re-orientation and in
part extension of the lecture notes I used during
the years I was teaching the hydrology students
of the Free University of Amsterdam an annual
course in Isotope Hydrology. During these years
my colleague and friend, Joe Pearson, and I set
ourselves to publish the lecture notes, but did not
find the time for the accomplishment of this task.
Now I have come to realise how much he taught
me and I gratefully acknowledge those days.
The  need for international agreement on defini-
tions and the use of symbols can not be sufficient-
ly emphasised. In this introductory volume I have
aimed at consistency as well as mathematical and
physical correctness. However, it is unavoidable
that, for historical reasons, the same consistency
could not be continued in all subsequent volumes.
The second important aim of this volume has
been to present no equations dealing with iso-
topes without the proper and understandable
mathematical derivation.
After an introductory chapter on the hydrologi-
cal cycle, this volume contains the principles of
radioactivity and of the isotope effects for stable
isotopes. The elements of hydrogen, carbon and
oxygen are being treated in detail, as they form
the ‘heart’ of isotopic applications in the wa-
ter cycle. The contribution of the other isotopes
is discussed less extensively in this volume.
Concrete isotopic applications in hydrology, here
only touched at in an illustrative manner, have
become greatly expanded by my colleagues in
the next volumes.
We felt that it is preferable that subjects of more
general interest to the other volumes, such as
the aqueous chemistry of inorganic carbon,
the treatment of water samples in the field and in
the laboratory, the techniques of isotopic analy-
ses, the statistical treatment of data, should be
treated in the first volume.
This series of 6 volumes are meant to be text-
books. This leads to certain requirements differ-
ent from the existing handbooks. Especially in
this introductory volume I have kept the number
of references to literature minimal, in favour of
the readability of the text.
I owe much gratitude to the ‘former’ co-work-
ers of ‘my lab’ for their assistance in reading
the manuscript, making many corrections, point-
ing out subjects that were failing and explana-
tions that could not well be understood, in short
for their continuing hospitality.
To my colleagues co-authors of this series I want
to express my appreciation for our highly stimu-
lating and pleasant co-operation
Groningen, 29 February2000
Willem G Mook
TABLE OF CONTENTS OF volume I

1. The Global Cycle of water............................................................................................... 1

1.1. Introduction.......................................................................................................................... 1
1.2. The Hydrosphere.................................................................................................................. 1
1.2.1. Origin of water on Earth........................................................................................ 1
1.2.2. The hydro-tectonic cycle....................................................................................... 2
1.2.3. Distribution of water over the various reservoirs.................................................. 3
1.3. The global water budget....................................................................................................... 4
1.4. Components of the hydrological cycle................................................................................. 5
1.4.1. Evaporation ........................................................................................................... 5
1.4.2. Precipitation and atmospheric circulation.............................................................. 6
1.4.3. Discharge from the continents............................................................................... 8
1.4.4. Groundwater ......................................................................................................... 9
1.4.5. Continental water surplus and water use............................................................. 12
1.5. The hydrosphere and global change................................................................................... 12
1.5.1. Climatic change................................................................................................... 12
1.5.2. The human factor................................................................................................. 14
1.5.2.1. Irrigation............................................................................................. 15
1.5.2.2. Wetland drainage................................................................................ 15
1.1.1.1 Ground cover damage......................................................................... 15
1.5.2.3. Deforestation...................................................................................... 16
1.5.2.4. Interbasin diversion............................................................................ 16
1.5.2.5. Streamflow management.................................................................... 16
1.5.2.6. Land use changes................................................................................ 16
1.6. Isotopes in the  hydrological cycle..................................................................................... 16

2. ATOMIC SYSTEMATICS AND NUCLEAR STRUCTURe....................................................... 19

2.1. Atomic structure and the periodic table of the elements.................................................... 19
2.2. Structure of the atomic nucleus.......................................................................................... 19
2.3. Stable and radioactive isotopes.......................................................................................... 20
2.4. Mass and energy................................................................................................................. 20

3. Abundance and fractionation of stable isotopes .......................................... 23

3.1. Isotope ratios and concentrations....................................................................................... 23
3.2. Isotope fractionation........................................................................................................... 23
3.3. Kinetic and equilibrium isotope fractionation.................................................................... 25
3.4. Theoretical background of equilibrium fractionation........................................................ 27
3.5. Fractionation by diffusion.................................................................................................. 30
3.6. Relation between atomic and molecular isotope ratios...................................................... 30
3.7. Relation between fractionations for three isotopic molecules........................................... 31

4. ABUNDANCE VARIATIONS by NATURAL PROCESSEs...................................................... 33

4.1. Use of δ values and isotope references.............................................................................. 33
4.2. Tracer concentration, amount of tracer.............................................................................. 34
 4.3. Mixing of reservoirs with different isotopic composition.................................................. 35
4.3.1. Mixing of reservoirs of the same compound....................................................... 35
4.3.1.1. Isotopic dilution analysis.................................................................... 36
4.3.2. Mixing of reservoirs of different compounds...................................................... 37
4.4. Isotopic changes in Rayleigh processes............................................................................. 37
4.4.1. Reservoir with one sink....................................................................................... 37
4.4.2. Reservoir with two sinks...................................................................................... 38
4.4.3. Reservoir with one source and one sink, as a function of time........................... 38
4.4.4. Reservoir with one source and one sink, s a function of mass............................ 40
4.4.5. Reservoir with two sources and two sinks, with and without fractionation........ 40

5. rADIOnuclide DECAY and production........................................................................ 43

5.1. Nuclear instability.............................................................................................................. 43
5.2. Nuclear decay and radiation............................................................................................... 43
5.2.1. Negatron (β−) decay............................................................................................. 43
5.2.2. Positron (β+) decay............................................................................................... 43
5.2.3. Electron capture (EC).......................................................................................... 44
5.2.4. Alpha (α) decay................................................................................................... 45
5.2.5. Spontaneous and induced fission, neutron emission............................................ 45
5.3. Recoil by radioactive decay............................................................................................... 45
5.4. Nuclear reactions................................................................................................................ 45
5.4.1. Natural production............................................................................................... 46
5.4.2. Anthropogenic releases of radionuclides............................................................. 46

6. EQUATIONS OF RADIOACTIVE DECAY AND GROWTH..................................................... 49

6.1. Law of radioactive decay................................................................................................... 49
6.2. Half-life and mean life....................................................................................................... 49
6.3. Activity, specific activity and radionuclide concentration................................................. 50
6.4. Mixture of independent radioactivities.............................................................................. 50
6.5. Branching decay................................................................................................................. 50
6.6. Radioactive decay series.................................................................................................... 51
6.6.1. Secular equilibrium.............................................................................................. 51
6.6.2. Transient equilibrium........................................................................................... 52
6.6.3. No-equilibrium..................................................................................................... 52
6.7. Accumulation of stable daughter product.......................................................................... 53
6.8. Radioactive growth............................................................................................................ 53

7. natural abundance of the stable isotopes of C, O and H.............................. 55

7.1. Table carbon isotopes......................................................................................................... 55
7.1.1. The natural abundance......................................................................................... 55
7.1.2. Carbon isotope fractionations.............................................................................. 55
7.1.3. Reporting 13C variations and the 13C standard .................................................... 59
7.1.4. Survey of natural 13C variations........................................................................... 59
7.1.4.1. Atmospheric CO2 ............................................................................... 60
7.1.4.2. Seawater and marine carbonate.......................................................... 60
7.1.4.3. Vegetation and soil CO2 ..................................................................... 60
 7.1.4.4. Fossil fuel........................................................................................... 60
7.1.4.5. Global carbon cycle............................................................................ 60
7.1.4.6. Groundwater and riverwater............................................................... 61
7.2. Stable oxygen isotopes....................................................................................................... 61
7.2.1. The natural abundance......................................................................................... 61
7.2.2. Oxygen isotope fractionations............................................................................. 62
7.2.3. Reporting 18O variations and the 18O standards................................................... 63
7.2.4. Survey of natural 18O variations........................................................................... 66
7.2.4.1. Seawater............................................................................................. 66
7.2.4.2. Precipitation........................................................................................ 66
7.2.4.3. Surface water...................................................................................... 68
7.2.5. Climatic variations............................................................................................... 68
7.3. Relation between 13C and 18O variations in H2O, HCO!, and CO$................................... 68
7.4. Stable hydrogen isotopes.................................................................................................... 69
7.4.1. The natural abundance......................................................................................... 69
7.4.2. Hydrogen isotope fractionations.......................................................................... 70
7.4.3. Reporting 2H variations and the 2H standard....................................................... 70
7.4.4. Survey of natural 2H variations............................................................................ 70
7.5. Relation between 2H and 18O variations in water................................................................ 70

8. NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H............................... 75

8.1. The radioactive carbon isotope.......................................................................................... 75
8.1.1. Origin of 14C, decay and half-life......................................................................... 75
8.1.2. Reporting 14C variations and the 14C standard..................................................... 76
8.1.3. Survey of natural 14C variations........................................................................... 77
8.1.3.1. Atmospheric CO2 ............................................................................... 77
8.1.3.2. Vegetation and soils............................................................................ 78
8.1.3.3. Seawater and marine carbonate.......................................................... 78
8.1.3.4. Groundwater....................................................................................... 78
8.1.4. 14C age determination.......................................................................................... 79
8.1.5. Dating groundwater............................................................................................. 80
8.1.5.1. Dating groundwater with DIC............................................................ 80
8.1.5.2. Dating groundwater with DOC.......................................................... 81
8.2. Relation between 13C and 14C variations............................................................................ 82
8.3. The radioactive hydrogen isotope...................................................................................... 82
8.3.1. Origin of 3H, decay and half-life.......................................................................... 82
8.3.2. Reporting 3H activities and the 3H standard......................................................... 82
8.3.3. Survey of natural 3H variations............................................................................ 82
8.4. Comparison of 3H and 14C variations................................................................................. 83
8.4.1. Relation between 3H and 14C in the atmosphere.................................................. 83
8.4.2. Relation between 3H and 14C in groundwater...................................................... 84

9. CHEMISTRY OF CARBONIC ACID IN WATER........................................................................ 87

9.1. Introduction........................................................................................................................ 87
9.2. Carbonic acid equilibria..................................................................................................... 87
9.3. The equilibrium constants.................................................................................................. 88
 9.3.1. Ideal solutions...................................................................................................... 89
9.3.2. Seawater............................................................................................................... 89
9.3.3. Brackish water..................................................................................................... 90
9.4. Carbonic acid concentrations............................................................................................. 90
9.5. Examples for open and closed systems.............................................................................. 93
9.5.1. Comparison of freshwater and seawater exposed to the atmosphere.................. 93
9.5.1.1. For freshwater..................................................................................... 94
9.5.1.2. For seawater........................................................................................ 94
9.5.2. System open for CO2 escape and CaCO3 formation............................................ 95
9.5.2.1. Starting conditions.............................................................................. 95
9.5.2.2. Escape of CO2 .................................................................................... 96
9.5.2.3. Precipitation of CaCO3 ...................................................................... 96
9.5.3. System exposed to CO2 in the presence of Caco3 ............................................... 97
9.5.4. Closed system, mixing of freshwater and seawater............................................. 97

10. Water sampling and laboratory treatment........................................................ 99

10.1. Water sampling and storage............................................................................................... 99
10.1.1. Sampling bottles.................................................................................................. 99
10.1.2. General field practice........................................................................................... 99
10.1.3. Precipitation....................................................................................................... 100
10.1.4. Surface water..................................................................................................... 100
10.1.5. Unsaturated zone water...................................................................................... 100
10.1.6. Groundwater...................................................................................................... 100
10.1.7. Geothermal water............................................................................................... 101
10.2. Laboratory treatment of water samples............................................................................ 101
10.2.1. The  18
O/16O analysis of water............................................................................. 101
10.2.1.1. Equilibration with CO2 for mass spectrometric measurement......... 101
10.2.1.2. Other methods.................................................................................. 102
10.2.2. The  2
H/1H analysis of water............................................................................... 103
10.2.2.1. Reduction of water to H2 for mass spectrometric analysis............... 103
10.2.2.2. Other methods.................................................................................. 103
10.2.3. The  3
H analysis of water.................................................................................... 103
10.2.3.1. Water purification............................................................................. 103
10.2.3.2. 3H enrichment.................................................................................. 103
10.2.3.3. Preparation of gas for PGC of 3H..................................................... 104
10.2.4. The  14
C analysis of dissolved inorganic carbon................................................. 104
10.2.4.1. In the field......................................................................................... 104
10.2.4.2. In the labo0ratory............................................................................. 105
10.2.5. The  13
C/12C analysis of dissolved inorganic carbon........................................... 105

11. measuring techniques.................................................................................................... 107

11.1. Mass spectrometry for stable isotopes............................................................................. 107
11.1.1. Physical principle............................................................................................... 107
11.2. Reporting stable isotope Abundance ratios...................................................................... 108
11.2.1. Measurement of 2H/1H in H2 ............................................................................. 108
11.2.2. Measurement of 15N/14N in N2 ........................................................................... 109
 11.2.3. Measurement of 13C/12C and 18O/16O in CO2 ..................................................... 109
11.2.3.1. Comparison with machine reference................................................ 109
11.2.4. Calibration......................................................................................................... 109
11.2.4.1. Isotopic corrections...........................................................................110
11.2.4.2. 18O correction for water–CO2 equilibration......................................111
11.2.4.3. Normalisation....................................................................................111
11.2.5. Measurement of 18O/16O and 17O/16 in O2 ...........................................................113
11.3. Radiometry for radioactive isotopes.................................................................................113
11.3.1. Gas counters........................................................................................................114
11.3.1.1. Ionisation chamber............................................................................114
11.3.1.2. Proportional counter..........................................................................114
11.3.1.3. Geiger Müller counter.......................................................................114
11.3.1.4. Counter operation..............................................................................115
11.3.2. Liquid scintillation spectrometer........................................................................116
11.3.2.1. Physical principle..............................................................................116
11.3.2.2. Counter operation..............................................................................116
11.4. Mass spectrometry for low-abundance isotopes...............................................................117
11.4.1. Principle and application of AMS.......................................................................117
11.5. Reporting 14C activities and concentrations......................................................................118
11.5.1. The choice of variables.......................................................................................118
11.5.2. The standardisation............................................................................................ 120
11.5.2.1. The question of isotope fractionation............................................... 120
11.5.2.2. The question of radioactive decay.................................................... 120
11.5.2.3. Definition of the 14C standard activity.............................................. 120
11.5.3. Final definitions................................................................................................. 121
11.5.4. Special cases...................................................................................................... 121
11.5.4.1. Hydrology......................................................................................... 122
11.5.4.2. Oceanography and atmospheric research......................................... 122
11.5.4.3. Geochemistry.................................................................................... 123
11.5.4.4. Enhanced 14C radioactivity............................................................... 124
11.5.4.5. 14C ages............................................................................................ 124
11.5.5. Summary............................................................................................................ 124

12. natural isotopes of elements other than h, c, o............................................ 127

12.1. Helium.............................................................................................................................. 128
12.1.1. Origin and characteristics.................................................................................. 128
12.1.2. Experimental and technical aspects................................................................... 128
12.1.3. Sources of 3He.................................................................................................... 128
12.1.4. Natural abundance............................................................................................. 128
12.1.5. Applications....................................................................................................... 129
12.1.5.1. Principle of 3H/3He dating................................................................ 129
12.1.5.2. Mass spectrometric measurement of 3H through 3He....................... 129
12.2. Lithium............................................................................................................................. 129
12.2.1. Natural abundance............................................................................................. 129
12.2.2. Experimental and technical aspects................................................................... 129
12.2.3. Applications....................................................................................................... 130
 INTRODUCTION

12.3. Beryllium.......................................................................................................................... 130

12.3.1. Origin and characteristics.................................................................................. 130
12.3.2. Experimental and technical aspects................................................................... 130
12.3.3. Natural abundance............................................................................................. 130
12.3.4. Applications....................................................................................................... 130
12.4. Boron................................................................................................................................ 130
12.4.1. Natural abundance............................................................................................. 130
12.4.2. Experimental and technical aspects................................................................... 131
12.4.3. Applications....................................................................................................... 131
12.5. Nitrogen............................................................................................................................ 131
12.5.1. Experimental and technical aspects................................................................... 131
12.5.2. Natural abundance and isotope fractionation..................................................... 131
12.5.3. Applications ...................................................................................................... 131
12.5.4. 18O/16O in nitrate................................................................................................. 131
12.6. Aluminium....................................................................................................................... 132
12.6.1. Origin and characteristics.................................................................................. 132
12.6.2. Experimental and technical aspects................................................................... 132
12.6.3. Natural abundance............................................................................................. 132
12.6.4. Applications....................................................................................................... 132
12.7. Silicon............................................................................................................................... 132
12.7.1. Origin and characteristics.................................................................................. 132
12.7.2. Natural abundance............................................................................................. 133
12.7.3. Experimental and technical aspects................................................................... 133
12.7.4. Applications....................................................................................................... 133
12.8. Sulphur............................................................................................................................. 133
12.8.1. Experimental and technical aspects................................................................... 133
12.8.2. Natural abundance............................................................................................. 134
12.8.3. Applications....................................................................................................... 134
12.9. Chlorine............................................................................................................................ 134
12.9.1. Radioactive 36Cl................................................................................................. 134
12.9.1.1. Origin and characteristics................................................................. 134
12.9.1.2. Experimental and technical aspects.................................................. 134
12.9.1.3. Abundance in nature......................................................................... 135
12.9.1.4. Applications...................................................................................... 135
12.9.2. Stable 35Cl and 37Cl............................................................................................ 135
12.9.2.1. Natural abundance and applications................................................. 135
12.9.2.2. Experimental and technical aspects.................................................. 136
12.10. Argon................................................................................................................................ 136
12.10.1. Origin and characteristics................................................................................. 136
12.10.2. Experimental and technical aspects.................................................................. 136
12.10.3. Natural abundance............................................................................................ 136
12.10.4. Applications...................................................................................................... 136
12.11. Krypton............................................................................................................................ 136
12.11.1. Origin and characteristics................................................................................. 136
12.11.2. Experimental and technical aspects.................................................................. 137

xviii
 12.11.3. Natural abundance............................................................................................. 137
12.11.4. Applications....................................................................................................... 138
12.12. Iodine................................................................................................................................ 138
12.12.1. Origin and characteristics................................................................................. 138
12.12.2. Experimental and technical aspects.................................................................. 139
12.12.3. Natural abundance............................................................................................ 139
12.12.4. Applications...................................................................................................... 139
12.13. Decay series...................................................................................................................... 139
12.14. The uranium series .......................................................................................................... 139
12.14.1. 238U/234U............................................................................................................. 139
12.14.2. 230Th −234U dating.............................................................................................. 140
12.14.3. 226Ra and 222Rn................................................................................................... 140
12.14.4. 210Pb................................................................................................................... 140
12.14.5. Experimental and technical aspects.................................................................. 141
12.15. The actinium series........................................................................................................... 141
12.16. The Thorium series........................................................................................................... 142

13. errors, means and fits.................................................................................................... 145

13.1. Errors................................................................................................................................ 145
13.2. Precision and accuracy..................................................................................................... 145
13.2.1. Definitions.......................................................................................................... 145
13.2.2. Significant figures and digits.............................................................................. 145
13.2.3. uncertainties....................................................................................................... 146
13.3. Instrumental uncertainties................................................................................................ 147
13.3.1. Mean values....................................................................................................... 147
13.3.2. Distribution of data............................................................................................ 147
13.3.3. Standard deviation............................................................................................. 148
13.3.3.1. Precision of data............................................................................... 148
13.3.3.2. Precision of the mean....................................................................... 148
13.4. Statistical uncertainties..................................................................................................... 149
13.5. error Propagation.............................................................................................................. 149
13.5.1. Standard deviation............................................................................................. 149
13.5.2. Weighted mean................................................................................................... 150
13.6. Least-squares fit................................................................................................................ 150
13.6.1. Fit to a straight line............................................................................................ 150
13.6.2. Fit to non-linear curves...................................................................................... 151
13.7. Chi-square test.................................................................................................................. 151

Symbols and units..................................................................................................................... 153

Literature...................................................................................................................................... 155

References..................................................................................................................................... 159
 The Global Cycle of water
1. The Global Cycle of water
1.1. Introduction
The global hydrological cycle together with
its driving force, solar radiation, forms the ba-
sic resource for primary biological production.
It provides the water that is required for the as-
similation of carbon and plays an important role
in the supply of nutrients and their transport.
Moreover, the hydrological cycle is responsible
for the moderate and favourable temperature con-
ditions prevailing on Earth through its linkage
with the global atmospheric cycle.
The hydrosphere is the interconnection between
the biosphere, the atmosphere and the litho-
sphere, notably integrating the  fluxes of water,
energy and geochemical compounds.
Water is able to execute these tasks because of
a number of exceptional properties:
(1) high and universal dissolving power, es-
sential for distributing geochemical mate-
rial and to transport nutrients and to remove
waste substances from living organisms
(2) high surface tension, causing high capillary
forces; together with osmotic forces, this
enables water and solute transport within
organisms and maintaining a high cellular
tension.
(3) large heat capacity and heat of vaporisa-
tion, inherent to its role as energy transporter
(4) maximum density above freezing point, at
4°C; this anomaly causes freezing to proceed
from the surface downward, slowing down
both the heat release and the advancement of
the freezing process, thus protecting living
organisms
(5) high freezing and boiling point relative to
its molecular weight, in comparison with
similarly structured compounds, such as H2S
and H2Se; compared to these compounds,
these temperatures would be between –50
and –100°C.
All these properties are related to the high co-
hesion and pseudo-crystalline structure of wa-
ter. This structure is caused by the eccentric-
ity of the positive hydrogen nuclei with respect
1) Original version by J.J. de Vries, professor of hydrology, Free University, Amsterdam
to the electrons and the oxygen nucleus, which
gives the H2O molecule an electrical polarity or
dipole character.
In this chapter we will discuss the composition of
the hydrosphere and the basic concepts of the hy-
drological cycle and its interaction with atmo-
spheric circulation. Subsequently, we will con-
sider the individual elements of the hydrological
cycle, and their mutual interaction. Finally, atten-
tion is paid to the impact of climatic change and
man’s interference with the hydrological cycle.
1.2. The Hydrosphere
1.2.1. Origin of water on Earth
Most probably water has been in our solar system
from the beginning and was formed by the ther-
monuclear fusion process that produced the el-
ements of the periodic system and their com-
pounds. The total amount of water contained on
Earth is estimated at some 0.4% by volume, suf-
ficient to form a sphere of ice with a diameter of
almost 2500 km and a volume of 8.2 × 109 km3.
Most of this water is chemically and physically
bound in rocks and minerals within the crust and
mantle. The amount of free water, forming the hy-
drosphere, is estimated at 1.4 × 109 km3 — i.e.
17% of the total amount of water on Earth — of
which 96% is stored in the oceans as saline water.
It is generally accepted that most of the water in
the hydrosphere has originated from degassing of
the Earth’s mantle by volcanic eruptions and sur-
facing lava (basalt) in the course of the 5 billion
years of the Earth’s existence. The production
by this process is estimated at about 1 km3/year.
However, it is known that Earth is also exposed
to collisions with cosmic material, including ice
comets. An extraterrestrial origin of at least part
of the Earth’s water is therefore likely. Some of
the other planet’s satellites and many comets con-
sist almost completely of ice. A well-known ex-
ample is Halley’s Comet. A rough estimate gives
a total amount of water in our solar system, that is
100 000 times the mass of water in our oceans [1].
1
 INTRODUCTION

1.2.2. The hydro-tectonic cycle the associated volcanic and magmatic activity.

As explained before, the Earth’s hydrosphere ac-
quires water both from the mantle and possibly
from space, a gain of the order of 1 km3/year.
On the other hand, a smaller quantity escapes
into space and another unknown amount returns
to the mantle through plate-tectonic processes.
This process is driven by thermal convection cur-
rents, which move the rigid lithosphere as a co-
herent layer over the more plastic asthenosphere
(Fig. 1.1). Magma moves upward into fractures
(spreading centres) in the  ocean floor, where it
forms new oceanic crust. This causes the litho-
sphere to move away from the spreading centre.
At the other limb of the convection cell, the lith-
osphere sinks downward in a subduction zone.
Where old lithosphere disappears in the mantle,
ocean water is dragged with the crust to depths
of hundreds of kilometres and becomes involved
in the re-melting of sediments into new magma.
Another part of this water is exhaled again by
This entire process is referred to as the hydro-
tectonic cycle. This cycle acts on a geologic time
scale of millions of years and is quantitatively
negligible compared to the amount and distribu-
tion of water in the present hydrological circula-
tion at the Earth’s surface and the lower atmo-
sphere. The difference in dynamics of this hydro-
logical cycle and the hydro-tectonic cycle is also
reflected in the respective energy fluxes involved.
The driving force behind the hydrological cycle,
solar radiation, produces a flux at the Earth’s sur-
face of 5.2 × 109 J/m2/year, whereas the driving
force behind the tectonic processes, the Earth’s
internal heat production, delivers about
2.0 × 106 J/m2/year. The volcanic and magmatic
exhalations, however, do have a qualitative effect
on the hydrosphere by producing chemical com-
pounds and concentrated heat. Volcanic dust and
gases may influence the Earth’s heat balance and

Fig. 1.1.  Schematic representation of the hydro-tectonic cycle, showing a cross-section through an ocean-conti-
nent boundary. The upward moving mantle material forces the oceanic crust to slide under (to subduct) the con-
tinental crust.
1. Precipitation 6. Fluid released by deformation
2. Evapo(transpi)ration 7. Fluid released from magma and metamorphic
3. Vapour transport reactions (juvenile water)
4. Topography driven flow (meteoric water) 8. Volcanic emissions
5. Sea(water) trapped in subducted sediments
(connate water)

2
 The Global Cycle of water

thus its climate and hydrological cycle over a pe- 1.2.3. Distribution of water over
riod of years. the various reservoirs

Plate-tectonics and continental drift change The hydrosphere can be characterised as a system

the shape of the earth on a time scale of mil-
lions of years by a geographic re-arrangement
of oceans and continents, uplift of the Earth’s
crust and the formation of mountain ranges. In
the course of the Earth’s evolution these morpho-
logical changes have caused changes in world-
wide climatic conditions and in the hydrosphere.
Other long-term influences on the planet’s climate
are caused by systematic shifts in the Earth’s orbit
and exposure to the sun, with associated changes
in incoming solar radiation, on time scales of 104
to 105 years.
of different reservoirs from which water, solutes
and energy are exchanged by the hydrological cy-
cle. On a large scale this circulation is driven by
thermal energy of solar radiation and by poten-
tial- and pressure energy produced by gravity. On
a small scale, capillary and osmotic forces play
a role in water transport in soil and plants, where-
as geothermal energy produces thermo-mineral
convection currents in deep aquifers.
As mentioned before, the total amount of water
in the hydrosphere is estimated at 1.4 × 109 km3,
of which 96% resides in the oceans. The remain-
ing 4% consists of freshwater, which exists and
moves only by the virtue of the continuous distil-

TABLE 1.1.  Volumes and fluxes of water and their

turn-over time in the different compartments of
the hydrosphere.
The volumes are mainly according to [2], with some additions.

Volume % of total flux turn-over time

in 103 km3 freshwater 103 km3/year year

Salt water
Oceans 1 350 000 425 3000 a 
Freshwater
Ice 27 800  69.3 2.4 12 000 b
Groundwater 8 000* 29.9 15 500 c
Lakes 220** 0.55
Soil moisture 70 0.18 90 0.48 d
Atmosphere 15.5 0.038 496 0.03 e
Reservoirs 5 0.013
Rivers 2 0.005 40 0.05 f
Biomass 2 0.005
Total 40 114 100

* < 5000 m depth, based on a porosity of 1%, rather than porosity of 1.5%, resulting in a volume
of 12 × 106 km3 (see Volume V)
** about 50% contains salt or brackish water; cf. volume of 177 × 103 km3 (Volume III)
a 
Flux is oceanic evaporation
b
Flux estimated from discharge
c
Flux estimated at 37% of total continental discharge (base flow)
d
Flux estimated at 80% of continental rainfall
e
Flux is total rainfall = total evaporation
f
Flux is total discharge from continents

3
 INTRODUCTION
lation process that turns salt water into a freshwa-
ter by evaporation and subsequent condensation.
Most of this freshwater is more or less locked
up in ice caps, icebergs and glaciers, notably
on Antarctica and Greenland. Were it to melt,
the world’s rivers could flow uninterruptedly for
more than 500 years on this quantity of water.
An estimate of the distribution of freshwater
over the various global reservoirs and the turn-
over time of the different reservoirs is given in
Table 1.1.
There is considerable uncertainty about some of
these figures, especially for groundwater at great-
er depths. Also estimates of the ice volume vary
considerably, from 22 000 km3 to 43 000 km3 .
Most of the freshwater reserve actively involved
in the hydrological cycle is found in the upper
few kilometres of the subsurface.
The state of the still deeper water is not well
known, but most of it is more or less isolated
from the hydrological cycle by impervious lay-
ers and takes part in it only on a geological time
scale. Moreover, most of this water is saline and
probably mainly connate, i.e. water (mainly sea
water) that was trapped during the deposition of
sediments. Part of this water is diagenetically al-
tered meteoric water (i.e. from atmospheric ori-
gin) or juvenile magmatic water. Hot brines with
a temperature of 200°C are still encountered in
the ultra-deep Kola Peninsula (N.Russia) bore-
hole at a depth of 12 km. Such mineralised wa-
ters normally reach the surface in thermo-mineral
springs connected with (past-)volcanism or deep-
seated fractures (Fig. 1.1).
Another part of the groundwater reserves
(Volume V, Chapter 1) at more shallow depths
can also be classified as fossil, if this water was
formed under different conditions than at pres-
ent and if it is isolated from active circulation,
either by less pervious layers or because of a lack
of recharge, like in arid regions. A huge ground-
water reservoir (more than 100 000 km3 ) is pres-
ent beneath the Sahara and the Arabian Peninsula
in sandstones and limestones locally reaching
a thickness of 3000 m. This water was dated at
10 000 – 40 000 years BP and was recharged dur-
ing pluvial periods in the last ice age. It is still
flowing under artesian pressure and constitutes
the source behind oases. Although this water is
not actively involved in the hydrological cycle, its
discharge adds water to the active part, thus add-
ing to the oceanic reservoir. Depletion of all fossil
4
reserves on Earth, either by natural discharge or
by artificial extraction, would rise the average sea
level by several decimetres.
Another relatively slow part of the cycle is formed
by the polar ice caps which, at least on a geologi-
cal time scale, must be considered a temporary
phenomenon. They have been gradually formed
since the temperature at the Earth’s surface start-
ed to decrease at the beginning of the Tertiary,
some 50 million years ago, from about 20°C to
the present 15°C. This eventually resulted 2 mil-
lion years ago in the present Quaternary with
glacial cycles of the order of 100 000 years and
temperature intervals of less than 10°C. During
more than 90% of the Earth’s history there were
no polar ice caps. The origin of this cooling of
the Earth is not fully understood, but a shift of the-
Antarctic landmass and the isolation of this con-
tinent by a circum-Antarctic ocean current during
the Tertiary and the subsequent uplift of this con-
tinent was certainly a prerequisite for the initia-
tion of the huge continental ice cap. The growth
of the Antarctic land-ice probably began during
the Middle Miocene, about 12 million years ago,
but the  first glaciers on the  Antarctic highlands
originate from the beginning of the Oligocene,
about 30 million ago.
1.3. The global water budget
A schematic overview of the global hydrological
cycle and water balance is presented in Fig. 1.2.
The hydrological cycle starts with evapora-
tion from the oceans, estimated at 425 000 km3
(1176 mm) per year. Rainfall over the oceans is
estimated at 385 000 km3 (1066 mm), leaving an
excess of 40 000 km3 (equivalent to 110 mm) of
water as vapour, which is transported by atmo-
spheric circulation (advection) to the continents.
The  main vapour flux travels from the  warm
equatorial to the cool high-latitude regions.
The vapour convergence at higher latitudes be-
comes clear from the areal distribution of the at-
mospheric vapour: the average annual vapour
content decreases from 50 mm water equivalent in
equatorial regions to less than 5 mm over the po-
lar regions. Condensation of the 40 000 km3 of
vapour originating from the oceans produces rain
on the continents. This precipitation is repeatedly
recycled by re-evaporation. The annual cumula-
tive evapotranspiration from the continents is es-
timated at 71 000 km3 (480  mm) so that finally
a total amount of 40 000 + 71 000 = 111 000 km3
 The Global Cycle of water

Fig. 1.2.  Schematic representation of the global hydrological cycle. The overall figures refer to the water fluxes
in 103 km3 per year (according to Table 1.2).

(746 mm) of precipitation is produced, leav-
ing an excess of 40 000 km3 (266 mm) returning
to the oceans via rivers, glacial meltwater and
groundwater. Table 1.2 shows the fluxes.
1.4. Components of
the hydrological cycle
1.4.1. Evaporation
Evaporation can only occur where a vapour pres-
sure gradient is maintained between the evaporat-
ing surface and the overlying atmosphere. Besides
this mechanism, evaporation also needs energy
to convert water into vapour (2.44 × 103 J/g at
15°C). This energy is provided by the evaporat-
ing water, and indirectly from solar radiation and
heat from the atmosphere. In fact, two factors
control the mechanism of evaporation. In the first
place the difference between the vapour pressure
of the overlying air (eA) and the saturated vapour
pressure (eS) at the temperature of the evaporating
surface. This difference (eS–eA) is called the satu-
ration deficit. Secondly, the  evaporation rate is

TABLE 1.2.  Annual water balance at the various oceans and

continents of the Earth [2].
Continents Oceans The Earth
Surface area in 10  km
6 2
149 361 510
(103 km3) (mm) (103 km3) (mm) (103 km3) (mm)
After [2]
Precipitation 111 746 385 1 066 496 973
Evapo(transpi)ration 71 480 425 1 176 496 973
Discharge 40 266 40 110 ­— —
After [3]
Precipitation 119 800 458 1 270 577 1 131
Evapo(transpi)ration 72 487 505 1 400 577 1 131
Discharge 47 313 47 130 — —

Note: [3] arrived at notably higher values for the oceans.

5
 INTRODUCTION
determined by the vapour transport. The upward
movement in a thin boundary layer is by mo-
lecular diffusion, but above this layer vapour is
transferred and removed by turbulent air move-
ment, related to the wind speed. Evaporation is
strongly dependent on the temperature determin-
ing the saturated vapour pressure, and the turbu-
lent air exchange that is related to wind speed and
surface roughness.
Methods to determine evaporation from cli-
matic data are normally based on a combina-
tion of the  energy balance for a  specific surface
and the aerodynamic conditions. The most well
known energy balance/aerodynamic method was
developed by [4]. Later [5] adapted Penman’s
formula so as to make it applicable to vegetated
surfaces as well, by introducing biological and
aerodynamic resistance factors that incorporates
structure and physiology of the vegetation cover.
Although evaporation is driven by solar energy,
the  distribution over the  oceans does not reflect
the latitudinal pattern of incoming radiation, nei-
ther in time nor place. This is because the latent
heat is for a large part extracted from the heat
stored in the water itself, and thus influenced by
warm and cold ocean currents. This occurs espe-
cially when relatively cold and dry air blows over
a warm ocean current.
The high vapour pressure gradient between
the warm water surface and the dry air stimu-
lates upward vapour transport and the energy will
be extracted mainly from the water. Therefore,
maximum evaporation occurs in the Western
Pacific and the Western Atlantic where this par-
ticular situation prevails (Fig. 1.3). Relatively
low values are found in the equatorial areas be-
cause of low wind velocity and high vapour pres-
sure. Advection of warm air masses and seasonal
variations in wind speed and turbulent exchange
are other factors that influence the distribution of
evaporation over the oceans in space and time.
Evaporation from a vegetated land surface is nor-
mally a combination of direct evaporation from
a wet surface, and water consumption or transpi-
ration by the vegetation. This combined effect
is called evapotranspiration. The evaporation
from an extensive water surface, like a lake or
ocean, depends exclusively on the available en-
ergy and the atmospheric condition. Evaporation
from a land surface however is often limited by
the availability of water. For a well-watered veg-
etated surface or a wet soil, evaporation is nor-
6
mally close to that of an open water surface and is
indicated as potential evapotranspiration.
The amount and the timing of rainfall is an im-
portant factor. Available energy, for instance, can
become the limiting factor if rainfall occurs dur-
ing the winter season, whereas at the other hand,
more regularly distributed rainfall with frequent
showers can increase evaporation from inter-
ception. Limited amounts of water at the right
moment and place is one reason that the total
evaporation on the continents is less than half
of the amount on the oceans. The other factor is
the lower net solar radiation received by the land
surface. This is mainly caused by the difference
in albedo (percentage incoming solar radia-
tion that is reflected back into the atmosphere at
the Earth’s surface), which is 6 – 10% for open
water and varies on the continents from 7% for
tropical rain forest to 35% for dry white sand (see
also Sect. 1.4.3).
1.4.2. Precipitation and
atmospheric circulation
In principle, rain is caused by condensation and
cloud formation in the atmosphere when air is
cooled to its dew-point. The cooling is normally
caused by adiabatic expansion of the uplifted air,
due to the decrease in atmospheric pressure with
height. Heat release by condensation can subse-
quently provide additional energy to cause further
rise of the air mass, which can result in convec-
tive thunderstorms. Most rain-producing vapour
has been subjected to advective transport by at-
mospheric circulation.
The general atmospheric circulation is main-
tained by the gradient in incoming solar radiation,
with an excess in the tropical belt where receipt
of heat exceeds the losses back into space, and
a permanent heat sink in the polar regions. Heat
consumption and heat release by evaporation and
condensation, respectively, are a secondary factor
in the global heat distribution. The air movement
itself is driven by the pressure gradient, which
is caused by spatial differences in heating, but
the movement deviates from the pressure gradient
because of the Earth’s rotation (the Coriolis ef-
fect). Other deviations superimposed on the gen-
eral north-south circulation are due to the distri-
bution of land and sea and the associated differ-
ential heating, including seasonal effects. Wind
fields are further influenced by mountain ranges.
 The Global Cycle of water
Fig. 1.3.  Global pattern of annual evaporation in cm [6]; after [7].
At low latitudes the air column rises and moves
poleward on either side of the equator. At higher
latitudes cooling air causes the column to de-
scend. This results in the development of the large
convective wind cells, the so-called Hadley Cells,
with low pressure along the equator and high
pressure around 30° Latitude. The Earth’s rotation
causes the separation of the high pressure belt into
divergent spiralling anticyclonic cells. The com-
pensating back- flowing air produces the  north-
easterly and south-easterly trade winds, which
converge in the equatorial area, and is therefore
also known as the Inter-Tropical Convergence
Zone (ITCZ). The rising air along the equato-
rial convergence zone produces the high rain-
fall of the wet-tropical rainforest areas, whereas
the high pressure belt with its heating of the air
by compression, results in the low rainfall zone
of the dry-tropical steppe and desert areas. These
arid zones extend northwards in the remote inte-
riors of the northern hemisphere because of their
distance from the moist oceanic air (Fig. 1.4).
Part of the warm air from the sub-tropical high
pressure belt moves to higher latitudes and
forms the prevailing Westerlies on the Northern
Hemisphere. Cold air sinks at the poles, spreads
along an easterly course and clashes at mid-lati-
tudes with the Westerlies. Here the warm subtrop-
ical air overrides the polar air and forms the so
called polar fronts along the different air masses.
The forced uplift of warm moist air, together
with low pressure pulsations in the meandering
Jetstreams in the upper part of the Westerlies,
causes the development of low pressure cells (an-
ticyclonic cells). Their inward and convergent,
spiralling movement forces the moist air to rise
and produces the frontal rains of the mid-lati-
tudes. Convective rains are formed mainly during
the summer in this area by free convection cells
in overheated air.
Extreme cases of convective rains are connected
with the development of devastating hurricanes
or typhoons. These develop in sub-tropical areas
when low pressure convection cells form over
warm sea surfaces of more than 260 C. Their en-
ergy is derived from the heat that is released by
condensation of the rising and expanding air. This
process is self- sustaining because the warm moist
air is continuously sucked up from the ocean.
Extreme rainfall of the order of 500 mm/day is
not uncommon during the passage of hurricanes.
Other heavy rain producing winds are the season-
al Monsoons. These represent wind systems that
reverse their direction because of the seasonal
change from high pressure to low pressure over
large continental areas. The Indian Monsoon is
particularly strong. During the summer the Indian
subcontinent becomes very hot and a strong
thermal low-pressure cell develops. Humid air
7
 INTRODUCTION
Fig. 1.4.  The global pattern of annual precipitation [8].
from the ocean moves in and brings high rain-
fall. A similar effect is caused by the southward
shifting ITCZ during the southern hemisphere
summer, bringing seasonal rain in the sub-tropics
of southern Africa. Orographic effects are other
causes of regional deviations in the global pat-
tern. High rainfall generally occurs at the  flank
where air is forced upward and low rainfall is
consequently observed at the lee side.
1.4.3. Discharge from
the continents
Part of the rainfall that reaches the earth will
disappear again by evaporation, either directly
from the wet soil surface or from interception on
the vegetation. The remaining water may partly
run off along the surface and partly infiltrate, re-
charging soil moisture (Volume V, Chapter 1).
Soil water will percolate further downward to
the saturated zone (or groundwater zone) after
the soil has reached a soil-specific concentration
of moisture. The remaining part is held against
gravity by capillary and other forces. Part of
the soil moisture and shallow groundwater is sub-
8
sequently re-evaporated, mainly via transpiration
by the vegetation.
Groundwater at a depth of more than 1 to 2 m be-
low the root zone hardly participates in the evap-
oration process, because capillary transport from
the water table upwards is then negligible. It is
important to realise that two-third of continental
rainfall originates from this re-evaporation and
transpiration from land surfaces.
The excess of surface water as well as ground-
water is eventually discharged by rivers and to
a less extent by direct groundwater discharge
into the sea. The character of rivers, or the river
regime, follows mainly the seasonal pattern of
rainfall and evapotranspiration with an attenu-
ation and delay by the storage processes. Rivers
respond fast in areas with shallow soils on steep
slopes and low infiltration capacity. In con-
trast, level areas with high infiltration capacity,
high subsurface storage and high permeability,
are characterised by slowly reacting rivers and
the  production of extended base flow. The  total
global discharge is released partly by base flow
and partly by flood flow. Flood flow is not exclu-
sively generated by surface runoff. The latter type
of flow, in fact, occurs only during exceptional
 The Global Cycle of water
high rainfall and in steep land with an impervi-
ous subsurface. Flood water is normally produced
by a  range of processes, including rapid flow
through the macro-pores of the upper soil layers
(throughflow) and infiltration-excess or satura-
tion-overland flow. These (near)surface processes
normally initiate rills and gullies to participate
in the drainage process during periods of high or
extended rainfall, so that the drainage system ex-
pands into an ephemeral and poorly defined sys-
tem of branches and associated depressions.
Soil moisture plays an important role in the ex-
change of water and energy with the atmosphere.
Wet soils absorb and store energy and contribute
to the return of moisture to the atmosphere by
evapotranspiration. Part of this vapour is eventu-
ally recycled as rain in the same zone, or reap-
pears as advective rain in adjoining areas. Water
often disappears rapidly from dry and barren soil
by sheet floods. Such surfaces receive less energy
because of their higher reflection rate, increas-
ing from 5 – 15% for dark, wet soils and veg-
etated surfaces, to 25 – 45% for dry, light sand. In
general, removal of vegetation similarly causes
unfavourable conditions; notably in semi-arid
regions this can inhibit the generation of con-
vective rain. Under specific conditions of high
infiltration capacity, a  reduction of vegetation
with its high water consumption can result in an
increase in groundwater replenishment. However,
an enhancement of groundwater recharge is not
always desirable, as semi-arid areas in Australia
exemplify. Removal of the vegetation in parts of
this country resulted in a rapid rise of the ground-
water table to near or at the surface. Evaporation
of this water causes severe and under the present
climatic conditions irreversible salinisation (see
Sect. 1.4.4).
Now we can consider the rainfall-runoff balance
on the continental scale (Fig. 1.5). Average annual
rainfall on the continents (estimated at 746 mm)
represents a surplus of 50% over average annual
evapotranspiration (480 mm), although on aver-
age the annual potential evaporation is higher
than rainfall. This is because rainfall in many
areas exceeds the maximum evaporation in one
season, whereas maximum evaporation is not
reached due to a lack of water in other seasons.
Changes in storage of soil water and groundwa-
ter play an important role in the smoothing of
these seasonal effects, and are therefore crucial
for the conversion of precipitation into runoff.
The reasons are (i) because of their buffering ef-
fect on the discharge itself, and (ii) because they
extend the evaporation beyond the rainy period
into the subsequent drier period and thus increase
total evapotranspiration.
The three components of the hydrological cy-
cle over the continents and oceans are listed
in Table 1.2. There is a global seasonal effect
in the runoff that is predominantly caused by
the detention storage of snow on the continents
of the northern hemisphere. The North American
and Eurasian landmasses receive a snow cover
over 60 – 70% of its surface, which reaches its
maximum in March-April. The maximum sea-
sonal depletion of this cover follows at the end
of the summer, causing a maximum storage in
the ocean around October. Furthermore, the  dis-
tribution of precipitation, evaporation and in-
flow from the  continents eventually produces
a surplus in the Indian and Atlantic Oceans, and
a net loss from the Pacific and the Arctic Ocean.
Consequently, there is a  continuous inflow from
the  Indian and Atlantic oceans into the  Pacific
and the Arctic oceans. Table 1.3 shows the water
balance between precipitation, evaporation and
discharge specifically over the various continents
and oceans.
1.4.4. Groundwater
The subsurface consists of an upper zone with
soil water and a lower saturated part with ground-
water; these zones are separated by the ground-
water table. The depth at which groundwater is
encountered depends on topography, subsurface
structure and climate. Total storage of ground-
water in a layer is determined by the porosity,
but the  ease at which groundwater can flow de-
pends on a combination of interconnection and
size of the pores. This property is parameterised
in the permeability. High porosity and high per-
meability are notably found in alluvial sandy de-
posits and to a lesser extent in sandstone. Clay
on the contrary shows about the same porosity
as sand (30 – 50 vol %), but the pores are small
and consequently the flow resistance is consider-
able, so that saturated water flow is often negli-
gible. Karstified limestone can produce very high
permeability due to dissolution features, and can
even develop subsurface streams. Relatively po-
rous and permeable subsurface layers are indicat-
ed as water bearing layers and are called aquifers.
Generally, claystones and crystalline rocks show
9
 INTRODUCTION
poor aquifer characteristics, but weathering, frac-
turing and jointing can locally produce permeable
structures.
Groundwater recharge normally takes place by
diffuse infiltration according to the  processes
described in Sect. 1.4.3. Concentrated recharge
takes place via water that has accumulated in de-
pressions or streams in cases where the stream
bed is above the groundwater table. The latter sit-
uation especially occurs in arid areas where deep
groundwater tables prevail. Recharge is then from
episodic floods in wadi’s or from river inflow
from surrounding, more humid areas. Complete
streams sometimes disappear underground in
karstified limestones of high dissolution perme-
ability.
Groundwater discharge normally takes place
by subsurface drainage to streams. The aver-
age turnover time of groundwater is determined
by the total flux, or recharge, and the  storage of
the  basin. The  flow density however, normally
decreases downward, so that the age of the water
roughly increases logarithmically with depth (see
Volume IV).
Water is stored during periods of high recharge:
this results in a rise of the groundwater table
and an increase of the hydraulic gradient, so
Fig. 1.5.  Global pattern of annual runoff in cm [9]; after [10].
10
that the discharge increases. Moreover, a rise of
the groundwater table often means that lower-
order and less deeply incised stream branches
are activated to take part in the drainage process,
which can amplify the drainage rate by an order
of magnitude. Saturation-excess overland flow
through rills and gullies is the extreme condition
which occurs when the groundwater table reaches
the surface (Sect. 1.4.3).
A dry period reverses the process: groundwater
is then released from storage because discharge
exceeds recharge. Consequently the groundwater
table drops, discharge decreases and stops when
the water table at the divide has reached the level
of the deepest incised channel and the hydraulic
gradient has become zero. In arid areas where re-
charge is low and groundwater tables are deep,
groundwater flow is more steady and fluctuations
are dominated by long term cycles of drought and
wet climatic spells.
Residence times of groundwater range between
months for shallow drainage systems to thousands
of years for deeper systems, and especially in arid
areas with low recharge and large turnover time.
Exceptional cases of fossil or residual groundwa-
ter flow can be found in extensive groundwater
basins in desert areas. Their relaxation time is
large because of a large volume of water stored
 The Global Cycle of water

and because of a  high flow resistance, due to
the large distances between (palaeo-)recharge and
discharge areas. An example is the Sahara where
huge fossil groundwater reserves from the last ice
age (dated 10 000 – 40 000 years BP) still flow
and feed springs, driven by a residual hydraulic
gradient. The hydraulic gradient is slowly de-
creasing by depletion, but this process can pro-
ceed for thousands of years to come, unless large-
scale groundwater abstraction, like in the Middle
East, accelerates the depletion.
The groundwater systems discussed above are
mainly driven by topography or potential en-
ergy, and their water is of meteoric origin.
Groundwater occurrences at greater depths below
impervious layers are more or less isolated from
the active part of the hydrological cycle and their
character is partly connate; i.e. they were trapped
during sedimentation and are often of marine ori-
gin. These waters therefore form the connection
with the geological cycle of erosion, sedimenta-
tion, diagenesis, tectonics and metamorphism,
and their dynamics are interlinked with these
processes. Their flow is driven by processes
on a geological time and areal scale, including
compaction by sediment accumulation, pressure
change by tectonic deformation, thermal and geo-
chemical convection, molecular diffusion and
osmotic processes. Fluid movement under these
conditions has often residual components because
of the long relaxation time of the pressure gradi-
ent. The interaction of these deep seated systems
with the active or meteoric part of the hydrologi-
cal cycle occurs by slow upward seepage and in
thermal and mineral springs in tectonically active
areas.
Groundwater and surface water in humid areas fi-
nally assemble in rivers which carry the continen-
tal surplus water back to the oceans. For this pur-
pose, stream systems consist of a highly efficient
network of hierarchic and nested branches, each
having their own sub-catchment. This network
forms a dynamic drainage and discharge system
that expands into the smallest gullies in time of
high water supply, and contracts to the larger
ones in dry periods.
Many arid basins do not produce a water surplus
and maintain an internal ground- and surface
water drainage. All rainwater eventually evapo-
rates and the dissolved salts present in the water
are left behind. The salinisation of large areas in

TABLE 1.3.  Annual water balance of continents and oceans [2].

P = precipitation, E = evaporation, D = discharge
Area P E D D/P
(103 km2) (103 km3) (mm) (103 km3) (mm) (103 km3) (mm) (%)
Europe 10 6.6 657 3.8 375 2.8 282 43
Asia 44.1 30.7 696 18.5 420 12.2 276 40
Africa 29.8 20.7 696 17.3 582 3.4 114 16
Australia 8.9 7.1 803 4.7 534 2.4 296 33
id. w.o. islands 7.6 3.4 447 3.2 420 0.2 27 6
N. America 24.1 15.6 645 9.7 403 5.9 242 38
S. America 17.9 28.0 1564 16.9 946 11.1 618 40
Antarctica 14.1 2.4 170 0.4 28 2.0 142 83
All continents 148.9 111 746 71.3 480 39.7 266 36
Arctic Ocean 8.5 0.8 97 0.4 53 0.4 44 45
Atlantic Ocean 98.0 74.6 761 111.1 1133 −36.5 −372 −49
Indian Ocean 77.7 81 1043 11.5 1294 −19.5 −251 −24
Pacific Ocean 176.9 228.5 1292 212.6 1202 15.9 90 7
All oceans 361.1 385 1066 224.7 1176 −39.7 −110 −10

11
 INTRODUCTION
Australia, for instance, is due to evaporation of
rising groundwater, which is loaded with the ac-
cumulated salt. Most of these areas experienced
wet pluvial conditions during the last ice age but
started with the accumulation of salt some 10 000
years ago at the beginning of the drier Holocene.
1.4.5. Continental water surplus
and water use
A special component of the continental wa-
ter balance is the use and diversion of part of
the water surplus by man. The estimated annual
40 000  km3 (266 mm) of runoff from the conti-
nents (Table 1.2) represents the excess water that
is left of the 111 000 km3 (746 mm) of rainfall, af-
ter evaporation and transpiration by natural veg-
etation and rain-fed agriculture have taken their
share. In principle, this excess water is available
for domestic and industrial use and for irrigated
agriculture. About 5000 km3 of this water is now-
adays withdrawn for these purposes. Irrigated
agriculture takes the highest share with 65%. It
is responsible for more than 50% of the world’s
food production on 20% of the world’s arable
land. The high amount of water needed for food
production is exemplified by the fact that the pro-
duction of 103 kg of corn, sufficient to feed six
people for one year, requires 300 × 103 kg of wa-
ter under average climatic conditions. The ratio
between water use and dry mass accretion differs
between crops and depends obviously on climatic
conditions, particularly the potential evaporation.
Observations on various types of vegetation give
values between 100 and 1000 kg of water per kg
dry mass production.
The uneven distribution of water resources in time
and space and the irregular spread of the world’s
population, restrict the possibilities for increas-
ing the application of this excess water. Most of
the water is available in the equatorial tropical ar-
eas (the Amazon River, for instance, discharges
20% of the world’s total runoff), whereas two-
thirds of mankind live outside the tropics. Another
negative factor is the variability of the supply in
time. Only one-third of the runoff forms a more
or less stable supply, while the remaining part oc-
curs in floods. The irregular distribution of water
in space and time has led from the earliest civili-
sations onwards to hydraulic engineering prac-
tices, notably the construction of water diversion,
transport and storage works, including large-scale
drainage and irrigation schemes. These modifica-
12
tions of the regional water balance have certainly
resulted in a  modification of the  regional atmo-
spheric and hydrological circulation and the asso-
ciated climate (Sect. 1.5.2).
Water resources assessment and sustainable re-
source development and management require
a sound knowledge of the hydrological process-
es involved. Especially Volume V of this series
is devoted to these aspects. Numerous tools and
models which have been developed for analys-
ing the hydrological situation are being treated in
Volume VI.
1.5. The hydrosphere and global
change
1.5.1. Climatic change
The Earth forms a dynamic system, with internal
processes driven by internal heat production and
external processes driven by solar energy. Both
type of processes interact in cycles of material
and energy flows, each with its own temporal and
spatial scales. A shift in one of the components
must lead to an adjustment elsewhere in the sys-
tem, which in turn can trigger changes in related
systems. Regional hydrological cycles are closely
linked with the prevailing climatic conditions and
associated vegetation covers, and can be expected
to react accordingly to changes in the meteoro-
logical forcing or large-scale transformation in
surface cover.
As explained before, the present climate deviates
from the average climate during the Earth’s his-
tory and is characterised by relatively low tem-
peratures and ice caps at the poles. The present
‘ice age’ is the sixth over the last billion years,
and was preceded by the Permian glaciation
some 250 million years ago. Apart from these
cold eras, the Earth has experienced shifts from
the domination of wet and hot swamps, as during
the Carboniferous, to the hot and dry prevailing
desert conditions during the Triassic. Such ma-
jor shifts are basically caused by plate-tectonics
induced shifts in the geographical position of
the continents as well as by changes in their el-
evation by uplift and mountain building.
Another major player in the global climatic sys-
tem is probably the carbon-dioxide content of
the atmosphere. CO2 is part of the global geo-
chemical carbon cycle which has the following
main fluxes: (i) CO2 extracted from the atmo-
 The Global Cycle of water
sphere by photosynthesis, producing organic ma-
terial, and by weathering of rock as well as de-
position of calcium minerals; (ii) CO2 released to
the atmosphere by decay of organic matter and
respiration by plants and soils; (iii) CO2 periodi-
cally evading from and taken up by the oceans;
(iv) CO2 recycling in the Earth’s interior by ab-
sorption in the mantle via the descending subduc-
tion zone and release through degassing by vol-
canic eruptions and by the extrusion of magma
in the oceanic ridges (Fig. 1.1). The oceans form
a large CO2 reservoir that act as a buffer through
their physico-chemical diffusion exchange with
the atmosphere. Algae play an important role in
this process.
An illustration of the possible influence of the geo-
graphical position of continents and oceans, and
the opening up and closing of ocean basins, as
well as the influence of atmospheric levels of CO2,
is presented by the change in conditions when
going from the Cretaceous to the Quaternary
era. The elevation of the continents was much
lower than at present, and the ocean-land ratio
much larger, especially during the second half
of the Cretaceous. The Antarctic Ocean was not
yet isolated from warm ocean currents, whereas
the landmass at the Arctic was isolated and situ-
ated far from snow producing oceans. Moreover,
geochemical budget modelling suggests that
the CO2 content of the atmosphere during the last
500 million years was several times higher than at
present, with a maximum of 18 times the present
content in the mid-Cretaceous, some 100 million
years ago. During the mid-Cretaceous the tem-
perature of deep ocean water was 150 higher than
at present and corals were found 1500 km nearer
to the poles.
At the onset of the Tertiary, about 60 million
years ago, the temperature gradually decreased,
probably because of a thermal isolation of the po-
lar regions. The separation of Antarctica from
the Australian continent and the shift of this
landmass to the South Pole led to the develop-
ment of a circum-Antarctic ocean current that
obstructs the heath exchange with warm ocean
water and allowed the accumulation of snow.
The Arctic opened up and came under the influ-
ence of precipitation-producing ocean water, but
at the same time remained to a certain extent
blocked by surrounding continents. Concurrently,
the Antarctic landmass rose, which contributed
further to the cooling. Probably already during
the Oligocene mountain glaciers were formed on
the highest mountains. Ice caps began to develop
by the mid-Miocene, about 10 million years ago.
This had a positive feedback effect, firstly by an
increase in the albedo, resulting in a reduction of
the net radiation, and secondly by a further rise
of land surface by ice accumulation by more than
1000 m. The latter effect is still clear in the Arctic
where Greenland with an altitude of over 2000 m
is still glaciated, whereas the Canadian Arctic at
the same latitude only shows a winter snow cover.
The elevation effect on temperature is a decrease
of 6°C/km under present conditions.
Another effect may have been the continental
uplift of other Alpine mountains in the course
of the Tertiary, notably the elevated areas of
the Himalayas and the Tibetan Plateau with their
associated cooling and blocking effect on atmo-
spheric circulation. This orogenesis also caused
an increase in weathering and erosion with its as-
sociated consumption of atmospheric CO2.
The Quaternary glacial period, which began
about 2.5 million years ago with a pronounced
fall in temperature, is characterised by 15 to
20 glacial-interglacial cycles. During the maxi-
mum glaciations, air temperatures at the temper-
ate climate zone dropped by 60 C relative to pres-
ent temperature. It is generally accepted now that
these cyclic fluctuations were primarily triggered
by minor variations in the amounts of solar radia-
tion reaching the top of the atmosphere. These
variations originate from regular oscillations in
(i) the Earth’s orbit (periodicity about 100 000
years), (ii) the tilt of the Earth’s axis (41 000
years), and (iii) a circular movement (‘wobble’)
of the spin of the Earth’s axis (23 000 years).
These are called the Milankovitch oscillations af-
ter the Serbian engineer and astronomer Milutin
Milankovitch who investigated these astronomi-
cal factors and their possible climatic impact at
the beginning of the 20th century.
Superimposed on the 20  000 – 100 000 years
astronomically driven climatic oscillations are
relatively strong fluctuations in temperature on
a time scale of hundreds of years during the gla-
ciations. Fluctuations on similar time scale but
lower amplitude have also been observed dur-
ing the last 10 000 years, i.e. during the present
(Holocene) climate. Within this climatic noise
main shifts over periods of hundreds to thousands
of years have been recognised in the records of
the Holocene. For the mid latitudes of the north-
ern hemisphere these climatic fluctuations seem
13
 INTRODUCTION
to be connected with the persistence of (i) periods
of strong zonal flow of the Westerlies with strong
oceanic influence, and (ii) periods with more po-
lar and continental influence and a  more south-
erly track of the Westerlies. This alternating sys-
tem is dominated by the pattern of high and low
pressure cells, which is probably influenced by
shifts in ocean currents. The impact of the shift in
pressure distribution seems to reach as far south
as the Sahel zone.
The most comprehensive review of climatic
fluctuations in Western Europe and the  Middle
East was produced by [11]. His system is based
on climatic proxy data (such as pollen, isotopes
and tree-ring analysis), global circulation recon-
structions and archaeological and historical in-
formation. A schematic review of fluctuations in
Holocene climate, mainly based on [11, 12], is
the following.
14000 – 8000 BC: end of glaciation; sudden and
strong temperature fluctuations due to insta-
bility of glaciers and the production of huge
masses of meltwater
8000 – 6000 BC: rapid warming and melting of
mountain glaciers; humid environment in
the Middle East and savannah conditions in
the Sahara
5000 – 3500 BC: Post-Glacial ‘Climatic Optimum’:
summer temperatures in NW Europe 2 – 3°C
above that of the present day; monsoonal
rains penetrate the Sahara; extensive irrigat-
ed agriculture in Mesopotamia
3500 – 1000  BC: drying of the Sahara
(3500 – 1000); desertification and salinisa-
tion in Mesopotamia, Nile flow reduced;
sharp decline in temperature about 1500 BC
with a strong advance and initiation of new
mountain glaciers (it has been suggested that
the latter cooling might be connected with
the huge eruption of the Santorin volcano in
the Aegean Sea about 1450 BC)
900 – 300 BC: Iron Age Epoch: Cool and wet in
northern areas; strong regrowth of bogs after
a much drier period
400 – 800 AD: severe North Sea floods; growth of
Alpine glaciers
800 – 1200 AD: Secondary (Early Medieval)
Climatic Optimum: summer temperature at
least 1°C above present day; drier in NW
Europe; Viking colonisation of Greenland
14
1430 – 1850 AD: Little Ice Age (polar conti-
nental climate): cool in W. Europe and
the Mediterranean; temperatures 1  – 
3°C
lower than at present; re-advancement of
mountain glaciers; severe winters
1850 AD – present: maritime Atlantic climate;
global temperature rise 0.5°C; N. Atlantic
sea surface warmer; increased rainfall in
NW Europe.
Our knowledge of the  causes of these fluctua-
tions is still imperfect and they are probably not
the same for the different periods. The exceeding
of threshold values within the internal instability
of the atmosphere-ocean system, which triggers
a chain of feedback loops, is a distinct possibil-
ity. Other hypotheses focus on external factors,
including variations in solar radiation (notably
sun spot activity) and volcanic activity. The in-
crease in temperature during the last century may
be attributed to the increase in CO2 as caused by
the combustion of fossil fuel, and possibly to
periodicities in the solar activity as revealed by
the sunspot numbers. The latter is in accordance
with the low sunspot activity during the Little Ice
Age, but the mechanism behind this correlation is
unclear and still a matter of debate.
1.5.2. The human factor
Our knowledge of man’s influence on the global
hydrological cycle is minor and mainly restrict-
ed to the direct consequences of water manage-
ment for the water balance and runoff regime on
the small and medium catchment scale. The long
term impact of large-scale manipulations of river
basins and land use change is difficult to evalu-
ate in the absence of long-term hydrological data.
Information on the  influence of land use change
on evapotranspiration is rather well known, but
the lack of adequate models that couple the ex-
change of water and energy at the surface with at-
mospheric circulation models make it difficult to
translate this information into changes in rainfall
pattern. It is even more problematic to reconstruct
the effects of the large-scale reclamation and cul-
tivation practices during the last 10 000 years, i.e.
since agriculture was introduced.
The most evident influence of mankind on the hy-
drological cycle from the dawn of civilisations
is the application of irrigation and drainage. In
fact, it seems that the transition from gathering
wild grains to the growth of cereal crops evolved
 The Global Cycle of water
concurrently with the beginning of diversion and
control of flowing water. The oldest traces of ir-
rigated agriculture were found with the remains
of the early urban civilisation of Jericho, where
already before 7000 BC water from a large spring
was applied for irrigation. Different views have
been developed on the impact of these early prac-
tices on the environment and on the question
whether changes in climate or destructive land
use and/or war caused desertification and salini-
sation and the fall of civilisations. Recent palaeo-
climatic and archaeological research have made it
plausible that wet and dry climatic episodes have
often been the trigger of disasters, but that man
helped to aggravate the situation.
Less direct, but probably of more regional and
even global influence, must have been the  ef-
fects of the large-scale removal of the temper-
ate forests, and more recently the destruction of
tropical forests. This process began more than
2000 years ago in the Mediterranean and China,
1000 years ago in Europe and 100 years ago in
North America, and proceeds with the current
destruction of the equatorial rain forest by log-
ging and slash-and-burn agriculture. In addition,
large-scale drainage and reclamation works have
destroyed wetlands. All these changes, together
with urbanisation, must be held, at least in part,
responsible for lower evaporation, accelerated
discharge and increased flooding.
The main question is if, and how, these changes
in soil moisture, evapotranspiration and catch-
ment runoff regimes have caused anomalies with-
in the regional dynamic equilibrium of the gen-
eral circulation, and how these in turn have af-
fected rainfall. What we do know is that combus-
tion of fossil fuel, irrigation and the loss of forest
have caused an increase in the global atmospheric
concentrations of greenhouse gasses CO2 and
CH4. The increase rate in methane is twice that
of carbon dioxide, while methane is 20 times as
effective in its greenhouse effect as CO2. During
the last century, the CO2 concentration rose from
290 ppm to 350 ppm, whereas the CH4 concen-
tration from 0.95 to 1.65 ppm. The global rise in
temperature of 0.3°C during the last century may
well be connected with these increased emissions.
At the same time, a rise in temperature will proba-
bly also result in a higher cloud cover. This might
counterbalance the greenhouse effect by an in-
crease in the atmospheric albedo. The same could
apply for the  influence of dust particles from
land clearance and industrial activities. However,
the physics of clouds and aerosols and their in-
teraction with radiation is not sufficiently under-
stood yet to assess these effects quantitatively.
In the  absence of concrete data, we will briefly
and qualitatively summarise the possible effects
of the respective man-induced environmental
changes on climatic-hydrological conditions (see
Volume V for a more detailed discussion).
1.5.2.1. Irrigation
About 3500 km3 of the surplus water is now used
for irrigation. Most of this water evaporates and
the atmospheric moisture content will increase.
Wet soils lower the albedo and thus enhance net
radiation. These effects together might stimulate
convective rain, especially in semi-arid areas.
Higher atmospheric moisture levels at the other
hand might hamper the moisture influx from sur-
rounding regions.
1.5.2.2. Wetland drainage
Large-scale drainage of wetlands diminishes
evapotranspiration. The same applies to large-
scale deforestation, because trees normally use
more water than grassland or agricultural crops,
partly because of high interception evaporation.
This means that the total runoff from these ar-
eas must have increased, whereas streamflow re-
gimes may have developed a more seasonal char-
acter due to the loss of retention storage. Losses
of atmospheric moisture associated with reduced
evaporation, and higher reflection may also have
resulted in lower rainfall. [13], citing Russian
sources, suggests that 10% of the precipitation
in temperate humid climates probably originates
from local evaporation. Much higher values
were recently suggested for the Great Plains in
the USA.
1.1.1.1 Ground cover damage
Semi-arid areas are very susceptible to damage
of ground cover. The soil will dry out and erode,
rainfall will generate surface runoff instead of in-
filtration, evaporation will be reduced, the reflec-
tion from both the surface and atmospheric dust
particles may increase and convective rainfall
might therefore decrease. The change in thermal
and moisture regimes is then expected to result
in an anomalous atmospheric situation that will
15
 INTRODUCTION
be propagated by advection to surrounding areas.
This may finally influence the atmospheric circu-
lation on a larger scale. This may lead to desic-
cation and desertification over extensive areas.
The above mentioned processes could be initiated
if plans to drain the huge swamps of the White
Nile in the Sudan materialise. The surface area
of these Sudd swamps is about 34 000 km2 and
can produce 25 km3 water, which would double
the White Nile’s discharge. The consequences for
the regional rainfall are not yet known, but pre-
liminary circulation modelling exercises suggest
that 19% of the present January evaporation re-
turns as rain on the Sudd [13].
1.5.2.3. Deforestation
Deforestation of tropical forest also results in
tremendous reduction of evapotranspiration and,
ultimately, of rainfall. Whereas early simula-
tions of large-scale conversion of, for instance,
the Amazonian rain forest to pasture predicted
major reductions in regional rainfall (up to 30%),
more recent simulations based on improved mod-
els suggest a more limited effect. Particularly
disastrous conditions are known to result from
the clearing of tropical steep land forest. Sheet
wash and flooding during the wet season are often
followed by lack of water during the dry season,
because of a loss of storage capacity in the soil
due to accelerated erosion [14].
1.5.2.4. Interbasin diversion
The proposed large-scale interbasinal diversion
schemes of the Russian Federation and the USA
would come to large-scale interferences in water
circulation. Both envisage the transfer of water
from the Arctic basins to the southern semi-arid
areas. Both plans are shelved for the time be-
ing for various, mainly political, reasons. One of
the scientific objections against the Russian plans
is the fear that a substantial reduction of the in-
flow of freshwater in the Arctic Ocean could re-
sult in a smaller ice cover during winter, accord-
ingly reducing the albedo. This would have a ma-
jor impact on the world’s heat balance. In China
huge water management projects are planned and
partly under construction, aiming at the trans-
fer of water from the Yangtze River (and per-
haps the Brahmaputra) to the Hwang Ho basin in
the dry northern plains around Beijing.
16
1.5.2.5. Streamflow management
Most of the human endeavours to fight the irregu-
larity in water supply are based on the manage-
ment of stream flow. An alternative is the  con-
trol of the atmosphere by triggering rain through
cloud seeding. Many experiments have been car-
ried out, but their effectivity is difficult to prove
and the scientific results are subject to much con-
troversy, not to speak of the social and legal as-
pects. Better forecast of local convective storms
with radar and satellites might increase the suc-
cess of this technique in the future.
1.5.2.6. Land use changes
Evidently, the impact of large-scale water man-
agement schemes and changes in land use must
create anomalies and changes in the regional
moisture and heat budgets, which -by the general
circulation- may be propagated to distant regions.
Evidence of this type of ‘tele-connection’ is no-
tably available from the ocean-continent interac-
tion. A clear example is the influence of the sur-
face temperature anomaly in the  tropical Pacific
and the occurrence of the El Nino-circulation.
Understanding of these processes with their re-
gional and seasonal variability and feedback
loops, and prediction of their effects, require
an improvement in resolution of the General
Circulation Models (GCM). Earth observation
by satellite remote sensing can be a great help to
monitor the input variables, whereas the applica-
tion of isotopic tracers is a useful tool in analysing
flow paths of vapour and identifying recycling of
moisture. Notably the question of moisture recy-
cling is challenging, because until now climate
models suggest a limited contribution of local
evaporation to rainfall (see e.g. Sect. 1.5.2.4),
whereas two-third of the precipitation on a con-
tinental scale originates from re-evaporated rain-
water (Sect. 1.4.3).
1.6. Isotopes in the  hydrological
cycle
The original studies on isotopes in water were
concerned with seawater and precipitation.
The first was primarily a survey on variations in
18
O/16O concentration ratios, soon to be followed
by a study of the 2H/1H ratios in natural waters
[15]. [16] observed in great detail 18O/16O varia-
tions in global precipitation, including a discus-
sion on the meteorological patterns. His work was
 The Global Cycle of water
the start of the global ‘isotopes-in-precipitation’
network of the international organisations WMO
and IAEA. In more recent years the observations
became supported by theoretical and numerical
modelling.
The  first study on 14C in groundwater, soon
in combination with 13C/12C, was started by
the Heidelberg group in the late 1950s [17, 18].
In later years this methodology became an impor-
tant tool in studying groundwater movement.
The revolutionary development of the introduc-
tion of nuclear accelerators as mass spectrometers
has greatly stimulated the hydrological applica-
tion of isotopes with extreme low abundances in
nature. Also 14C research has gained tremendous-
ly by this new technological approach.
The  first sections in this chapter have presented
a broad picture of the global water cycle, consist-
ing of the origins of water, the sizes of the global
water reservoirs and the  fluxes between them.
However, in our day-to-day life, where we are
dealing with stream-flow management, drink-
ing-water supply, the propagation of the effects
of surface pollution underground, et cetera, we
are no less confronted with regional water bod-
ies, streams, lakes, aquifers, their sizes and their
fluxes. It will be shown that the  application of
isotopes as they occur in nature are an invaluable
help in studying the behaviour of water and find-
ing solutions for water problems. The remainder
of this volume and the other volumes of the series
are devoted to this.
The nature of the isotopic applications is of
course dictated by the  specific character of iso-
topes, radioactive and non-radioactive. We can
distinguish three different types of applications.
(1) Stable and radioactive isotopes can be used
as tracers, marking a water body or a certain
quantity of water; a nice example is the phe-
nomenon that the rain water during a heavy
storm is often depleted in the heavy isotope
(stable 2H, deuterium, or stable 18O) with re-
spect to the most abundant isotope (1H and
16
O, respectively). This offers the possibility
to follow the rain water in the surface runoff
and even quantitatively analysing the runoff
hydrograph.
(2) During the transition of compounds such as
water or carbon dioxide from one phase to
another, the concentration ratio of the iso-
topes of an element often changes, undergoes
so-called isotope fractionation. Conversely,
observing differences in especially the sta-
ble isotopic concentration ratios informs us
about certain geochemical or hydrological
processes that took place. For instance, as
a result of a series of processes, the isotopic
composition of carbon as well as oxygen of
calcium carbonate is different for the ma-
rine and the freshwater origin. Furthermore,
the isotopic composition of oxygen and hy-
drogen in rainwater varies with latitude, alti-
tude, climate and time of the year.
(3) Radioactive decay offers the possibility to
determine an age, provided certain condi-
tions are met. Noteworthy in this respect is
the frequent application of dating groundwa-
ter –i.e. determining the time elapsed since
the  infiltration of the  water- by comparing
the 14C or 3H (tritium) activities in a ground-
water sample with that of the recharge wa-
ter. Moreover, also concentration differences
of radioactive isotopes can also be used as
a tracer.
The following chapters serve to present and ex-
plain the fundamental background of the abun-
dance and behaviour of isotopes in nature, as well
as some practical information on sample handling
and analysis. The mentioning of examples will be
brief; the other volumes of this series are dealing
with the various compartments of the water cycle,
treating the role of isotopic applications in detail.
Besides the occurrence of natural isotopes in our
environment, man is able to produce radioac-
tive isotopes. Also these can be applied as trac-
ers, to follow water movement or reservoir leak-
age. The methods of applying artificial tracers
are parallel to the use of chemical tracers, often
recognisable by their fluorescent character. This
methodology will not be the main subject of these
volumes, despite the many successful applica-
tions. We will restrict ourselves to the isotopes
found in our environment by nature. Only at few
occasions we can not avoid mentioning the artifi-
cial isotopes.
17
 ATOMIC SYSTEMATICS AND NUCLEAR STRUCTURe
2. ATOMIC SYSTEMATICS AND NUCLEAR STRUCTURe
In this chapter the principles and systematics of
atomic and nuclear physics are summarised brief-
ly, in order to introduce the existence and charac-
teristics of isotopes.
2.1. Atomic structure and
the periodic table of
the elements
Atoms consist of a nucleus surrounded by elec-
trons. Compared to the diameter of an atom,
which is of the order of 10 – 8 cm, the size of
the nucleus is extremely small (~10 – 12 cm).
The dense concentration of matter of the nucleus
mainly consists of two kinds of particles, neu-
trons and protons, which have about the same
mass. The neutron carries no electric charge,
while the proton is positively charged. The num-
ber of protons (Z), the atomic number, is equal to
the number of electrons surrounding the nucleus.
Electrons have a mass that is about 1/1800 that of
the proton mass and carry an equal but negative
electrical charge, so that the atom as a whole is
neutral. Atoms missing one or more electrons are
referred to as positive ions, atoms with a number
of electrons exceeding the atomic number are
called negative ions.
Protons and neutrons, the building stones of
the nucleus, are called nucleons. The sum of
the number of protons and neutrons (N) in a nu-
cleus is the nuclear mass number:
A = Z + N (2.1)
Fig. 2.1.  Part of the  periodic table of the  elements,
containing the light elements. Also shown are the elec-
tronic configurations of the respective atoms.
The notation describing a specific nucleus ( = nu-
clide) of element X is:
A
Z XN
Because the chemical properties of an element
(X) are primarily determined by the number
of electrons in the atom, the atomic number Z
characterises the element. Therefore, writing AX
alone defines the nuclide. The cloud of electrons
circulating around the nucleus is well structured
and consists of shells, each containing a maxi-
mum number of electrons. The chemical prop-
erties of an atom are now mainly determined by
the number of electrons in the outer, incompletely
filled electron shell. Because of this systematic,
all atoms can be arranged in a Periodic Table of
the Elements (part shown by Fig. 2.1).
2.2. Structure of the atomic
nucleus
The atomic nuclei are kept together by extreme-
ly strong forces between the nucleons (protons
and neutrons) with a very small range. As repul-
sive electrical (Coulomb) forces exist between
the protons, the presence of neutrons is required
to stabilise the nucleus. In the most abundant nu-
clides of the light elements, the numbers of pro-
tons and neutrons are equal. Nuclei such as
2
H
  He2
4
  C6
12
  N7
14
  O8
16
1 1 2 6 7 8
are stable, as is the single proton (1H = hydro-
gen). For the heavy elements the number of neu-
trons far exceeds the number of protons: 238U con-
tains only 92 protons, whereas the largest stable
nuclide, the lead isotope 208Pb has an atomic num-
ber of 82.
Instabilities are caused by an excess of protons or
neutrons. Examples of such unstable or radioac-
tive nuclei are
3
H       14  C
1 2 6 8
For the light elements, a slight excess of neutrons
does not necessarily result in unstable nuclei:
  C7    15  N
13
6 7 8       O
8 9       O
17 18
8 10
are stable. For these ‘asymmetric” nuclei (Z ≠ N)
however, the probability of formation during
19

14
N 15
12 13
C C
10
B 11
B clei are unstable and have a small chance of natu-
number of protons Z 9
Be 10
Be
6 7
Li Li
3
He 4
He
1
H 2
H 3
H
n number of neutrons N
Fig. 2.2.  Part of the  chart of nuclides, containing
the light elements. The  isotopes of an element (equal
Z) are found in a  horizontal row, isobars (equal A  )
along diagonal lines, isotones (equal N) in vertical
columns. The  natural radioactive isotopes of H, Be,
and C are marked grey.
the ‘creation’ of the elements, -nucleosynthesis-,
was smaller, resulting in smaller natural concen-
trations for these nuclides.
The naturally occurring stable and radioac-
tive isotopes of the light elements are shown in
a part of the Chart of Nuclides (Fig. 2.2). Another
part, showing some heavy nuclides is given by
Fig. 11.2. Note that in the higher A range N and
Z are no longer about equal (238U with Z  =  92 and
N = 146).
2.3. Stable and radioactive
isotopes
The atomic nuclei of an element containing dif-
ferent numbers of neutrons are called isotopes
(iso topos = at the same place in the periodic
table of the elements). Many elements have two
or more stable, naturally occurring isotopes. In
general, nuclei with even numbers of protons or/
and neutrons are more stable. Nuclei of which
the number of protons or/and neutrons corre-
sponds to some specific even number, belonging
to the series of so-called magic numbers 2, 8, 20,
28, 50, 82, and 126, have a relatively high stabil-
ity and consequently large natural occurrence.
These magic numbers can be explained by a nu-
clear shell model with closed nucleon shells
within the nucleus, similar to the closed electron
shells in atoms, the basis of the periodicity in
20
INTRODUCTION
16 17 18
the periodic table of the elements. An example of
O O O
the occurrence of the magic numbers is the large
N number of stable isotopes of lead: the largest sta-
14
ble nuclide, 208Pb (with Z = 82 and N = 126) is
C
double magic. Especially the uneven-uneven nu-
ral occurrence. Most uneven-Z elements have
only one or at most two stable isotopes.
The earlier statement that the chemical properties
of an element only depend on the atomic number,
implying that the chemical properties of isotopes
are equal, needs revision if we look in detail.
The fact is that in nature variable relative concen-
trations of isotopes are observed. There are two
causes for this phenomenon:
(1) the chemical and some physical properties of
the isotopes of one element are not exactly
equal, resulting in slightly different chemical
and physical properties -and consequently
different concentrations- of isotopic mol-
ecules, i.e. molecules that contain different
isotopes of that element;
(2) if the isotopes concerned are radioactive,
the process of radioactive decay causes
the concentration of the isotopic molecules
concerned to diminish in time; this may re-
sult in concentration differences that are
much larger than as caused by the isotope
processes as mentioned under 1).
These phenomena will be discussed separately in
the next chapters.
2.4. Mass and energy
It is inconvenient to use the real mass of atoms
and molecules. Instead we define the  atomic
mass as the mass expressed in atomic mass units
(amu). Originally this was equivalent to the mass
of a proton; later for practical reasons, the atomic
mass unit has rather become defined as 1/12 times
the mass of a 12C atom:
1 amu = 1.6605655 × 10 – 27 kg (2.2)
In chemistry it is now convenient to use the mole
quantity, defined as the number of grams of the el-
ement equal to the atomic weight. The number of
atoms in one mole of the element or the number
of molecules in one mole of a chemical com-
pound is then equal for any substance and given
by Avogadro’s number = 6.02252 × 1023.
 ATOMIC SYSTEMATICS AND NUCLEAR STRUCTURe
If we now add up the atomic masses of the build-
ing stones of a certain nucleus X, for instance of
12
C consisting of 6 protons and 6 neutrons, it ap-
pears that the atomic mass of X is smaller than
the sum of the 12 constituent particles:
6 protons = 6 × 1.007825 amu =  6.04695 amu
6 neutrons  = 6 × 1.008665 amu =  6.05199 amu
total mas =  12.09894 amu
compared to A of C
12
= 12.00000 amu
(by definition)
difference = 0.09894 amu
This so-called mass defect has been converted into
the  binding energy, the potential energy ‘stored’
in the nucleus to keep the particles together. This
equivalence of mass and energy is defined by
Einstein’s special theory of relativity as
EB = Mc2 (2.3)
where EB is the binding energy, M is the mass, and
c is the velocity of light (2.997925 × 108 m/s).
According to this definition the  equivalence be-
tween mass and energy is expressed as
1 amu = 931.5 MeV (million electronvolt) (2.4)
where 1 eV = 1.602189 × 10 – 19 J
(electrical charge unit = electron charge =
1.602189 × 10 – 19C).
All energies in nuclear physics, such as the par-
ticle energies after nuclear decay, are presented in
MeV or keV (kilo or 103 electronvolt). In our case
of 12C the binding energy turns out to be 0.09894
amu = 931.5 MeV/amu = 92.16 MeV or 7.68
MeV per nucleon.
21
 abundance and fractionation of stable isotopes

3. Abundance and fractionation of stable isotopes

In classical chemistry isotopes of an element are 3.2. Isotope fractionation

regarded as having equal chemical properties. In
According to classical chemistry, the chemical
reality variations in isotopic abundances occur
characteristics of isotopes, or rather of molecules
far exceeding measuring precision. This phenom-
that contain different isotopes of the same element
enon is the subject of this section.
(such as 13CO2 and 12CO2) are equal. To a large
extent this is true. However, if a measurement is
3.1. Isotope ratios and sufficiently accurate — and this is the case with
concentrations the modern mass spectrometers (Chapter 11) —
we observe tiny differences in chemical as well
Before we can give a more quantitative descrip- as physical behaviour of so-called isotopic mol-
tion of isotope effects, we must define isotope ecules or isotopic compounds. The phenomenon
abundances more carefully. Isotope (abundance) that these isotopic differences exist is called iso-
ratios are defined by the expression
tope fractionation. (Some authors refer to this
abundance of rare isotope phenomenon as isotope discrimination; however,
R = we see no reason to deviate from the original ex-
abundance of abundant isotope
pression). This can occur as a change in isotopic
composition by the transition of a compound
(3.1)
The ratio carries a superscript before the ratio from one state to another (liquid water to water
symbol R, which refers to the isotope under vapour) or into another compound (carbon diox-
consideration. For instance: ide into plant organic carbon), or it can manifest
itself as a difference in isotopic composition be-
tween two compounds in chemical equilibrium
[13CO2] [C18O16O] (dissolved bicarbonate and carbon dioxide) or in
13
R(CO2) = 18
R(CO2) = physical equilibrium (liquid water and water va-
[12CO2] [C16O2]
pour). Throughout this volume examples of all
[2H1HO] [H218O] these phenomena will be discussed.
2
R(H2O) = 18
R(H2O) =
[1H2O] [H216O] The differences in physical and chemical proper-
ties of isotopic compounds (i.e. chemical com-
(3.2) pounds consisting of molecules containing dif-
We should clearly distinguish between an isotope ferent isotopes of the same element) are brought
ratio and an isotope concentration. For CO2 for about by mass differences of the atomic nuclei.
instance, the latter is defined by: The consequences of these mass differences are
two-fold:
[13CO2] [13CO2] 13
R
= = (3.3a) (1) The heavier isotopic molecules have a low-
[ CO2] + [ CO2]
13 12
[CO2] 1 + 13R er mobility. The kinetic energy of a mol-
ecule is solely determined by tempera-
Especially if the rare isotope concentration is ture: kT = ½mv2 (k = Boltzmann constant,
very large, as in the case of labeled compounds, T = absolute temperature, m­ = molecular
the rare isotope concentration is often given in mass, v = average molecular velocity).
atom %. This is then related to the isotope ratio Therefore, molecules have the same ½mv2,
by: regardless of their isotope content. This
means that the molecules with larger m nec-
R = (atom %/100) / [1 - (atom %/100)]
essarily have a smaller v. Some practical
(3.3b) consequences are:
(a) heavier molecules have a lower diffu-
sion velocity;

23
 INTRODUCTION

(b) the collision frequency with other mole-

cules — the primary condition for chem-
ical reaction — is smaller for heavier
molecules; this is one of the reasons
why, as a rule, lighter molecules react
faster.
(2) The heavier molecules generally have higher
binding energies. The chemical bond be-
tween two molecules (in a liquid or a crystal
for instance, or between two atoms in a mol-
ecule) can be represented by the following
simple model. Two particles exhibit compet-
ing forces on each other. The one force is re-
pulsive and rapidly increases with decreas-
ing distance (~1/r13). The other is attractive
and increases less rapidly with decreasing
distance (in ionic crystals (~1/r2, between
uncharged particles ~1/r7). As a result of
these forces the two particles will be locat-
ed at a certain distance from each other. In
Fig. 3.1 the potential energies corresponding
to each force and to the resulting net force
are drawn schematically. If one particle is
located at the origin of the co-ordinate sys-
tem, the other will be in the energy well.
Escape from the well is possible only, if it
obtains sufficient kinetic energy to overcome
the net attractive force. This energy is called
the binding energy of the particle. A simple
example is the heat of evaporation.
Although the particle is in the energy well, it is not
at the bottom of the well, even at the zero point
of the absolute temperature scale (–273.15°C).
All particles have three modes of motion: transla-
tion, i.e. displacement of the molecule as a whole,
vibrations of the atoms in the molecule with re-
spect to each other, and rotations of the molecule
around certain molecular axes. In the energy well
representation: the particle is not at the bottom
of the well, but at a certain (energy) level above
the zero energy. In Fig. 3.1 an energy level is in-
dicated by a horizontal line. The higher the tem-
perature of the substance, the higher energy level
will be occupied by the particle.
The energy required to leave the well — i.e. to
become separated from the other particle — is
indicated as the binding energy EB, whereas EB’
is the binding energy for the rare (heavy) parti-
cle. The energy of a certain particle at a certain
temperature depends on its mass. The heavier
isotopic particle is situated deeper in the energy
well than the lighter (heavy line in Fig. 3.1) and,
Fig. 3.1.  Schematic representation of the  potential
energy distribution caused by the  repulsive and at-
tractive forces between two particles, in this case be-
tween oppositely charged ions. The  resulting potential
is well-shaped (solid line). The one particle is situated
at the  origin (r = 0). The  second particle is situated
in the  well. The  small horizontal lines in the  well are
the energy levels of the system, the thin and heavy lines
referring to the light and the heavy isotopic particle, re-
spectively. The  arrows indicate the  respective binding
energies at the zero temperature T0 and a higher tem-
perature T, respectively. At higher temperatures the dif-
ference between the  binding energies for the  isotopic
particles is smaller, resulting in a smaller isotope effect.
therefore, escapes less easily: the heavier isotopic
particle (atom or molecule) generally has a higher
binding energy: EB’ > EB (Fig. 3.2: normal case).
Examples of this phenomenon are:
(1) 1H218O and 1H2H16O have lower vapour pres-
sures than 1H216O; they also evaporate less
easily and
(2) in most chemical reactions the light isoto-
pic species reacts faster than the heavy. For
example Ca12CO3 dissolves faster in an acid
solution than does Ca13CO3.
In an isotope equilibrium between two chemical
compounds the heavy isotope is generally con-
centrated in the compound which has the largest
molecular weight.
The depth of the energy well may also depend on
the particle masses in a more complicated man-
ner. Under certain conditions with poly-atomic
molecules the potential energy well is deeper for
the light than for the heavy isotopic molecule.
Due principally to this phenomenon the bind-
ing energy of the heavy molecule can be smaller.

24
 1
1) H218O et 1H2H16O ont des pressions de vapeur plus faibles que 1H216O; ils s’évaporent donc
moins facilement, et
2) dans la plupart des réactions chimiques, les espèces à isotopes légers réagissent plus vite que
abundance and fractionation of stable isotopes
celles à isotopes lourds. Par exemple, Ca12CO3 se dissous plus vite dans une solution acide que ne
le fait Ca13CO3. Fig.3.2 Représentation schématique de l’effet isotopique normal (à gauche) et
Because the isotope effects discussed above gen- If wequelques
Pour are dealing with changes
interactions, in isotopic
le creux d’énergie potentielle pour les
Lors de l’équilibre isotopique entre deux composés chimiques, l’isotope lourd est généralement
erally result in lower vapour pressure for the iso- composition,
(ligne épaisse) for instance
est moins C isque
profond oxidised to les particules lég
celui pour
concentré dans le composé
topically qui aspecies
heavy le poids (normal
moléculaire le plus effect),
isotope élevé. CO2, the carbon isotope spécifiques,
fractionationl’énergie
refers de liaison pou
Dépendant d’interactions
this effect is referred to as the inverse isotope ef-
La profondeur du puits d’énergie peut aussi dépendre de la masse des particules the ‘new’ 13
R(CO
d’une façon ) value
2beaucoup to the ‘old’ 13
R(C), in
isotopiquement 13 lourde13 peut être 13plus importante (côté gauche: effet norm
plus complexe.fectSous
(Fig. 3.2).
certainesPractical
conditions,examples of the inverse
si l’on considère les molécules
other words
poly-atomiques,
a =  R(CO
le creux 2)/ R(C).
(côté droit: effet inverse) que pour une particule légère.
isotope effect are the higher vapour pressure of
d’énergie potentielle est plus profond pour les molécules légères que pour les molécules lourdes. Et
13
CO2 in the liquid
simplement en raison
phase as well as the lower sol-
de ce phénomène, l’énergie de liaison des molécules In general
lourdesisotope plus are small: α ≈ 1.
peut êtreeffects
ubility of 13CO2 in water than of 12CO2, both at Therefore, the deviation of α from 1 is widely
faible. Parce que les effets isotopiques discutés plus haut produisent
En général,généralement
les effets des pressions
isotopiques sontdefaibles: α ≈factor.
1. Ainsi,
room temperature [19]. used rather than the fractionation Thisune déviation d’α p
vapeur plus faibles pour les espèces isotopiquement lourdescouramment (effet isotopique normal),
utilisée plutôt cet
queeffetle est à de fractionnement. Cette quantité, qu
facteur
quantity, to which we refer as the fraction-
rapprocher deAt highisotopique
l’effet temperatures
inverse the differences between
(Fig.3.2). Des exemples pratiquesation,
fractionnement, de est
l’effet isotopique
définie
is defined par: by:inverse
binding energies of isotopic
13 molecules becomes
sont la pression de vapeur élevée de CO2 dans la phase liquide ainsi que la plus faible solubilité de
13 smaller, resulting in smaller — an ultimately dis- R
CO2 par rapport à 12CO2, les deux processus se produisant à température ε B/A ambiante
= α B/A − 1(Vogel
= B −et1 al., (×10
(×10 3‰3
) (3.5)
‰)
appearing — isotope effects (Fig. 3.1). R
1970). A  
Aux températures élevées, la différence entre les énergies εdereprésente ε represents
molécules the enrichment
l’enrichissement
liaison des (ε > 0) or the de-
(ε > 0) ousel’appauvrissement
isotopiques (ε < 0) de l’isotope rare
3.3. Kinetic and equilibrium pletion (ε < 0) of the rare isotope in B with
réduit, provoquant des effets isotopiques moindres, et disparaissant en phaseαultime
Les symboles B/A et ε (Fig.3.1).
B/A sont équivalents à α A(B) et εA(B). Dans un processus irrév
isotope fractionation respect to A . The symbols εB/A and εB/A  are
est le changement de composition isotopique; en d’autres termes: la nouvelle comp
The process of isotope fractionation is math- àET equivalent to αA(B) and εA(B). In the one-way
3.3 FRACTIONNEMENTS ISOTOPIQUES CINETIQUE comparée l’ancienne.
A L’EQUILIBRE
process (A  → B) ε is the change in isotopic
ematically described by comparing the isotope
Le processusratios
de fractionnement isotopique estinmathématiquement
of the two compounds chemical equilib- que ε composition,
Parce décrit en un nombreinpetit,
estcomparaison other
des il words:
rapports the new isotopic
est généralement donné en ‰ (pour mille, é
composition compared to the old.
isotopiques derium
deux(A ⇔ B) or
composés of the compounds
en équilibre chimique (Abefore and
Notons
⇔ B) ou deuxnous
deque ne définissons
composés aprèsε un
avant et pas en ‰, comme de nombreux auteurs le procla
processus de after a physical
transition physiqueorou chemical
chimique (Atransition
→ B). Leprocess
ne Because
le fontdepas
facteur réellementε puisqu’ils
fractionnement is isotopique
a smallajoutent
number, it islegenerally
est toujours symbole ‰). Une valeur de
(A → B). The isotope fractionation factor is then given in ‰ (per mill, equivalent
alors défini comme le rapport de deux rapports isotopiques 5‰ est égale à 0.005. La conséquence est que, dans les to 10  – 3
). Note
équations mathématique
defined as the ratio of the two isotope ratios:d’utiliser ε/10that
3 we do not define ε in ‰, as many authors
à la place du simple ε. L’étudiant doit se souvenir que ε est un peti
claim they do. (In fact they do not, as they al-
R(B) RB équations, " −25‰ de " −25/103 ".
α A (B) = α B/A = = (3.4) il doit
waysêtre
addnumériquement
(3.4) écritAn
the ‰ symbol). " àof,
ε value la place
for in-
R(A) RA stance, 5‰ is equal to 0.005. The consequence
Le fractionnement de B par rapport à A est toujours noté εB/A ou εA(B). De cette dé
is that in mathematical equations it is incorrect
which
qui exprime le expresses
rapport the isotope
isotopique de la phaseratio
ou leincomposé
the phase or rapport
déduisons
B par simplement:
to àuse ε/10
celui de3 lainstead of du
phase ou merely ε. The student
compound B relative to that in A .
composé A.

Si nous considérons les changements de composition isotopique, par exemple C oxydé en CO2, le
fractionnement isotopique du carbone rapporte la « nouvelle » valeur 13R(CO2) à la valeur
« ancienne » 13R(C), ou, en d’autres termes : 13α = 13R(CO2)/13R(C).

34

Fig. 3.2.  Schematic representation of the normal (left) and the inverse (right) isotope effect. For some interac-
tions the potential energy well for the heavy particle (heavy line) is less deep than for the light particle (thin line).
Depending on the specific interaction the binding energy for the isotopically heavy particle can be larger (left-
hand side: normal effect) or smaller (right-hand side: inverse effect) than for the light particle.

25
 INTRODUCTION

is to be reminded that ε is a small number; in [22]. In practice, however, these data are often
equations one may numerically write, for in- not known in sufficient detail. With kinetic iso-
stance, ‘–25‰’ instead of ‘–25/103’. tope effects we are confronted with an additional
difficulty which arises from the  fact that natural
Again, the fractionation of B with respect to A is processes are often not purely kinetic or irrevers-
denoted by εB/A or εA(B). FromChapitre 3
the definition of ε ible. Moreover, kinetic fractionation is difficult
we simply derive: to measure in the laboratory, because (i) com-
plete irreversibility can not be guaranteed (part
− ε A/B of the water vapour(3.6) will return to the liquid), nor
ε B/A = ≈ −ε A/B (3.6)
1 + ε A/B can the  degree of irreversibility be quantified;
(ii) the vanishing phase or compound will have
the last step because in natural processes the ε a non-homogeneous and often immeasurable iso-
en dernière étape, puisque dans les processus naturels, les valeurs de ε sont faibles.
values are small.
topic composition, because the isotope effect oc-
Il est important de distinguer entre deux sortes de fractionnement isotopique: le fractionnement
It is important to distinguish between two kinds curs at the surface of the compound. For example
cinétique et ofle isotope
fractionnement
fractionation: kinetic Le
à l’équilibre. fractionnement
fractionation and cinétique provient
the surface de of
layer processus
an evaporating water mass
chimique et equilibrium
physique irréversibles, i.e. en sens unique.
fractionation. Kinetic fractionation C’est, par exemple, l’évaporation
may become enriched de inl’eau
18
O and 2H if the mixing
results from
avec un éloignement irreversible
immédiat i.e. one-way
de la vapeur, physical
l’absorption or
et la diffusion des gaz,
within ainsi que
the water mass d’autres
is not rapid enough to keep
chemicalirréversibles
réactions chimiques processes. Examples
telles que include the evap- bactérienne
la décomposition its contentdes homogeneous
plantes ou throughout.
la
oration of water with immediate withdrawal
précipitation rapide de calcite. Ces effets de fractionnement sont premièrement of déterminés par les
the vapour from further contact with the water; Isotope fractionation processes in nature which
énergies de liaison des composés originaux (Part.3.2) dans lesquels, lorsare desnot
processus
purely physiques,
kinetic des
(i.e. one-way processes)
the absorption and diffusion of gases, and such ir-
molécules isotopiquement légères ont des vitesses plus importantes etwill de be
plusreferred
faibles énergies
to as de
non-equilibrium fraction-
reversible chemical reactions as the bacterial de-
liaison ; pendant les processus chimiques, les molécules
cay of plants or rapid calcite precipitation. These légères ations. An example is the evaporation of ocean or
réagissent plus rapidement que les
molécules lourdes. Dans quelques cas toutefois, c’est
fractionation effects are primarily determined by l’inverse. Cet fresh
effet surfacecinétique
isotopique water bodies:
inverse the evaporation is not
the binding
se produit plus communément energies
dans of les the original compounds
réactions impliquant des atomes d’hydrogène (Bigeleisen et water vapour con-
a one-way process (certainly
(Sect. 3.2) in that during physical processes iso-
Wolfsberg, 1958). denses), neither an equilibrium process as there is
topically lighter molecules have higher veloci- a net evaporation.
Le second type de fractionnement est le fractionnement
ties and smaller binding energies; in chemical à l’équilibre (ou thermodynamique). C’est
Equilibrium fractionation, on the other hand, can
essentiellement cet effet
processes lightqui est impliqué
molecules react moredansrapidly
les réactions
than à l’équilibre (ou réactions
be determined by laboratory experiments and
the heavy.
thermodynamiques). Comme In some cases,
exemple however,
formel, nous avonsthe opposite
choisi les réactions d’échanges isotopiques:
in several cases reasonable agreement has been
is true. This inverse kinetic isotope effect occurs shown between experimental data and thermody-
most
*A + Bcommonly
⇔ A + *B in reactions involving hydrogen namic calculations.(3.7)
atoms [20].
dans lesquelles l’astérisque indique la présence de l’isotope rare. Le facteur The general condition
de fractionnement pourforcet the establishment of
The second type of fractionation is equilibrium
équilibre entre phases ou composés A et B est la constante d’équilibre isotopic
pour equilibrium
l’équation d’échange between
3.7: two compounds is
(or thermodynamic) fractionation. This is essen-
the existence of an isotope exchange mechanism.
tially the isotope effect involved in a (thermody-
[Aequilibrium ] /[B] RAs
] [*B] [*Breaction. This can be a reversible chemical equilibrium
namic)
K= = = B =a formal
α B / A exam- (3.8)
such as:
ple we [*Achoose
] [B] the isotope
[*A] /[A] exchange RA reaction:

*A + Bsuffisantes
⇔ A + *B H 16O + C18O16O ⇔ H C18O16O ⇔ H 18O + C16O
(3.7) et molécules
2 2 2
Si des informations sur les énergies de liaison des atomes sont disponibles, les
where
fractionnements the asterisk
peuvent points
être calculés, aussitobien
the presence of
pour l’effet cinétique (3.9a)
(Bigeleisen, 1952) que pour
the rare
l’effet à l’équilibre isotope.
(Urey, 1947).The fractionation factor
En pratique toutefois, ces for this ne sont
données or such a reversible
pas souvent connuesphysical
avec process as evapora-
equilibrium between phases or compounds A and tion/condensation:
suffisamment de détails. Avec les effets isotopiques cinétiques, nous sommes confrontés à une
B is the equilibrium constant for the exchange re-
difficulté supplémentaire qui provient du fait que les processus naturels ne sont jamais purement
action of Eq. 3.7: H216O(vapeur) +H 2 O(liquide)
18
cinétiques ou irréversibles. De plus, le fractionnement cinétique est difficile à mesurer en laboratoire,
parce que (i) la complète
⇔ H2 O(vapeur) + H216O(liquide)
18
(3.9b)
[A] [*B]irréversibilité
[*B] / [B]ne peutRB pas être garantie (une partie de la vapeur d’eau va
retourner versKla=phase = pas plus que
[*A]liquide),
[B] [*A]
=
/ [A] neRpeut
αB/A
=être (3.8)le degré
quantifié The reaction rates of exchange
de cette irréversibilité; (ii) processes and,
A
consequently,et the periods
la phase ou le composé qui disparaît aura une composition isotopique non-homogène souvent non- of time required to
If sufficient
mesurable parce que l’effet information about àthe 
isotopique se produit bindingdeen-
la surface reachPar
ce composé. isotopic
exemple,equilibrium,
la pellicule vary greatly. For in-
ergies of atoms and molecules is available,
18 2stance, the exchange of H2O ⇔ CO2 proceeds on
de surface d’une masse d’eau qui s’évapore peut s’enrichir en O et H si le mélange interne de la
the fractionation effect can be calculated, the ki- a scale of minutes to hours at room temperature,
masse d’eau n’est pas assez rapide pour conserver sa composition isotopique homogène durant tout2–le
netic effect [21] as well as the equilibrium effect while that of H2O ­⇔­ SO requires millennia.
processus.
Les processus de fractionnement isotopique dans la nature, qui ne sont pas purement cinétiques (i.e.
26
processus univoque) appartiendront à la catégorie des fractionnements hors équilibre). C’est, par

36
 r' k'[H CO 3 ]

A l’équilibre isotopique, le bilan des effets isotopiques, en d’autres termes:

13 – 13
R(Δ
abundance and fractionation CO
of stable R(ΔCO 2 )
3 ) = isotopes

de telle manière qu ‘en combinant les résultats des Eqs.3.11 et 3.13:

The fractionation resulting from kinetic iso- so that combining Eqs.3.11 and 3.13 results in:
tope effects generally exceeds that from equilib-
αk ' 13
R(CO 2 ) [13 CO 2 ][H12 CO 3– ]
rium processes. Moreover, in a kinetic process = 13 = = αe
the compound formed may be depleted in the rare αk R(HCO 3– ) [12 CO 2 ][H13 CO 3– ]
isotope while it is enriched in the equivalent (3.15)
equilibrium process. This can be understood ce quibymontre que le fractionnement isotopique à l’équilibre αe est équivalent
which shows that the isotopic equilibrium frac-
comparing the fractionation factor in a reversible d’équilibre de la réaction d’échange isotopique:
tionation αe is equivalent to the equilibrium con-
equilibrium with the kinetic fractionation factors stant of the isotope exchange reaction:
involved in the two opposed single reactions. As H13 CO 3− + 12 CO 2 ⇔ H12 CO 3 + 13 CO 2
an example we take the carbonic acid equilibrium H13CO –3 + 12CO2 ⇔ H12CO3 + 13CO2 (3.16)
of Eq. 3.9a: La plupart des valeurs de αk et αk' sont inférieures à 1 de plus de un pour cent. Les
Most αk and αk’ values are less than 1 by more
CO2 + H2O ⇔ H  + HCO!
+
leurs rapports sont moindres – de l’ordre de quelques pour mille -. Plus loin, n
than one per cent. Differences between their18 ra-
For the single reactions l’évaporationtios
de l’eau peut —
are less provoquer un appauvrissement
in the order of several per O de la vapeur d’eau
en mill.
fois supérieur
Later we will see that rapid evaporation of waterdu au fait que la mo
à celui de la vapeur en équilibre avec l’eau. Ceci est
12
CO2 + H2O → H+ + H12CO –3
également favorisée dans lethe water
might cause processusvapour
de condensation.
to be about twice as
and depleted in 18O as the vapour in equilibrium with
En considérant l’ Eq.3.15, il est évident que, alors que α16k d’une phase de transition
13
CO2 + H2O → H+ + H13CO –3 the water. The reason for this is, that H2 O is fa-
petit que 1, α e peut être supérieur à 1. On a un exemple dans le système CO2 dis
voured also in the condensation process.
the reaction rates are, respectively: teneur en13C du CO2 retiré rapidement d’une solution à CO2 aqueux est inférieur
From Eq. 3.15 it is obvious that, while αk for
12
r = 12k[12CO2]  et  13r = 13k[13CO2] (3.10) a certain phase transition is smaller than 1, αe
38 might be larger than 1. An example is to be found
where 12k and 13k are the reaction Chapitre
rate3 constants. in the system: dissolved/gaseous CO2: the 13C
The isotope ratio of the bicarbonate Chapitre 3 formed content of CO2 rapidly withdrawn from an aque-
(∆HCO!) is: 13 13 13 ous CO2 solution is smaller than that of the dis-
r k[ CO ] 13
13
R(ΔHCO 3 ) = 1213 = 1213 1213 2 = α k R(CO 2 ) solved CO2 (i.e. 12(3.11)
C moves faster: αk<1), while
rr kk[[ COCO22]] 13
13
R(ΔHCO 3 ) = 12 = 12 12 = α k R(CO 2 ) under equilibrium (3.11) conditions the gaseous CO2
r k[ CO 2 ] contains relatively more 13C (αe>1; inverse iso-
ou αk est le facteur
(3.11) de fractionnement cinétique pour cette réaction. A l’inverse, pour: Sect. 3.2).
tope effect,
ou αk est le facteur de fractionnement cinétique pour cette réaction. A l’inverse, pour:
where α is the kinetic
− fractionation factor for this
H + + H12k CO 3 → 12 CO 2 + H 2 O
reaction. Conversely, for: 3.4. Theoretical background of
H + + H12 CO 3 − → 12 CO 2 + H 2 O
H+ + H12CO –3  → 12CO2 + H2O equilibrium fractionation
et
et and In this section we will present a discussion
H++ + H1313 CO–3  − →1313 CO 2 + H 2 O of the origin of isotope effects, in particular
H  + H CO 3  →  CO2 + H2O the mass-dependent isotope fractionation, based
H + + H13 CO 3 − → 13 CO 2 + H 2 O
on some principles from thermodynamics and
les taux de réaction
the reactionsont rates are
statistical mechanics. The treatment here will not
les taux de réaction sont
− be exhaustive and so, for full details, the reader
rʹ' = 
= 1212k 'ʹ[[H ] 13rʹ = 
et 13kʹ[H1313CO 
12 −
12
H1212CO 
CO3–3]  et   r ' =–3] 13k '(3.12)
[ H 13CO3 ]is referred to textbooks
(3.12)on these subjects. A basic
12 12 12 − 13 13 13 −
r ' = k '[ H CO3 ] et r ' = k '[ H CO ] (3.12)
The carbon dioxide formed (∆CO ) has an iso- 3 discussion has been given by [23, 24].
2
Le gaz carbonique formé (ΔCO2) a un rapport isotopique:
tope ratio A basic principle of quantum physics is that
Le gaz carbonique formé (ΔCO2) a un rapport isotopique: the energy of the particle can take only certain
13
r' 13 k'[H13CO 3– ] ' 13 discrete values. This is true for any kind of mo-
13
R(ΔCO 2 ) = 1213 = 1213 = α k R(HCO 3 ) –
(3.13)
r'r' k'
k'[H CO3–3– ]]
[H1213CO ' 13 tion. These discrete energy values were already
13
R(ΔCO 2 ) = 12 = 12 = α k R(HCO 3 ) –
(3.13)
r' k'[H12 CO 3– ] mentioned in Sect. 3.2, where we discussed
A l’équilibre (3.13)
isotopique, le bilan des effets isotopiques, en d’autres termes: the position of a particle at a certain time at a cer-
A l’équilibre isotopique, le bilan des effets isotopiques, en d’autres termes: tain level in the energy well (Figs.3.1 and 3.2).
At isotopic
13 equilibrium the isotope effects bal-
R(ΔCO 3– ) = 13 R(ΔCO 2 ) A basic principle (3.14)
of statistical mechanics states
ance,
13
in other
–
words:
13
R(ΔCO 3 ) = R(ΔCO 2 ) that the chance that(3.14)
a particle is at a certain en-
de telle manière
13 qu ‘en –combinant les résultats
R(ΔCO 3 ) =  R(ΔCO2) (3.14)
13 des Eqs.3.11 et 3.13: ergy level εr is:
de telle manière qu ‘en combinant les résultats des Eqs.3.11 et 3.13:
αk ' 13
R(CO 2 ) [13 CO 2 ][H12 CO 3– ]
= 1313 = = αe (3.15) 27
αk ' (CO 23–)) [[1213CO
RR(HCO ][H1312CO
CO22 ][H CO3–3– ]]
= = = αe (3.15)
α k 13 R(HCO 3– ) [12 CO 2 ][H13 CO 3– ]
ce qui montre que le fractionnement isotopique à l’équilibre αe est équivalent à la constante
d’équilibre de la réaction
ce qui montre d’échange isotopique:
que le fractionnement isotopique à l’équilibre α est équivalent à la constante
seulement que certaines valeurs discrètes. Ceci est vrai pour n’importe quel déplacement. q Ces
* q Bénergies
*q /q
Un principe de base de la physique quantique stipule que l’énergie des α A (particules
B) = K =ne Apeut = B B
prendre
discrètes ont déjà été mentionnées dans la partie 3.2, où nous avons discuté de la *position
Un principe de base de la physique quantique stipule que l’énergie des particules ne q A qB d’une
peut * qA / qA
prendre
seulement que certaines valeurs discrètes. Ceci est vrai pour n’importe quel déplacement. q A Ces
* q Bénergies
* qB / qB
seulement que certaines valeurs discrètes. Ceci est vrai pour n’importe
particule à un instant donné et à un certain niveau dans le creux d’énergie (Figs.3.1 α
quel A ( B ) = K =
déplacement.
et 3.2). Ces =
énergies
discrètes ont déjà été mentionnées dans la partie 3.2, où nous avons discuté de la *position
discrètes ont déjà été mentionnées dans la partie 3.2, oùNous nousdevons
avons maintenant
discuté de évaluer
q q
A les
la position
* q A / q A fonctions de répartition.
d’une
B différentes
d’une
Un principe
particule à unde base donné
instant des états et à de
un la mécanique
certain niveau statistique est
dans le creux que la « chance
d’énergie
INTRODUCTION (Figs.3.1 » qu’une
et 3.2). particule se
particule à un instant donné et à un certain niveau dans le creux d’énergie (Figs.3.1 et 3.2).
trouve à un niveau d’énergie donné ε est: Dans
Nous la Part.3.2,
devons les troisévaluer
maintenant modesles dedifférentes
déplacement sont nommés
fonctions translation, rotation
de répartition.
Un principe de base des états de la rmécanique statistique est que la « chance » qu’une particule se
Un principe de base des états de la mécanique statistiquefonction est que dela partition
« chancetotale d’unparticule
» qu’une système àseun composé ou une phase est en relation a
trouve à un niveau d’énergie donné εr est: Dans la Part.3.2, les trois modes de déplacement sont nommés translation, rotation
trouve à un niveau ed’énergie
− ε r /kT donné εr est: de partition des the molecule around molecular
différents déplacements par: axes, and inter-
pr = fonction de partition
molecular totale d’un système
(external) à un composé
motions, such as ou une phase est en relation a
vibrations
e −−εεqrr/kT
/kT de partition des
qand différents
= qtrans déplacements par:
qrotqvibr of molecules with respect to each
rotations
pr = e
p r = kq is the Boltzmann constant and T the ab-
where other, in a crystal lattice, for instance. Most sys-
ou k est la constante de q Boltzmann et T la température absolue du composé. q = qLa valeur
qvibrde
qrottoo q, la fonction
solute temperature of the compound. The value of Chaque fonction
tems de
transpartition
are résulte
complicated de mouvements
to allow an intramoléculaire
exact cal- (interne), tels l
de partition, est déterminée par l’obligation que la somme de toutes les chances soit égale à l’unité :
q, the partition
ou k est la constante de Boltzmannfunction,
et T laistempérature
determined byatomes
the re-
absolue les uns
du composé. par
Larapport
culation auxq,autres,
of the partition
valeur de les rotations de
functions.
la fonction la molécule
The only sim-autour de l’axe mo
ou k est la constante de Boltzmann et T la température absolue du composé.
Chaque fonction La q, la fonction
valeur derésulte
de partition de mouvements intramoléculaire (interne), tels l
quirement
de partition, est that the sum of all chances mouvements ple systems
intermoléculaires
déterminée par l’obligation que la somme de toutes les chances soit égale à l’unité : are ideal mono-atomic
(externes) telles les or di-atomic
rotations et les vibrations des mo
de partition, est∞ déterminée par l’obligation que la somme de toutes les chances soit égale à l’unité :
atomes les uns par rapport aux autres, les rotations de la molécule autour de l’axe mo
∑
equals pr =unity:
1 par rapport aux gases.
mouvements bouring
The translations
autres, dans un treillis
intermoléculaires
arecristallin,
not hindered by neigh-
par exemple ; La plupart des sys
r∞=0 compliqués pour permettre atomsunor(externes)
molecules
calcul
telles
and
exact des
les intermolecular
rotations et les vibrations des mo
fonctions de partition. Les gaz id
∑
r∑
∞

=0
p =
prr = 1
1 par rapport aux autres,
diatomiques, vibrations
représententand
dans un treillis
rotations
les seuls
cristallin,
do not
sytèmes
par
exist,Les
simples. soexemple
that only; La plupart des sys
translations ne sont pas gênée
donc que : r =0 compliqués pour permettrecomponents
the internal un calcul exact des fonctions de partition. Les gaz id
ou les molécules voisins et les vibrationsofet the partition func-
les rotations intermoléculaires n’exist
∞ diatomiques, tions have
représentent to
lesbe calculated.
seuls In
sytèmes simples.order Lesto point out
translations ne sont pas gênée
donc que : so
donc que : q =that: ∑
r∞=0
−
e rε /kT manière que seul les composants internes
ou les moléculesthe massvoisins dependence (3.17) doivent être calculés.
of fractionation
et les vibrations factors
et les rotations and
intermoléculaires n’exist
q = ∑ e −εr /kT
∞ − εr /kT Afin
manièrede montrer
to la dépendance
illustrate the 
(3.17) que seul les composants internes des
influence facteurs
of de fractionnement
temperature
(3.17) doivent être calculés. on frac-et pour illustrer l
= r∑
q partition e est donc la sommation de la population (3.17)
La fonction de =0
r =0
température tionation,
de tous les
sur niveaux
le we will
d’énergies
fractionnement,briefly
pour
nousmention
unallonsthe various
brièvement parti-
mentionner les divers
système donné, ainsi l’étatisd’énergie
et détermine function Afin deC’est
dudit système. montrer
tion la dépendance
une functions.
donnée importante,des parce
facteurs de fractionnement et pour illustrer l
The partition
La fonction de partition est donc la sommation de la population partition.
thus the summing up
de tous les
La fonction
que de partition est
les considérations donc la sommationmontrent
thermodynamiques quetempérature
de la population surniveaux
les deconditions
tous les niveaux
d’énergies pour
led’équilibre
fractionnement,
d’énergies
peuvent pour
un allons brièvement mentionner les divers
nous
un
être
of the population of all energy levels
système donné, et détermine ainsi l’état d’énergie dudit système. of
La a cer- Translation
C’est une
translation d’unedonnée of a molecule
importante,
molécule dans sonparce as a whole
ensemble has the par-
a la fonction de partition suivante:
système donné,
exprimées entain et détermine
tant system
que rapport ainsi
des l’état d’énergie
fonctions dudit
de partition. partition.
système. C’est une donnée importante, parce
and so determines the energy
que les considérations thermodynamiques montrent que les conditions state of titiond’équilibre
function: peuvent être
que les considérations
the system. thermodynamiques
It isd’échange
anfonctions
important montrent
quantity,quebecause
Lales conditions
translation d’uned’équilibre peuvent
molécule dans 3
être
son ensemble a la fonction de partition suivante:
exprimées en encore
Considérons tant quelarapport
réactiondes de partition.
isotopique de l’ Eq.3.7:
exprimées enthermodynamic
tant que rapport des fonctions de partition.
considerations show that equi- ⎡ 2πmkT ⎤ 2
qtrans = ⎢ ⎥⎦ 3 V (3.20)
librium
Considérons encore laconditions can be isotopique
réaction d’échange expresseddeasl’a ratio
Eq.3.7: of ⎣ h
2
Considérons *A
encore
+ B la⇔réaction
A + *Bd’échange isotopique de l’ Eq.3.7: ⎡ 2πmkT ⎤ 2
partition functions. qtrans = ⎢
(V = volume 2 ⎥ V
⎣− h lesinmolécules
⎦ which the molecules are free to
*A + B ⇔ A + *B (V = volume dans lequel sont
Consider
*A + B ⇔ again
ou A et B représentent Adeux the isotope
+ *Bcomposés exchange
différents (parreaction
exemple, ofCO2 etmove, HCO 3 ) is
m outhe mass
deux phases du libres de sehmouvoir,
of the molecule, Planck’s
m est la masse de
même composé Eq. 3.7:
(par exemple, H2O liquide et vapeur d’eau),(V constante
et = de Planck).
l’astérisque se rapporteDans un gaz,
àa gas
la la
présence contribution du mouvement
de libres de contribution au rapport de la fonc
ou A et B représentent deux composés différents (par exemple, volume
CO constant).
2 etdans HCO −
lequel In deux
3 −) oules moléculesthe translational
phases sont
du se mouvoir, m est la masse de
ou A et Brare
représentent deux composés
(13C, 18O, différents
2 (par la est alorsCO
exemple, (M 2=et
to poids
HCO moléculaire):
the partition ) fractionnement
ou deux phases-i.e.du
àunlafunction ratio
de thenduismouvement
(M = molar
l’isotope dans la molécule H, etc.). Dans définition du facteur 3de
même composé *A (par
+ B exemple,
⇔ A + H2O liquide et vapeur d’eau),constante
*B de Planck).
et l’astérisque se Dans
rapporte gaz, la contribution
présence au rapport de la fonc
même composé
la constante (par exemple,
d’équilibre- H132O liquide
les concentrations,
18 2
et vapeur
ou d’eau),
plutôt les et l’astérisque
activités, weight):
sont se
doncrapporte à
représentéesla présence
3 par de
des 3
est alors (Mdu=facteurpoids
l’isotope rare dans la molécule ( 13C, 18O, 2H, etc.). Dans la définition
l’isotope
fonctions rare dans laA and
molécule ( C, O, H,different la définition du ⎛facteur
etc.). Danscompounds * q ⎞ moléculaire):
de fractionnement
⎛*m ⎞2 3 ⎛*M
de fractionnement
-i.e. 2
-i.e.⎞
la constante where lesBconcentrations,
denote two
de partition: ⎜⎜ donc ⎟⎟ représentées
=⎜ ⎟ =2 par
⎜ ⎟3 2
3
d’équilibre- ou plutôt les activités, sont  * q   * m  des
* M 
la constante (for
d’équilibre-
instance,lesCO
concentrations, − ou plutôt les activités, sont
2 and HCO 3 ) or two phases of
  
⎝⎛*qqdonc =⎝⎛ *mm ⎠⎞ 2  par
⎠⎞trans représentées 3
⎝= Mdes⎠ 2 (3.21)
⎛ *M ⎞ 
⎜⎜ q ⎟⎟ trans= ⎜  m⎟ = ⎜  M
fonctions de partition:
partition: compound (for instance, liquid H2O and
fonctions de the same ⎟ 
qui est dépendante ⎝ q ⎠de ⎝ m ⎠
la température. ⎝ M 39⎠
water vapour), and the asterisk refers to the pres- trans

ence of a rare isotope in the molecule (13La C, 18O, de which is temperature independent.

quifonction partition
est dépendante de la pour le mouvement
température. 39 de rotation interne d’une molécule diatom
39
2
H, etc.). In the definition of the fractionation fac-
The partition function for internal rotational mo-
tor — i.e. the equilibrium constant the concentra-
La fonction de partition2 pour2le mouvement de rotation interne d’une molécule diatom
tion or rather the activities are now 3represented
Chapitre tion of8π μ r0 kT molecule is:
a diatomic
qrot =
by the partition functions: sh 2 2
8π 2 μ r0 kT
qrot = (3.22)
q A * qB * qB / qB ou r est la distance sh 2
d’équilibre
entre deux atomes et µ la masse réduite de la molécu
α A ( B) = K = = (3.18)
o (3.18)
* q A qB * q A / q A m2); l’énergiewhere
de rotation
r is the equilibrium distance between µ tourne autour
ou ro est la distance d’équilibre
o
est égale à celle d’un système dans lequel
entre deux atomes et µ la masse réduite de la molécu
masse à la place de m1atoms
the two et m2 autour
and µdeischacun d’eux. Nous
the reduced massdevons
of de plus rappele
We must now evaluate the various partitionrépartition.
Nous devons maintenant évaluer les différentes fonctions dem
func-
2); l’énergie de rotation est égale à celle d’un système dans lequel µ tourne autour
moment d’inertie
the molecule = m1m2/(m1 + m2); the energy of ro-molécule consiste
d’une masse en rotation, et que s = 1, sauf si la
tions. masse à la place de m1 et m2 autour de chacun d’eux. Nous devons de plus rappele
Dans la Part.3.2, les trois modes de déplacement sont nommés translation,tationrotation
is equalettovibration.
that of a system
La where µ rotates
In Sect. 3.2 the three modes of motion 40 were d’inertie
moment d’une masse enof rotation, et que s of
= 1,msauf si la molécule consiste
fonction de partition totale d’un système à un composé ou une phase around
est en the centre
relation avec les mass
fonctions instead 1 and m2
mentioned, translation, rotation and vibration. around each other. We should further remember
de partition des différentspartition
The total déplacements par: of a system40of one
function Fractionnement en isotopes stables
that µr0 is the moment of inertia of a rotating
2
compound or one phase is related to the partition mass, and that s = 1, unless the molecule consists
qfunctions
= qtransqrotof
qvibrthe different motions by: (3.19)
égaux, cas pour lequel s est égal à 2.which
of two equal atoms in Dans case s = 2.
un gaz, In a gas de la rotation
la contribution
Chaque fonction the rotational
: tels les contribution
vibrations des to the partition func-
q = qdetrans 
partition
qrot qvibr résulte de mouvements intramoléculaire
(3.19) est(interne),
partition donc
tion ratio thus is:
atomes les uns par rapport aux autres, les rotations de la molécule autour de l’axe moléculaire, et les
mouvements Each partition function
intermoléculaires results
(externes) telles from intramolec-
les rotations μ * m1 lesMunes
⎛ * q ⎞ des *molécules
et les vibrations s
ular (internal) motions, such as vibrations of at- ⎜⎜ ⎟⎟ = = (3.23)
par rapport aux autres, dans un treillis cristallin, par exemple ; La plupart
oms with respect to each other, and rotations of ⎝ q ⎠ des
rot
μ
systèmes m1
sont
* Mtrop
* s
compliqués pour permettre un calcul exact des fonctions de partition. Les gaz idéaux, mono ou
diatomiques, représentent les seuls sytèmes simples. Les translations ne sont rare
avec *m1, isotope pas gênées par les
de l’atome m1.atomes
Ce rapport est également dépendant de la tempér
28 voisins et les vibrations et les rotations intermoléculaires n’existent pas, de telle
ou les molécules
La fonction de partition de la vibration est:
manière que seul les composants internes doivent être calculés.
− hν / 2 kT
Afin de montrer la dépendance des facteurs de fractionnement et pour e l’influence de la
qvibr illustrer
=
− e hν / kT fonctions de
température sur le fractionnement, nous allons brièvement mentionner les 1diverses
 Fractionnement en isotopes stables
égaux, cas pour lequel s est égal àFractionnement
2. Dans un gaz, la contribution
en isotopes stables de la rotation à la fonction de Chapitre 3
partition
égaux, casestpour
donclequel
: s est égal à 2. Dans un gaz, la contribution de la rotation à la fonction de
1
partition est donc : ⎡dehν ⎛
égaux, cas pour lequel s est égalFractionnement
à 2. Dans un
en gaz,
isotopesla contribution
stables de q
la M
fractionation=of stable*
* *
rotation
⎛ ⎞à2 lamfonction
s μ ⎞⎤
⎛*q ⎞ * μ * mFractionnement
1 M
abundance
s en isotopesand stables ⎜ ⎟ isotopes
exp ⎢ ⎜1 − ⎟⎥
⎜⎜ :⎟⎟ = = q ⎝ M ⎠ m *s (3.23) ⎜ *μ ⎟
partition est donc
⎛⎝ *qq ⎞⎠ rot *μμ *mm11 *M M *ss ⎢⎣ 2kT ⎝ ⎠⎥⎦
égaux, cas pour ⎜⎜ lequel
⎟⎟ =s est égal
= à 2. Dans un gaz, la contribution de la rotation à la fonction de(3.23)
partition ⎝ q lequel
égaux, cas pour
where
est donc
μ the rare
⎠ rot*ms is
est
⎛ * q:⎞ égalmà1 2.*isotope
M
1* μ
* sun of
Dans gaz, la contribution
atom m . This ra-
*m M s
de la rotation à la fonction
tion between 1 α anddeK contains a factor 2 such that
⎜⎜ also ⎟⎟ is = = m1 1. Ce où m et *m sederéfèrent aux isotopes échangés. Le facteur de fractionnement à l’équ
2 arising(3.23)
*
avec m1, est
partition isotope
donc
tio :rare deindependent
l’atome of rapport est également
temperature. dépendant la température.
the factor from s/*s is cancelled in cal-
q
⎝ ⎠ rot μ m 1 * M * s gaz diatomiques A et B est donné par l’Eq.3.18. Il faut noter que, si A ou B consistent
avec *
m1, isotope q ⎞rare de
⎛ *partition * μl’atome m m1. Ce
1 M
*vibration rapport est également dépendantculating
sest: α. A simple numerical example is given
de la température.
La fonction deThe vibrational
⎛⎜⎜ * q ⎞⎟⎟ = *de μ la
= partition
m function is: que O2 (3.23)
* 1 M s équivalents (tels in Sect. 3.7. ou CO ), la véritable relation entre α et K contient un fact
La fonction de q ⎟⎟⎠ rot = μ
⎜⎜⎝ partition de m1 * M *est:
= vibration s (3.23) 2
/ 2la
*
avec m1, isotope ⎝ q ⎠rare de
− hμν l’atome
kT m1 m * 1. Ce
M * s rapport est également dépendant
facteur 2 de la température.
provenant de s/*s s’annule lorsque l’on calcule α. Un exemple numérique s
rot e
qvibr = − hνh/ν2/kTkT (3.24) A general approximate (3.24) expression for the frac-
La fonction
avec *
de partition
m , isotope rare1ede de la vibration
− el’atome m1. Ce rapport dans la partie
est: est également dépendant 3.7.
de la tionation
température.
* 1
avec m1, isotope qvibrrare= de l’atome m1. Ce rapport est également dépendant de la température.
factor as a function
(3.24) of the temperature is
hν / kT
1ν−−is heν /la
of Une obtained from Eqs.3.18 and 3.29:
oùLa fonction
est la de
La νfonction dewhere partition
fréquence
partition e de vibration
vibrationest:
dedethe frequency
2 kT
la vibration of vibration
de deux
est: atomes l’un parexpression
the two rapport à générale
l’autre. La approximative
fréquence estdu facteur de fractionnement en tant que
q = température est obtenue à partir (3.24)
des équations
où ν est la atoms
généralement vibr
connue
fréquence 1ewith
− ede νrespect
/ 2hkT
− hνpar donnéesto spectroscopiques
/ kT
vibration each
de other.
deux The frequency
atomes expérimentales.
l’un par rapportαIlà= peut B/T être
l’autre.
Ae Lamontré
(3.30) fréquenceque la 3.18 et 3.29:
est
is q =
vibrgenerally
− hν / 2 kT
e hla ν / kT known from experimental spec-
(3.24)
dépendance vis-à-vis
généralement = 1 −de
connue
qvibr epar température de l’effet de fractionnement
données spectroscopiques expérimentales. est du,Il enpeut
première hypothèse,
B/T être(3.24)
montré queà la
où ν est la troscopic fréquence 1 − e hde ν / kT vibration de deux atomes l’un par rapport
data. The temperature dependence of α à Ae
=
where l’autre.
the  La fréquence A and
coefficients est B do not depend
dépendance thermique
vis-à-vis dedelala vibration. de l’effet de fractionnement est du, en première hypothèse, à la
température
où ν est la the fractionation
généralement fréquence
connue de parvibration
donnéeseffect can
deuxbe shown
despectroscopiques
atomes l’untoexpérimentales.
be caused
par rapport à l’autre.Il La fréquence
peut être est que la
montré
où ν est la thermique
dépendance fréquence de de la vibration
vibration.
on temperature
de deux atomes l’un par rapport à l’autre. La fréquence est but contain all temperature-inde-
Lagénéralement
dépendance
dépendance primarily
vis-à-visconnue
de masse deparlabydedonnées
la the temperature
spectroscopiques
fréquence
température dedel’effet
vibration
dedependence où les of
expérimentales.
de l’oscillateur
fractionnement coefficients
Ilest
peut être
harmonique
du, en
pendent Amontré
et
est
première Bdonnée
ne
que dépendent
lapar:
hypothèse,
quantities (mass,à pas
la de la température
vibration mais contiennent tou
frequency).
généralement connue par données spectroscopiques expérimentales. Il peut être montré que la
dépendance the vibration.
vis-à-vis de la température de l’effet de fractionnement est du,
thermiquement en première hypothèse,
indépendantes
The natural à la
(masse,
logarithm fréquence de vibration). Le logarithme natur
La dépendance
dépendance
dépendance thermique
vis-à-vis de masse de dela de la la fréquence
vibration.
température de vibration
de l’effet de l’oscillateur
de fractionnement harmonique
est du, en première est donnée
hypothèse, à lapar: of the fractionation factor
dépendance thermique de la 1vibration. fractionnement est approché par les séries de puissance:
The mass is approximated by the power series:
Ladépendance
dépendance thermique 1 ⎛dek 'dependence
de masse lade
⎞ 12vibration.
la fréquence of dethe vibration frequency harmonique
vibration de l’oscillateur est donnée par:
La dépendance νof= de masse ⎜
the harmonic
⎜ ⎟ de ⎟ la fréquence de vibration
oscillator is given by: de l’oscillateur harmonique est donnée par: (3.25)
1π ⎛⎝ kμde
La dépendance de 2masse C2
' ⎞⎠ 2la fréquence de vibration de l’oscillateur harmonique est donnée par: C
ν= ⎜ ⎟⎟ 1
⎜ ln α = C1 + + 32(3.25) (3.31a)
2π ⎝ μ 1⎠ 2 T T
1 ⎛ k ' ⎞
⎛⎜k 'la⎞ ⎟ masse réduite de la molécule et (3.25)
νν ==µ11 est
12
ou de nouveau ⎜⎛⎜k ' ⎟⎞ 2⎟ k' est la constante de (3.25) (3.25)une
force. Dans
ν = 22ππ ⎜⎜⎜⎝⎝μμ⎟⎟⎟⎠ ⎠ with the often
avec l’approximation souvent used approximation
(3.25)utilisée for the frac-
pour le fractionnement:
approximation
ou de nouveau µ2πest de premier μ la ordre,
masse k' n’est
réduite pas
de altéré
la par
molécule la substitution
et k' est lad’un isotope
constante dans
de la
force. molécule,
Dans et
une
⎝ ⎠ tionation:
donc:
approximation where de premier again µ isréduite
ordre, the reduced
k' n’est pas altéré mass parofla the mole-
substitution d’un ε ≈isotope
ln(1+ε) dans la molécule, et
ou de nouveau µ est la masse
ou de nouveau µ est la masse réduite de la molécule et k' est la constante de la molécule et k' est la constante de de=Dans
force. C 1 + une
force. C2Dans
/T une
ou
donc: de nouveau
approximation de
culepremier µ and k’ is the 
est la masse force constant. In a  first order
réduite de la molécule et k' est la ε ≈ dans
constante ln(1+ε)
de force. = C1 +etC2/T (3.31b)
Dans une
approximation de premierordre, k' n’est pas altéré par la substitution d’un isotope
1ordre, k' n’est pas altéré par la substitution d’un isotope dans la molécule, et
la molécule,
approximation
donc:
approximation de premier ordre, k’k'isn’estnot altered
pas altéré parby an
la isotope
substitution
On sub-
d’un isotope
peut de dansmontrer
plus la molécule, qu’àet très hautes températures, la contribution de
donc: stitution *ν ⎛ μin⎞the molecule, 2
and so: It can further be shown, that at very high tem-
donc: = ⎜⎜ ⎟⎟ 1 fractionnement contrebalance le produit (3.26) des facteurs translation et rotation, ce qui fina
*νν ⎛⎝ *μμ ⎞⎠1 2 peratures the vibrational contribution to the frac-
= ⎜⎜ ⎟⎟12 1 à α = 1, et donc les effets isotopiques(3.26)
disparaissent quand les températures sont suffisa
*νν ⎛⎝ * μ μ⎞ ⎠ tionation balances the product of the translational
*νν ⎜ μμ ⎟
= ⎜
⎛ ⎛ ⎟
⎞ ⎞ 2 2 (3.26) (3.26)
Aux températures ν ==normales
⎜⎝⎜* μ ⎟⎠ ⎟ (T < hv/k), la fonction exponentielle A partir dude ceand
qui rotational
dénominateurprécède,dans nousfactors,
(3.26) pouvons
l’Eq..3.24 so
(3.26) that finally
déduire
peut at very high
les conclusions suivantes:
ν ⎜⎝⎜⎝**μμ⎟⎠ ⎟⎠ temperatures α = 1, and thus, isotope effects dis-
être négligée.
Aux températures Le rapport
normales de la (Tfonction
< hv/k), de partition exponentielle
la fonction est alors: du dénominateur dans l’Eq..3.24 peut
Aux températures At normal
normalestemperatures (T < hv/k), la fonction (T < hv/k) 1)
the exponen-
exponentielle Dans unappear
du dénominateur processus
dans at cinétique
l’Eq..3.24 peut (irréversible),
sufficiently high temperatures.la phase ou le composé formé
être
Aux négligée.
températures Le rapport
normales de(Tla<fonctionhv/k), la de partition
fonction est alors:du dénominateur dans l’Eq..3.24 peut
exponentielle
Aux négligée.tial
être températures function
Le rapportnormales de lain (T the denominator
< hv/k),
fonction la fonction
de partition est in Eq. 3.24 isotopes
exponentielle
alors: can lourds pardans
du dénominateur rapportl’Eq..3.24 peutou au composé originel (αk < 1); les prédic
à la phase
être négligée.⎛Le ⎞
* qrapport de hla(ν fonction
−*ν ) / 2 kT de partition est alors: From the foregoing we can draw the following
être négligée.be ⎟⎟ = de
⎜⎜Leneglected.
rapport e la The partition
fonction de partition functionestratio alors: then suris: le degré de fractionnement (3.27)
ne peuvent être que qualitatives (un corps d’eau
conclusions: 18
⎛⎝⎛⎜ **qqq⎞⎠⎞⎟ vibr = eh (νh−(ν*ν−)*/ν2)kT/ 2 kT rapide sera appauvri en O relativement
(3.27) à l’eau elle-même) ;
⎜⎛⎜ *qq ⎟⎞⎟⎟ = e h (ν −*ν ) / 2 kT (3.27)
⎜⎜⎝⎝⎛ *qq⎟⎟⎠⎠⎞vibrvibr = e (3.27) (1) In a kinetic (3.27) (one-way or irreversible) process
ou, en insérant q ⎠⎟vibr = e h (ν −*ν ) / 2 kT
⎝⎜⎜ l’Eq.3.26: 2) Dans un processus d’équilibre
the phase isotopique
(3.27)
or compound (réversible),
formed on ne peut
is depleted in pas prédire avec
⎟
⎝ q ⎠ vibr phase (ou un the heavy
composé) sera enrichie
isotope withourespect
appauvrie to en isotopes lourds. Toutefois
the origi-
ou,
ou,eneninsérant
insérant l’Eq.3.26: l’Eq.3.26:
ou, en insérant or,l’Eq.3.26: inserting Eq. 3.26:
⎛*q ⎞ ⎡ hν ⎛ μ ⎞⎟⎤
(liquide plutôt nalquephase
vapeur) or compound
ou le composé (α <
ayant
k 1);la theoretical
masse moléculaire la plus im
ou, en insérant ⎜⎛⎜ l’Eq.3.26: ⎟ = exp ⎜
⎡ ⎢⎡hν ⎛ ⎜⎛ μ ⎞⎤ ⎟⎞⎥⎤1 − vs CO2) contient predictions
normalement (3.28)
about the degree
l’abondance la of
plusfractionation
importante d’isotopes lourds.
⎛ * q ⎞⎟⎞
⎛⎜⎜⎝ **qqq⎞⎟⎟⎠⎟ vibr ==exp ⎡⎢ ⎣⎢h2 νhkTν⎛⎜1⎝⎜− μ *⎞⎟μμ ⎤⎥ ⎠⎟⎦⎥ (3.28)
⎜⎜⎝ qq ⎟⎟⎠⎟vibr = exp ⎢⎣ 2kT exp ⎢ ⎜ 1 −
⎜⎝1⎜− * μ ⎟⎠⎥ ⎟ ⎟ ⎥ (3.28) can only be qualitative
(3.28) (fast evaporating wa-
(3.28) et en supposant que des données spectroscopiques su
2kT *μ ⎦ 3) En conditions d’équilibre
⎝⎝⎛ *qq⎠⎠⎞vibr vibr ⎢⎣ 2⎣⎢⎡kThν⎜⎝ ⎛⎝ * μ ⎟⎠μ⎥⎦ ⎞⎠⎦⎥⎤ ter is depleted in 18O relative to the water it-
avec µ = m1m⎜⎜2(m1⎟⎟+ m2=). exp ⎢ ⎜1 − ⎟⎥ énergies de liaisonself) sont disponibles,(3.28) αe peut être calculée; les mesures de αe de
avec µ = m1mwhere ⎝2(m q 1 ⎠+vibrmµ2).= m1m⎣⎢22(m kT +⎜⎝ m ). * μ ⎟⎠⎦⎥
avec
avec µµ== m 1m22(m
m1de (mfonction
11 ++m m2).2). de partition 1 2 sont reportées dans le chapitre 6.
Le rapport la d’un gaz diatomique aux températures (2) normales
In an isotopicest alorsequilibrium
obtenu (reversible) pro-
Le rapport deThe partition la fonction de partition function d’un gaz
ratio diatomique
of a di-atomic aux températures
gasEnat règlenormales est alors obtenu
en
Le
Le combinant
rapport de les
la équations
fonction de 3.19,
partition 3.21,
d’un 3.23
gaz et 3.28:
diatomique aux 4)
températures générale,
normales cess
est it le
alors fractionnement
can
obtenunot with décroît
certainty avec l’augmentation des tempé
be predicted
enrapport
avec µ = m1de
combinant mnormal la
(mfonction
2les 1 + m2). de
équations temperatures 3.19, partition
3.21, 3.23 d’un
is thus
gaz diatomique aux températures normales est alors obtenu
et 3.28:
obtained
Chapitre 3 by combin-
en combinant
en combinanting les équations
les Eqs.3.19,
équations 3.19, 3.19, 3.21, 3.23
3.21, 3.23et 3.28:
et3.28:
3.28: whether the one phase or
montré, par exemple, dans le Chapitre 6, pour les échanges compound is en-
à l’équilibre CO2 ⇔
Le rapport de la fonction de 3.21,
partition 3.23d’un andgaz diatomique aux températures normales est
riched or depleted alors obtenuin the heavy isotope.
41 41
en combinant les équations 1 3.19, 3.21, 3.23 et 3.28: However, the dense 41 phase (liquid rather than
*q ⎛*M ⎞ *m s 2 ⎡ hν ⎛ μ ⎟ ⎞ ⎤ 41
=⎜ ⎟ exp ⎢ ⎜1 −
⎜ ⎟ ⎥ 42(3.29) vapour)(3.29) or the compound having the largest
q ⎝ M ⎠ m *s ⎣⎢ 2kT ⎝ * μ ⎠⎦⎥
molecular mass (CaCO 41 3 versus CO2) usually
contains the highest abundance of the heavy
où m et *m se where réfèrent m and aux isotopes *m refer to the exchanging
échangés. isotopes.
Le facteur de fractionnement à l’équilibre entre deux
isotope
gaz diatomiques A et B est donné par l’Eq.3.18. Il faut noter que, si Atwo
The equilibrium fractionation factor between ou B consistent en deux atomes
équivalents (telsdi-atomic que O2 gases ou CO2A and B is given
), la véritable relation byentreEq. 3.18. It
α et K contient
(3) Under equilibrium conditions and provided
un facteur 2, tel que ce
should be noted that, if A or B consists of two
facteur 2 provenant de s/*s s’annule lorsque l’on calcule α. Un exemple numérique simple est donné
sufficient spectroscopic data on the  binding
equal atoms (such as in O2 or CO2), the true rela- energies are available, αe may be calculated;
dans la partie 3.7.
Une expression générale approximative du facteur de fractionnement en tant que fonction de la
température est obtenue à partir des équations 3.18 et 3.29: 29

α = AeB/T (3.30)

où les coefficients A et B ne dépendent pas de la température mais contiennent toutes les quantités
 *D *M A + MB M A ×MB
α= =
D * M AM B M AM B

Dans l’exemple de la diffusion de vapeur d’eau dans l’air, le facteur de fractionneme

INTRODUCTION
l’oxygène est (MB de l’air est considéré comme égal à 29, MA = 18, *MA = 20):

measurements on αe of various isotope equi- 1

libria will be reported in chapter 6 ⎡ 20 + 29 18 × 29 ⎤ 2

18
α =⎢ = 0.969 (3.35)
⎣ 20 × 29 18 + 29 ⎥⎦
(4) As a rule fractionation decreases with in-
creasing temperature; in Chapter Par 6 diffusion
this By diffusion through air water vapour thus will
dans l’air, la vapeur d’eau18s’appauvrie donc en 18O (en accord avec les l
is shown, for instance, for the exchange become depleted in O (in agreement with
fin de la Part.3.4) ‰: 18ε at
de 31 given
the rules = −31 ‰. of Sect. 3.4) by 31‰:
the end
equilibria of CO2 ⇔ H2O and H2Oliquid ⇔
H2Ovapour. At very high temperatures
Fractionnement en isotopesthe iso-
Lestables 18
ε = −31‰. en 13C pour la diffusion du CO2 dans l’air est:
facteur de fractionnement
topic differences between the compounds The  13C fractionation factor for Chapitre 3
diffusion of CO2
disappear. through air is:
⇔ H2Ovapeur. A très hautes températures, les différences isotopiques entre les composés
Fractionnement
Fractionnement en
en isotopes
isotopes stables
stables
disparaissent. 1

3.5. Fractionation by diffusion ⎡ 45 + 29 44 × 29 ⎤ 2

α =⎢ 13
= 0.9956 (3.36)
⇔ H22Ovapeur . A très hautes températures, les différences isotopiques⎣ 45 entre + 29 ⎥⎦
× 29 les44 composés
3.5 FRACTIONNEMENT
As was mentioned inPAR
vapeur DIFFUSION
Sect. 3.2 isotope fraction-
disparaissent.
Comme cela ation
a été might occurenbecause
mentionné Part.3.2,oflethe different mobili-
fractionnement isotopique
en d’autres inpeut
other
termes εwords
survenir
13
= −4.4en‰,ε = −4.4‰, a depletion
113 raison des
correspondant 3 of
à un appauvrissement
Chapitre de 4.4 ‰.
ties of isotopic molecules. An example in nature 4.4‰.
mobilités différentes des molécules isotopiques. Dans la nature, la diffusion de CO2 ou H2O à travers
3.5 FRACTIONNEMENT
is the diffusion of CO2PAR or HDIFFUSION
2O through air.
l’air en est un exemple. 3.6 RELATION ENTRE 1 RAPPORTS ISOTOPIQUES ATOM
Comme cela According
a été mentionné en Part.3.2,
to Fick’s law the le net
fractionnement
flux of gas, isotopique
F, peut ⎡survenir
45 + 29 en44raison ×between ⎤ des
29Chapitre
2
Selon la loi de Fick, le flux net de gaz, F, à travers une unité de surface, est:α = ⎢ 3.6.
MOLECULAIRES
13 Relation 3 atomic and
throughdes
mobilités différentes a unit surfaceisotopiques.
molécules area is: Dans la nature, la diffusion de⎣ 45 CO×22 29 ou H44 22O+à29 ⎥⎦ = 0.9956
travers
molecular isotope ratios
l’air en est un exemple. Nous devons considérer plus attentivement 1 la signification du rapport isotopique dan
dC We ⎡ 45
want + 29 44
torares × 29 ⎤
have⎥d’un a closer
élémentlook dansatlesthe meaning
2
F = −D (3.32) termes
l’abondance desα =isotopes molécules poly-atomiques con
13
13
⎢⎣ 45 = 0.9956
(3.32) (3.36)
Selon la loi de Fick, ledflux en
ded’autres ×ε 29
= −4.4 44 + 29 ‰, ⎦ correspondant à un appauvrissement de 4.4 ‰.
x net de gaz, F, à travers une unitédeux surface, est:
atomes of de the isotope
cet élément. Le ratio in the context
rapport isotopique correspond of the abun- à la « chance » que l’
where dC/dx is the concentration gradient soitenremplacé
d’autres dance
in termes
13
par εun =of −4.4 rare isotopes
‰, correspondant
isotope rare. Pour
ofappauvrissement
à un an element
être plus précis, de 4.4in‰.poly-
nous définissons le ra
d C
ou dC/dx est le gradient de concentration dans la direction 3.6 de diffusion et atomic molecules,
D la constante
RELATION containing
de diffusion.
ENTRE RAPPORTSat least two atoms
ISOTOPIQUES ATOM
F = −D
the direction of diffusion and D is the diffusion atomique (R ) comme l’abondance (3.32) de tous les atomes isotopiquement rares du com
dx à la température et à 1/√m,3.6avec m,of lathis element.ENTRE The isotope Cette ratio is the chance
atom
Cette dernière est proportionnelle MOLECULAIRES
RELATION masse moléculaire. RAPPORTS ISOTOPIQUES ATOMIQUES ET
constant. The latter is proportional to the temper- l’abondance that de tous les isotopesisotope abondants. Pour
proportionnalité the abundant
MOLECULAIRES
la mêmehas been être replacedplus explicite,
by nous avons
aturerésulte
and todum–fait
½ que toutes
, where les molécules
m is the molecular Nousdans
mass.
exemple
un gaz
devons
simple,
(mélange)
considérer plus ont
attentivement la signification du rapport isotopique dan
ou dC/dx est et
température le donc
gradient
un de
½mvconcentration
2
moyen dans la direction
équivalent. de diffusion
La vitesse
Nous devons
moyenne
the 
et Dles
des
rare
la
considérer isotopes
isotope.
constante
plus
molécules,
dedel’hydrogène
attentivement
et
To diffusion.
donc,
la moredans
besignification
leur
du la
specific, molécule
rapport we define
isotopiqued’eau:
dans le contexte de
This proportionality results from the fact that all
l’abondance desisotopes
l’abondance the atomicisotopes rares
raresisotope d’un ratio élément
(R dans les molécules poly-atomiques con
atom) as the abundance
des d’un élément dans les molécules poly-atomiques contenant au moins
Cette dernière est proportionnelle
sont molecules à la température et à 1/√m,deuxavec m, la masse moléculaire. Cette
mobilité inversement inproportionnelles
a gas (mixture) have equal
à √m. tempera-
deux atomesatomes de cet élément.2Le 16
ofde all
cet rare
élément.
[ H OPour
rapport
isotopic
Le 1 isotopique
atoms
rapport
H]la+être 2 17
[même
correspond
in
isotopique
1 à la2 « chance
the compound 18 1 » que l’isotope
correspond
H O H] + [ H O H] + 2[ H O H] + ........ àdi-
la2 16abondant
« chance2
» que l’
proportionnalité
turerésulte
and thusdu equal
fait que toutes ½mv
average les molécules
2 dans
. The average un gaz
soit remplacé 2 par (mélange)
R un = isotope rare.ont plus précis, nous définissons le rapport isotopique
Si le processus de diffusion implique gaz soit remplacé vided
)par
atom by
un the abundance
isotope
1 16 rare.
1 Pour 1of 17all
H être 1 abundant
plus+ 2[précis,
1 isotopic
18
Odunous
1
+ [définissons
1 16 1 ra
H] +le......
température et donc
velocity unof½mv 22
moyenle équivalent.
the molecules
mouvementLa du vitesse
and, thus, their
A au travers
atomique
moyenne
mobili-
du
(Ratom
des gaz
comme B,l’abondance
m
2[
molécules, doit
H O toutefois
et de H]tous+les
donc, être
2[leur
atomes O H]
isotopiquement Hrares H]
composé Hdivisée
O par
remplacée par la masse réduite: atomique (R
l’abondance atoms.
de
atom ) comme
tous lesFor the sake
l’abondance
isotopes abondants. of declarity,
Pour tous
être we
les
plus select
atomes
explicite, a simple
isotopiquement
nous avons rares
sélectionné un du com
mobilité sont ties are inversely
inversement proportional
proportionnelles to m½.
à √m. example,
exemple simple, les isotopesthe isotopes
de l’hydrogène dans of lahydrogen
molécule d’eau: in water:
l’abondance
Les abondances de tousde “second les isotopes ordre”, abondants.
telles quePour par êtreexemple plus 2explicite,
H218O en nous avons
nominateu
Si le processusIf dethe diffusion
diffusion
m A mB implique process of interest
le mouvement du gazinvolves
A au
exemple travers du
simple, gaz
les B, 2 m 16 doit
isotopes detoutefois
l’hydrogène être dans la molécule d’eau:
dénominateur,2 Ront =été négligées. (3.33)ce contexte, le rapport isotopique(3.37) moléculaire
[ H O H] + [ HDans
1 2 17 1 2 18 1 2 16 2
O H] + [ H O H] + 2[ H O H] + .........
μ=
remplacée parthe movement
la masse mB of gas A through gas B, however,
m A + réduite: comme l’abondance2[de
atom
H O H] + 2[ 1H17 O1H] + 2[ 1H18 O1H] + [ 1H16 O1H] + ........
1 16 1
l’isotope rare d’un élément spécifique dans un type spécifi
m has to be replaced by the reduced mass: 2 [ 2H 16 1
H] +que
O telles [ 2abondant.
Hpar17 O 1
H] +2H[ 218H 18 1
O H] (3.37)
+ 2[ 2 H1 16 2
H] + ........d
divisée par l’abondance de l’isotope 2O
Les abondances R =
de “second ordre”, exempleDans notre exemple
2 O en nominateur et H H O en
du 18deutérium
m AA mBB atom 1 16 1
2[ HDans O ceH] + 2[ H 1 17 1
+ 2[ H
O H]isotopique 1 18 1
O 1 16 1
+(R[ molH) estOdéfini
H] + ......
μ = sur la théorie cinétique des gaz).
(voir le document d’eau:
dénominateur,
(3.33) The ‘second-order’
ont été négligées. abundances,
(3.33)
contexte, le rapport such as forH]in-
moléculaire
m AA + mBB comme l’abondance de 2l’isotope rare d’un élément spécifique dans un
stance H22 O16 in1 the nominator and H H O in
18 1 type
2 18 spécifique de molécule

Les
divisée par l’abondance de
abondances de=que [ l’isotope
the denominator, H Oordre”,
“second H]
abondant. Dans notre exemple du deutérium
have been
tellesneglected.
que par exemple In this con-2 dans la molécule
H218O en nominateu
Les équations ci-dessus sont valables pour les isotopes abondants d’eau: aussiRbien
2
pour les isotopes
(see textbooks on the kinetic theory of gases). mol
[ 1H 16 1
isotope ratio (Rle
(voir
rares.leLedocument sur la théorie
fractionnement cinétique
résultant desdonné
est alors dénominateur,
gaz). par le rapport text
des coefficients été2 2de
ontthe molecular
négligées. O H] Danspourceles contexte, ) is defined
molrapport isotopique moléculaire
[ H16 Odiffusion
1
H]
The above equations hold for the abundant as well
comme as
2
R
l’abondancethe abundance
= de
1 16l’isotope
of the rare
rare d’un isotope
élément of a specific
spécifique dans un (3.38) type spécifi
deux espèces isotopiques. De plus, les masses moléculaires peuventréaliste
La valeur être remplacées
mol
2 [ cette
de H O H] 1
par les se
définition poidsréfère, par exemple, à labymesure des rapport
Les équations as for the rare
ci-dessus sontisotope.
valables The resulting
pour les fractionation
isotopes abondants element
aussi bien in
que a specific
pour les type
isotopes of molecule divided
moléculaires M en numérateur et dénominateur: divisée par l’abondance de l’isotope abondant. àDans notre exemple du deutérium d
is then given by the ratio spectrométrie the abundance
laser
La valeur réaliste (voir
de cette définition ofsethe abundant
Sect.10.2.1.2), isotope.
la mesureIn
ou l’absorption
réfère, par exemple, our
lumineuse
des ex-isotopiques
rapports permetsparla comp
rares. Le fractionnement résultant est alors of the diffusion
donné coef-
par le rapport
d’eau: des coefficients de diffusion pour les
spectrométrie laser (voir Sect.10.2.1.2), ou l’absorption lumineuse permets la comparaison de deux
molécules, ample of
différant deuterium
seulement d’uninisotope,
water: contrairement à la spectrométrie de mas
deux espècesficient * D
for the two
isotopiques. *De
M +
isotopic
plus,
M lesM
species.
masses
× M
Furthermore,
moléculaires peuvent différant
molécules, être remplacées
seulement d’unpar lescontrairement
isotope, poids à la spectrométrie de masse (Kerstel et al.,
the molecular
α = = masses can be replaced by the mo-
A B A B 1999 ; comm. pers.).
1999 ; comm.2pers.).
2 16 1
[ H O H](3.34)
moléculaires M en D numérateurMet M
lar weights M*in
dénominateur:
numerator M B denominator:L’équation 3.37Rpeut
M Aand mol = 1 16telle (3.38)
A B
L’équation 3.37 peut 2ré[-écrite
êtreêtre H O1H]
ré -écrite que:telle que:

*D *M + M M ×M [ 2 H17 O1H] [ 2 H18 O1H] 2[ 2 H16 O 2 H]
Dans l’exemple = * M AA de
α =de la diffusion +M B MA
vapeur
B × M BBdans l’air, La
d’eau
A valeur de
le(3.34)
facteur The 
réaliste realistic
de[ 2cette
fractionnementH 16 O1H]
value
1 + 2 of
définition
résultant H16 Ose
[ (3.34) 1this
pour
H]
2+ 2definition
[réfère, 16 par
H[ 17HO OH]
+ 2refers,
1 1 exemple,
H] [[ 2 HH
18 à1 la for 2[ 2 Hdes
.......
O H] H] mesure
16 1O
16 rapport
O 2 H]
D * M M M M * instance,
2
Ratom = 1 to the measurement 1 + of +
isotope ratios + (3.39) ....
l’oxygène est (MB de l’air est considéré
A
A B
B commeA
A B
à 29, Mspectrométrie
Bégal A = 18, MA =laser 20): 2(voir
[ H[ 2O
16
HSect.10.2.1.2),
1 16 1 [ H O H]ou
H] O1 +H]1 16 1 [ 2+H[ 116l’absorption
1 17 1 1
HOO
18 1 H] [ 2H lumineuse
H] + [ 1 H16O16 O
1 1 16 2
H]1H] permets
2 16 1la comp
....... [ H O H]
by
molécules, différant
2
R laser= spectrometry
atom seulement (see
1 [ H isotope,
Sect. 10.2.1.2),
O H] 1 [ 17 16 1
H O1 H] 2[ 1H 18 1where
Oà H] de mas
In the example [ 1H16 Od’un
2absorption H]is compared [ H contrairement
O H] Ola1H]
[ H isotopic spectrométrie
[ 1H16 O 2 H]
Dans l’exemple de la diffusionofdewater
vapeur 1vapour
d’eau diffusing
dans l’air, through
le
1999facteur de
Le ;premier
comm.
the light
fractionnement
pers.).
facteur résultant 1 +
pour
à droite dans l’équation Eq.3.391 est16le rapport 1
of+two
isotopique
1 16 moléculaire.
1
+ En
1 bonne
16 1
.....
air, the resulting
⎡ 20 + 29 18 fractionation
× 29 ⎤ 2 factor for oxygen is** molecules, only differing [inH oneO H] [
isotope, H O
contraryH] 2[ H O H]
18
l’oxygène est (M α B=de l’air est considéré⎥ comme = 0.969 égal à 29, MAA =approximation,
18, MAA = 20): les rapports isotopiques (3.35) moléculaires dans le second facteur peuvent être remplacés
(MBB of⎢⎣ 20 18 +to29be⎦ 29, MA = 18, MA = 20):
air×is29taken *
L’équation 3.37
par les rapports mass
to isotopiques spectrometry
peut être ré -écrite telle
atomiques: [25] que:(priv.comm.).
Le premier facteur à droite dans l’équation Eq.3.39 est le rapport isotopique moléc
1 17 18 2
1 1 + R + R + R + ....... 2 17 1 2 18 1 2 16 2
à[ laH Omol H] + [ H O H] + 2[ H O H] ....
⎡ 20 +la29 18 ×d’eau
29 ⎤ 22 s’appauvrie donc en approximation,
18
2
les≈ rapports
Ratom 2
Rmol 17 isotopiques moléculaires
= 2R dans le second facteur (3.40) peuven
Par diffusion18
18dans
α = l’air, vapeur = 0 . 969 O (en accord avec les
1 +lois R +données
18
+ 2R
R(3.35) 1++.......
30 ⎢⎣ ⎥
⎦ par les rapports isotopiques 2
[ H O H] atomiques:
16 1
[ H O H] [ H O H] [ H16 O1H]
2 16 1 2 16 1 2
fin de la Part.3.4) de 3120 ׉:2918ε18 + 29‰.
= −31 2
R =
44 atom
2 [ 1H16 O171H] 18 [ 1H2 17 O1H] [ 1H18 O1H] [ 1H16 O 2 H]
Le 13 1 + R +1 +R +1 16 R +1.......+ 1 2 16 1 + 1 16 1 .....
Parfacteur de dans
fractionnement en Cd’eau
pours’appauvrie
la diffusion donc
du COen2 dans l’airaccord est:
2
diffusion l’air, la vapeur 18
18O (en Ratom ≈ 2les
avec Rmol
lois données
17 18 à[laH2 O H]
=[ HRmol
O H] 2[ H O H]
18
1 + R + R + R + .......
fin de la Part.3.4) de 31 ‰: ε = −31 ‰.
18
 d’eau: 2 [ 2 H16 O1H] important que celui considéré pour les isotopes les moins lourds:
R =
Généralement,
mol 2 16 11 le16 fractionnement
1 pour les isotopes les plus lourds est pris comme(3.38)
deux fois plus
2 [ H2 [O H
H] O H]
R =
important (3.38)
2 [ 1que
H16 Ocelui
H] considéré pour les isotopes les moins lourds:
( ) ( )
mol 1
2 2
La valeur réaliste de cette définition se réfère, par exemple, à la mesure
14
α
des
13
α
= rapports et 18α = par
isotopiques
17
α
La valeur réaliste de cette définition se réfère, par exemple, à la mesure des rapports isotopiques par
spectrométrie laser(voir
spectrométrie laser (voir ( )
14Sect.10.2.1.2),2
etabundance
ou l’absorption
α = 13ouα l’absorption
Sect.10.2.1.2), 18 and
α = 17permets
lumineuse α ( )
2 fractionation of stable isotopes
lumineuse permets
la comparaison
molécules, différant seulement d’un isotope, contrairement à la spectrométrietandis
de masseque
de deux la comparaison de deux (3.41)
(Kerstel et al.,
molécules, différant seulement d’un isotope, contrairement à la spectrométrie de masse (Kerstel et al.,
1999 ; comm. pers.).
1999 ; comm. pers.).
tandis que
Eq. 3.37
peut être récan betellerewritten as: α = 1 + 14ε = (1 + 13ε ) = 1 + 2 13ε + (13 ε ) 2 ≈ 1 + 2 13ε
14 2
L’équation 3.37 -écrite que:
L’équation 3.37 peut être ré -écrite
[ 2 Htelle
17 1 que:
O H] [ 2 H18 O1H]
( )
2 16 2
2 2[ H O H]
[ 2 H 16 O1α
14 1+ 14
= +1[+2 H13
ε 1H] 16 ε1
+ 2+ 162 13 ε +.......(13 ε ) 2 ≈ 1 + 2 13ε
H] = 1[+2 H16 O O H] = 1 [ H O1H]
donc,
O1H]nous2[(3.39) avons
2 16 pour
H O 2 H]le prélèvement du CO2 par les plantes ainsi que pour l’échange
2
Ratom = 1 16 1 2 17 1 2 18
2 [ H O H] [ 1H17 O1H][ H [ 1H18O O1H]
H] [ 1[H16H O 2 H] so that for.......
the CO2 uptake by plants as well as
1 + 1 + + ++ le .......
CO +
et l’eau, 16respectivement:
[ 2 H 16 O 1 [ H O H] 2 [ H
[ H16 OO1H]
H]le prélèvement [ H2 HO 16 1 2
Oles
H]plantes [ 2 Hainsi
O1que
H] pour l’échange isotopique entre
1 16 1 1 16 1 1 16 1
donc, nous avons pour H]du 2[
CO parH]
2
Ratom = 2 the isotope exchange between CO2 and water, re-
(3.39)
Le premierle (3.39)
CO2à et
facteur [ 1Hrespectivement:
2 dans
l’eau,
droite 16 1
O H] Eq.3.39[ 1est
l’équation H17le O 1
rapport [ 1H18 O
H] isotopique 1
H] [En
moléculaire. 1 16 2
H O H]13
spectively:
bonne
1 +
approximation, les rapports isotopiques moléculaires1 dans +
16 le 1second facteur
1 16peuvent
1
+ 14
être remplacés
1 16 1
ε ε
≈ 2 .......et 18
ε ≈ 2 17ε
The first factor on [
the right Hin O H]
Eq. 3.39 [ H
is O H]
the mo- 2[ H O H]
par les rapports isotopiques atomiques:
14
ε ≈ratio.
2 13ε2 Toeta very 18
ε ≈good
2 17 εapproxima- ε ≈ 2 ε and 18ε ≈ 2 17ε (3.42)
14 13
(3.42)
lecular isotope 17 18 L’approximation qui postule que ces fractionnements diffèrent d’un facteur 2 tire s
Le premier facteur 1 + R + R + R + .......
2à droite dans l’équation2 Eq.3.39 est le rapport isotopique moléculaire. En bonne
tion
2
Ratom ≈the molecular
Rmol 17 isotope= ratios Rmol in the second (3.40) The approximation that these fractionations dif-
approximation, les rapports
1 + R + 18 R + 2 R + ....... relation entre les masses moléculaires comme présentée dans les équations 3.21 e
factor may be isotopiques
L’approximation qui postulebymoléculaires
replaced the atomic
que dans le second
isotope
ces fractionnements facteur
ra-diffèrent
fer by peuvent
d’una factorêtre remplacés
m+2 of 2 originates from the relation
facteur 2 tire son origine de la
par 44 tios:
les rapports isotopiques isotopes les plus lourds, α est une fonction de type (M+2)/M, tandis que m+1α
relation entre lesatomiques:
masses moléculaires comme présentée dans between the molecular
les équations masses
3.21 et 3.23. Pouras les
presented in
m+2 similaire de type
Eqs. (M + 1)/M.
3.21 and m+1For the heaviest isotope m+2α
3.23.
isotopes les plus1lourds,
2 + 17 R + 18 Rα+est 2 une fonction de type (M+2)/M, tandis que
R + ....... 2 is a function
α est une fonction
of (M+2)/M, α is a similar
while isotopiques
m+1
Ratom ≈de2 R
similaire type
mol (M17 + 1)/M.18 2
= RAyant
mol discuté les bases théoriques (3.40)
des effets dans les paragraphes p
1 + R + R + R + ....... function of (M + 1)/M.
pouvons faire une approximation de l’exposant θ dans la relation générale :
Ayant
(3.40) discuté les bases théoriques des effets isotopiques dans les paragraphes précédents, nous
Having discussed the theoretical background of
44 pouvons faire une approximation de l’exposant θ dans la relation générale :
This result means that to a first-order approxima- isotope
m+2 effects
⎛ m+1 in⎞ the preceding
θ m + 2 sections, we are
ln α A / B
RA R
tion the atomic isotope ratio θis equal to a molecu- able to = ⎜⎜ m+1 anA approximation
make ⎟⎟ ou =θ
of the exponent θ
lar isotope mratio.
m+2
in RB ⎝ Rrelation:
the general B ⎠ ln m+1α A / B
+2
R A Although
⎛ m+1 R A ⎞it was shown
ln m+for
2
α A /one
specific molecule, = ⎜⎜ m+reasoning
⎟⎟ ou B
=θ (3.43)
m+2
RB the ⎝
1
R B ⎠
is equally
ln m +1 valid
α A/ B
for the other molecules in Eq. 3.39. Also for ou more
m = 12 pour le carbone, ou 16 pour l’oxygène. Les fractionnements par diffusion
or (3.43) 3.35 et 3.43 im
complicated molecules the demonstration of Pour la diffusion de vapeur d’eau dans l’air, les équations
calculables.
ou m = 12 pour le carbone, ou 16 pour l’oxygène. Les fractionnements par diffusion sont facilement
the proof is analogous.
calculables. Pour la diffusion de vapeur d’eau dans l’air, les équations 3.35 et 3.43 impliquent
The approximations made are indicated as ‘first- where m = 12 for carbon or 16 for oxygen.
order’. However, if we use δ values the approxi- The fractionations by diffusion are easily
45 calcu-
mation is even better, because almost equal ap- lated. For the diffusion of water vapour through
proximations occur in the R values of the nomi- air Eqs.3.35 and 3.43 result in:
nator as well as the denominator of Eq. 3.40 (cf.
Sect. 4.3.1). ln 18α / ln 17α = 1.93
whereas according to Eqs.3.36 and 3.43 for
3.7. Relation between the diffusion of CO2 through air:
fractionations for three
ln 14α / ln 13α = 1.96
isotopic molecules
For some isotope studies, it is of interest to know In terms of fractionation this comes to:
the relation between the fractionations for more
than two isotopic molecules. For instance, wa-
18
ε ≈ 1.93 17ε       and       14ε ≈ 1.96 13ε
ter contains three different isotopic molecules Calculating the exponent θ for fractionation ef-
as far as oxygen is concerned: H216O, H217O and fects in general is quite elaborate. The relatively
H218O; carbon dioxide consists of 12CO2, 13CO2 as simple case for the CO ⇔ O2 isotopic equilib-
well 14CO2. The question now is, whether there rium may serve as an example [23]. The isotope
is a theoretical relation between the 17O and 18O exchange reactions are:
fractionation with respect to 16O (for instance,
during evaporation) and between the 13C and 14C 18
O16O + 12C16O ⇔ 16O2 + 12C18O
fractionation with respect to 12C (for instance,
during the uptake of CO2 by plants). and
Generally the fractionation for the heaviest iso- 17
O16O + 12C16O ⇔ 16O2 + 12C17O
tope is taken twice as large as that for the less
heavy isotope: Inserting the proper mass numbers and the vibra-
α =( α ) α =( α )
2 2
14 13
and 18 17
(3.41) tion frequencies: ν(12C16O) = 6.50 × 1013/s and

ν(16O16O) = 4.74 × 1013/s in Eqs.3.18 and 3.29,
while the α values at 20°C are:

31
 Dans
Dans lele premier
premier cas,
cas, une
une détermination
détermination expérimentale
expérimentale dede lala relation entre 1717OO etet 1818OO
relation entre
Une
Unesérie
séried’échantillons
d’échantillonsd’eau
d’eaunaturelle
naturelleaaété
étéélectrolytiquement
électrolytiquementconvertie
convertieenenoxygèn
oxygèn
. analysé
analysépar
parspectrométrie
spectrométriededemasse.
masse.La
Larelation
relationrésultante
résultanteentre
entreles
lesvaleurs de1717δδetet181
valeursde
. INTRODUCTION
. (Meijer
(MeijeretetLi,
Li,1998)
1998)selon:
selon:

δδδ===(1(1(1
11+++181818 ++17+δδ))δ),(1.8935
8935±±00,±
17 17(1(1,8935 005
, 005))
0.005)
(3.45)
.
. Despite this, in many routine cases, where the ob-
Malgré
Malgré cela,
cela, dans
dans de
de nombreux
nombreux cas
cas de
de routine
routine pour
pour lesquels
lesquels lala précision
précision obtenue
obtenu
and . tainable precision is limited or irrelevant, we may
irréaliste,
irréaliste,nous
nouspouvons
pouvonsquand
quandmême
mêmeutiliser
utiliserlalarelation
relationsuivante:
suivante:
. still use the relation:
lnmm++22αα
ln
αα ==((mm++11αα))
mm++22 22
so that: ==22 etet
and (3.46)
. lnmm++11αα
ln
.
. ou:
ou: or:
.
ε = 2m+1
m+2
ε (3.47)
(h = 6.626 * 10 – 34 Js; k = 1.38 × 10 – 23 J/K). εε ==22 mm++1ε1ε
mm++22

at least with a precision of 10%. In this respect,

Applying the equations
. to poly-atomic molecules
avec,
avec,au we will
auminium,
minium, une continue
uneprécision
précisionde to10%.
de apply
10%.Dansthe factor
Dans cette of 2 innous
cetteoptique,
optique, the re-
nous continuerons
continueronsd’appli
d’appl
can only result in approximate θ values. However, 13
13 1212 14
14 1212
dans
dans
calculations on the exchange equilibria such asles
les lation
relations
relations between
entre
entreles
les the 
rapports
rapports13
C/ C and
isotopiques
isotopiques
12 14
C/
C/ C
12
CCetisotope
et C/
C/ C Cra-
pour
pour les
lesprocessus
processusna
n
CO ⇔ CO2 et CO2 ⇔ CH4 result in: tios for natural processes:
14
14
εε==221313εε
. ε = 2 13ε
14
(3.44)
comme
commeoriginellement
originellementutilisée
utiliséepar
parCraig
Craig(1954).
(1954).La Laprécision
précisionde del’analyse
l’analysedudu1414CCn’e
n’e
.
. pour
pour permettreas originally
permettre une used
une vérificationby [28]. The precision
vérification expérimentale
expérimentale de of a 
de lala relation
14
C
relation dede l’équation
l’équation
rather than in θ = 2 [26]. analysis ismolécules
not sufficient to allow
fractionnements
fractionnements pour
pourles
les molécules contenant
contenant lele1313CCan experimen-
etetlele14
14
C.
C.
In one case an experimental determination of tal verification of the relation of Eq. 3.42 between
D’un
D’unautre
autrecôté,
côté,l’équation
l’équation3.44
3.44doit
doitêtre
êtreappliquée
appliquéesisiles lesfractionnements
fractionnementsimpliqués
impliquésso s
the relation. between 17O and 18O has been pos- the fractionations for 13C and 14C containing mol-
les
lesmesures
sible. A series of natural water samples was mesuressuffisamment
elec- suffisammentprécises.
précises.
ecules.
trolytically converted into oxygen which was
then analysed mass spectrometrically. The result- On the other hand, Eq. 3.44 is to be applied if
ing relation between the  δ and δ values was
17 18 the fractionations involved are large and the mea-
reported as [27]: surements sufficiently accurate.

32
 ABUNDANCE VARIATIONS by NATURAL PROCESSEs

4 4. ABUNDANCE VARIATIONS
VARIATIONS by NATURAL
DES ABONDANCES PROCESSEs
PAR
LES PROCESSUS NATURELS Chapitre 4

In the preceding chapter we have defined isotope For the  specific isotopes mentioned in Eq. 4.1

4 (abundance) ratios in various chemical

VARIATIONS DES ABONDANCES PAR
pounds. Furthermore, we have presented a theo-
Pour les isotopes
Chapitre com-
indiquées
4
par les
bols:
spécifiques
the respective
symboles:
mentionnés
δ values dans l’équation
are indicated 4.1, les valeurs respec
by the sym-

retical treatment of the physical phenomenon

Dans le chapitre
LES PROCESSUS NATURELS
Pour les isotopes spécifiques mentionnés dans l’équation 4.1,
of isotopeprécédent,fractionation.
nous avons In défini
this chapter we will
les rapports
2
(abondances)
( 2 H/ 1H) A respectives
δ =les 2 valeurs
isotopiques
1
− 1 dans 13
δdes
13 12
de( δC/sont C)
= 13 12 A − 1 18δ = 18 16 A − 1
(18 O/ 16 O)
indiquées par les symboles: ( H/ H) ( C/ C) r ( O/ O) r
discuss très
composés chimiques the background
variés. Nous avons of variousensuiteprocesses
présenté un oc-traitement théorique rdu phénomène
curring in
physique de fractionnement nature,
2
H/ 1H)
(isotopique. thatA may
Dans ce cause
13 chapitre,
variations
(13 12
C/ nous inquediscuter
C) Aallons
sachant les
18 symboles
18
(les O/ 16
bases O)plus
les des souvent utilisés sont δ2H ou δD, δ13C, et δ18O, respec
A nombreux
the isotope
2
δ =
ratios. − 1 δ = − 1 δ = − 1 (4.2b) (4.2b)
processus qui se produisent ( 2 H/ dans1
H) rla nature, pouvant (13 C/ 12Toutefois,
C) r desdans
induire variations 18
ce (volume,
O/dans16
O) nous
r
les rapports

écrirons les nombres de masse représentant l’isotop
isotopiques. The equations that will be derived can be ex-
Dans le sachant
chapitreque précédent,
les symboles nouslesavons défini utilisés
plus souvent par un
les rapports
sont δ2H exposantwhere
(abondances)
ou δD, δavant
13
etleδδ18, O,
C,the more
isotopiques comme often pourused
dans
respectivement. le symbole
des symbols R etare
le symbole
δ2H or isotopique lui-mê
Les équations pressed
qui practically
en sont without
dérivées approximation
peuvent être in iso-
exprimées pratiquement, et sans aucune
composés chimiques très variés. Nous avons ensuite présenté une simplification
un traitementδD, δthéorique
deC,
13 cesand δdu O,
symboles 18
respectively.
et libérant de l’espace pour d’autres exposants ou i
phénomène
tope ratios
Toutefois, dans (R values) as
ceisotopiques
volume, nouswell as in les
écrirons a more
nombres or less desous
masse représentant l’isotope rare concerné
approximation, en
physique de fractionnementrapports isotopique. (valeurs R) aussi bien que, une forme plus approximative,
approximated
parδ.un exposant avant format in δDans
le δ, comme values.ce chapitre, nous allons discuter
pour le symbole CommeR et leles However,
valeurs
symbole
les bases
de δ in
isotopique dans thisdesvolume
nombreux
la nature sont
lui-même, wepetites,
faisant will
ainsiwrite
elles the mass
sont généralement données3
en notation
processus qui se produisent dans la nature, pouvant induire des number variationsindicatingdans les the rare rapports isotope concerned by
−3
une simplification de ces symboles et libérant de l’espace définiespour — en ‰ (pour
d’autres mille ≡ ou
exposants parties
indices. par millier ≡ 10 ). Nous devons insister sur l
isotopiques. a superscript−3 before the δ, as with the R sym-
4.1. lesUse ofde δDESvalues andδsont isotope équivalent à bols un facteur 10 et que ce
and the isotope n’est pas
symbol une unité, même si c’est ce qui est
itself,
4.1 Comme
Les équations
UTILISATION
qui valeurs
en sont
VALEURS
δdérivées
dans la nature
peuvent
ET DES
petites,
être
REFERENCES
elles sont
exprimées
ISOTOPIQUES
généralement
pratiquement, données3
et sans – bien que
aucune non thus making
references suggéré. valeur δ est simplement
Unethe symbols simpler and un nombre
leavingpetit spaceet sans dimension. De façon sim
for other
définies
approximation,
Les rapports en— en ‰
rapports
isotopiques que mille ≡(valeurs
tels(pour
isotopiques parties R) paraussi
millier
bien 10−3).sous
≡ que, Nousune devons
forme insister
plus sur le fait que ‰
approximative, 3 est
dans la Part.3.3, super- il est and subscripts.
incorrect d’utiliser δ/10 à la place de δ dans les équations ma
en notation δ.Isotopeà ratios
équivalent un facteur such10 as−3 et que ce n’est pas une unité, même si c’est ce qui est le plus souvent
façon à éviter d’oublier que δ est uninpetit nombre, il est possible
suggéré. Une2 valeur δ est13 simplement un 18nombre petit et sans dimension. As the values De façon of δsimilaire nature à ε are small,
défini they arede choisir d’écrire da
H C O δ(en ‰)10given −3
δ, peu pratique
2
R= 1 13
R = 12 18
R = 16 3
mathématiques:
(4.1) generally à la -although
place
(4.1) d’un simple not defined- in ‰ tel qu’il est.
4.1 dansUTILISATION
la Part.3.3,
H il estDES incorrect
C
VALEURS d’utiliser δ ETOδ/10 la place de δ dansISOTOPIQUES
DESà REFERENCES les équations mathématiques. De  – 3
(per mill ≡ parts per thousand ≡ 10 ). We have
façon à éviter d’oublier que δ est un petit nombre,Les il estvaleurs de δdenégatives
possible choisir d’écrire indiquent des abondances
équations toplus faibles en isotope rare dans
are generally
Les rapports isotopiques tels not
que reported as absolute numbers. to emphasise that dans‰ isles equivalent the factor
mathématiques:
ne sont généralement (en ‰)10−3comme
pasδconsidérés à la place desd’un
nombres queδ, dans
simpleabsolus. le matériel
peu pratique
Les tel and
10 – 3
principales de référence,
qu’il is not a unit
est.
raisons enetsont
desasvaleurs
is often
les δ positives des
desuggested. A δteneurs plus importa
The main reasons are:
suivantes: value is merely a small, dimensionless number.
Les (1)
valeurs 2 de δ négatives
H 13 indiquent des
C spectrometers, 18 abondances
O suitable En comparant
plus faiblesles en définitions
isotope rarededans ε (Eq.3.5) et δ, la seule différence est que, tandis q
les échantillons
2 the type
R = 1 de masse, 13of mass
R = 12 utilisables 18
R =pour for Similarly to ε defined (4.1) in Sect. 3.3, it is incor-
1) les spectromètres
que dans measuring
le Hmatériel deisotope référence,
C et des valeurs
abundances
16 mesurer
O with les
δ positives
decomme abondances
highle rapport
des teneurs
rect isotopiques
isotopique
to use plusδ/10 d’un avec
importantes. une
3 composé (ici B) relativement à un autre composé (A
instead of δ in mathematical
sensibilité suffisamment importante pour
sensitivity in order to detect very small pouvoir détecter
tant des
que variations
rapport naturelles
isotopique
equations. In order très
d’un faibles,
composéto ne avoid(maintenant A) relativement à un matér
the negligence
En comparant les définitions de ε (Eq.3.5) et δ, la seule différence est que, tandis que ε a été défini
permettent
ne sont généralementabsolument
natural pas d’obtenir
variations,
pas considérés aredesbasically
comme rapports
des nombres isotopiques
suitablefiables
standard
not absolus. (voir
to
(r). principales
Les Part.11.2);
realise that δenissont
raisons a smallles number, one may
comme le rapport isotopique d’un composé (ici B) relativement àchoose un autreto composé
write (A),
in δmathematical
est défini en equations:
suivantes:
2) la nécessité forcomparaisons
obtaining reliable absolute ratios (see
tant que de rapport isotopique
Sect. 11.2);
internationales
d’un composé implique Bien
(maintenant l’utilisation
que A)dans de
les références
relativementéquations
δ  (in ‰)10 à un auxquelles
 – 3tirées de cede
matériel
instead
lesréférence
chapitre,
of merely
le format δ, puisse être appliqué à p
δ, impractical
échantillons
1) les spectromètres doivent être rapportés;
standard (r). de masse, utilisables pour mesurer les lesprocessus
abondancesnaturels avec
isotopiques une précision
avec une accessible par l’instrumentation analytiq
though it is.
sensibilité (2) suffisamment
the necessity importante of pourinternational
pouvoir compari-
capacité
détecter des de calcul
variations des
naturelles petits très calculateurs
faibles, ne de poche utilisés sur le terrain a géné
3) l’utilisation des rapports isotopiques conduirait à reporter des résultats avec un grand nombre de
Bien que son dansrequires
les équations the usetiréesofdereferences
ce chapitre,tole which format δ, puisseNegative être appliqué
δ values à indicate
pratiquement lowertousabundances of
permettent
chiffres après absolument
la virgulepas (5 ou d’obtenir
6); des rapports isotopiques superflue fiables (voir Part.11.2); Les valeurs de δ déterminées par les laboratoires isot
les approximations.
les processus naturels have
the samples avec to unebe précision
related; accessible the rare isotope
par l’instrumentation in these samples
analytique moderne,than
alors être transformées en valeurs R en appliquant (réécriture de l’équation 4.2):
la in the refer-
2) la nécessité de
capacité absolus
4) les rapports comparaisons
de calcul sont,desenpetits internationales
calculateurs
principe, implique
moins utiles de poche l’utilisation
(et moins utilisés ence
de
sur le
utilisés) material,
références
queterrain positive
auxquelles
a généralement
les variations δlesvalues
de ces rendue point to higher
échantillons
(3) the use
doivent
of
êtreles
isotope
rapportés;
ratios would lead to report- abundances.
R = Rr(1 + δ)
même rapports
superflue pendant
les approximations. transitions Lesentre
valeursphasesde δoudéterminées
entre molécules.
ing results as numbers consisting of a large par les laboratoires isotopiques peuvent
3) alorsabondance
Ainsi,l’utilisation
une êtredestransformées
rapports
number oren6)valeurs
(5 isotopiques
isotopique of R en appliquant
conduirait
estdigits;
généralement à reporter(réécriture
ou
reportée les deComparing
desvaleurs l’équation
résultats
comme Rune
r avec un the 
les4.2):
sontdéviation rapports
grand definitions
nombre
du rapport de of εdes
isotopiques (Eq. 3.5)
matériaux anddeδ,référence internatio
définis the only difference is that, whereas ε was defined
chiffresd’un
isotopique après la virgule
(4) échantillon.
R = Rr(1
absolute
(5Une
+ou
ratios δ)6);
définition
are in principle relativeless rapport plus
par relevant à unloin dans le Chapitre
échantillon de référence 7. Enou(4.3)se référant à la relation entre le rapport
as the isotope ratio
concentration isotopique (Part. 3.1), cette concentration of a compound (then B)isotopique,
rel- C, peut
standard, r:
4) les rapports than the changes
absolus in ratios occurring (et during
ou les valeurs Rrsont,
sont en lesprincipe,
rapports moins
isotopiquesutiles des moins
matériaux utilisés)
ative que les variations
to another
de référence compound
internationaux de cesqui(A ), seront δ is defined as
transitions transformée en δ par insertion de l’équation 3.3b:
même rapports
définis plus pendant
loin dans lesbetween
transitions
le Chapitrephases
entre
7. Enor molecules.
phases ou entre àmolécules.
se référant the isotope
la relation entre leratio rapport of a compound
isotopique et(now la A ) relative
RA to the standardised reference material
δ A/r = −isotopique
1an isotope R 1 C être (r).
3
Ainsi, une Therefore,
concentration
abondance isotopique (× 10 est‰)abundance
(Part. 3.1), cetteis concentration
généralement generally
reportée comme isotopique,
δ =une −déviation1 =C, peut du(4.2a)
maintenant
rapport
− 1
Rr Rr
isotopique reported
transformée
d’un enas
échantillon.δ para deviation
insertion
Une définition deof the isotope
l’équation
relative3.3b: rapportof à unAlthough
par ratio échantillon in R de r 1 −C
the equations
référence ou to be derived in this
standard, r: a sample A relative to that of a reference sample chapter the δ format can be applied to practically 13
R 1 C Exemples: leallcarbone natural naturel
processes contient
to environ 1%attainable
49
the precision d’atomes by de C; le carbone,
or standard, δ = r: − 1 = −1 (4.4)
13
Rr Rr 1 − C concentrationthe modern
élevée, et bien sur absurde,
analytical en C de 99% the calcu-
instrumentation, atomes a donc une valeur δ (
RA
δ A/r = −1 (× 10 ‰)3
(4.2a)
= 0,0112372,lation capacity
Sect.137.1.3) de 8809 of (4.2a)
small
× 10 ‰. 3
pocket calculators used
Exemples: Rle r carbone naturel contient environ 1% d’atomesin de the  C; field le generally
carbone, enhas prenant
come une to make the  ap-
concentration élevée, et bien sur absurde, en 13C de 99% atomes a donc une valeur δ (vs PDB-CO2: Rr
= 0,0112372, Sect. 7.1.3) de 8809 × 103‰. 50 49
33

50
 que dans le matériel de référence, et des valeurs de δ positives des teneurs plus importantes.
de façon similaire
En comparant les définitions à l’équation
de ε (Eq.3.5) et δ, la 3.6
seulepour ε. Les valeurs
différence R et α
est que,detandis quesont
ε amultiplicatives,
été défini tandis que les
valeurs de
comme le rapport isotopique δ et
d’un ε peuvent
composé seulement
(ici B) et approximativement
relativement à un autre composé s’additionner.
(A), δ est définiEn
en d’autres termes, le
fractionnement
tant que rapport isotopique ε, tel que
d’un composé défini parA) l’équation
(maintenant 3.5,à un
relativement
INTRODUCTION est matériel
presque de
équivalent
référenceà la différence de
standard (r). composition isotopique entre deux phases:

Bien que dansproximations

les équations tirées de ce chapitre,
superfluous. δ Rformat
The  le values δ,R puisse
deliv-
B / Rr
être appliqué
1 + δ B / r à pratiquement tous
les processusered by isotope ε = α
laboratories − 1 = B
can easily − 1 = − 1 = −1 ≈ δ B / r − δ A/ r (4.8) (4.8)
naturels avec une précision accessible R A parbel’instrumentation
Rtrans- 1 + δanalytique moderne, la
B / A B / A
A / Rr A/ r
formed into R values by applying (rewritten from
capacité de calcul des petits calculateurs de poche utilisés sur le terrain a généralement rendue
superflue lesEq. 4.2):
approximations. Les valeurs
Pour la réaction A→B, de εB/Aδcorrespond
déterminéesaupar For the reaction
les laboratoires
changement
A→B,
isotopiques
de composition
εB/A is the change in iso-
peuvent
isotopique (égal au "nouveau"
topic composition (equal the ‘new’ δ minus
alors être transformées en valeurs R en appliquant (réécriture
δ moins l’ "ancien" δ; cf. Part. 3.3). de l’équation 4.2):
R = Rr(1 + δ) (4.3) the ‘old’ (cf. Sect. 3.3).
R = Rr(1
where Du δ) quevalues
+ fait
the R des conventions strictes gouvernent
are the isotope ratios of l’utilisation
Becausedesstrict (4.3)nous allons généralement
références,
conventions govern the use of
r
the international
supprimer reference
l’indice r et materials
désigner to be
l’échantillon de-
par
ou les valeurs Rr sont les rapports isotopiques des matériaux de référence un references,
indice δ ou δwe will
(A)
internationaux
A à quigenerally
la seront A / rdrop
place de δ the subscript
et δr(A).
fined later
définis plus loin dans in Chapter
le Chapitre 7. Referring
7. En se référant to the relation
à laderelation r
entre and designate the sample
le rapportapprochée
isotopique by a subscript δA or
betweenLa possibilité
isotope ratiod’additionner les valeurs
and isotope δ et ε est
concentration couramment par:et la
δ(A ) instead
concentration isotopique (Part. 3.1), cette concentration isotopique, C, peut maintenant être
of δ A / r and δr(A ).
(Sect. 3.1), the isotope concentration, C, can now
deδl’équation The additivity of δ and ε values is commonly ap-
beδtransformed
transformée en par insertion into δ δby
B≈ εB/A
3.3b: Eq. 3.3b:
A +inserting (4.9)
proximated by:
R 1 C
δ= Ceci− 1 =signifie que,− si 1 un CO2 de l’air avec une (4.4) valeur en 13δ de −8‰ est assimilé (4.4) par les plantes avec un
Rr Rr 1 − C δB ≈ δA +13 εB/A (4.9)
fractionnement isotopique en carbone de −17‰, la valeur de δ du carbone organique sera de −25‰.
de 13C;This means that if air-CO une2 with a  δ value of
13
Exemples: leExamples: carbone naturel natural carbon
contient contains
environ
Variations 1%about
d’abondances d’atomes 1 atom isotopiques le carbone, en prenant
concentration%élevée, of 13C; carbon sur with an en
Variations
Variations absurdly
d’abondances
13
d’abondances highatomes13
C con-
isotopiques
isotopiques a donc −8‰ is assimilated
δ (vs PDB-CO by plants with a carbon iso-
et bien absurde, C de 99% une valeur 2 : Rr
centration of 99 atom % thus has a δ value (vs tope fractionation of −17‰, the 13δ value of
= 0,0112372, Sect. 7.1.3) de 8809 ×Variations 103‰. d’abondances isotopiques
Si les valeursPDB-CO δ doivent2: êtreRrdonnées  = 0.0112372, Variationspar rapport
d’abondances à uneisotopiques
Sect. 7.1.3) référence the plant carbon
of secondaire, r', plutôt is −25‰.
que par rapport à 51
Si
Si les
les valeurs δδ doivent
valeurs8809 × 10 doivent être être données
données par rapport
par rapport àà une
une référence
référence secondaire, secondaire, r', r', plutôt
plutôt que que par par rapport
rapport àà
3
‰.
la référence primaire r, une équation de conversion est alors nécessaire.
la
Si référence
la les valeursprimaire
référence δ doivent
primaire r,
r, une être équation
une données de
équation parconversion
de rapport à une
conversion est alors
alors nécessaire.
est référence secondaire, r', plutôt que par rapport à
nécessaire.
If δ values are to be given relative to a secondary 4.2. r',Tracer concentration, Chapitre 4
A50
Sipartir
la
A
les valeurs
des
référence
partir des
δ doivent
rapports
primaire
rapports r, être équation
isotopiques:
une
isotopiques:
données de parconversion
rapport à une est référence
alors secondaire,
nécessaire. plutôt que par rapport à
A partir des rapports
reference, isotopiques:
r', rather than to the primary reference amount of tracer
la référence primaire r, une équation de conversion est alors nécessaire.
r, a conversion
A partir des rapports isotopiques: equation is needed. 4.2 CONCENTRATION
RAAA R
R Risotopiques:
/Rrr r Natural isotopes canETbeTAUX used DE as TRACEUR
tracers to fol-
A partir des rapportsR R A/R
/R Chapitre 4
==the isotope ratios:
= (4.5)
A
From A
low elements of (4.5)
the water
(4.5) cycle in their natural
R
Rr'r'Ar' = R RRr'r'Ar'/R/R Les isotopes naturels peuvent être utilisés comme traceurs pour suivre les élément
rr r
course. For instance, (4.5) the abundance
l’eau au cours18de leur trajet naturel. Par exemple, l’abondance de 2H et 18O dans les pr
of 2
H and
4.2 R Rr'A R RCONCENTRATION
A /R/R ET TAUX DE TRACEUR
= rr O in precipitation can
(4.5) be applied to unravelling
être(4.5)
r'
Rr' Rr' /Rr appliquée pour séparer les différents composants de l’hydrogramme de crue. C
ouou
ou the various components of the runoff hydrograph.
Les isotopes naturels peuvent être utilisés commepermet traceurs alorspourde suivre les
calculer élémentsdeconstitutifs
la quantité deles différents compartiments du bi
ou This application comestraceur dans
to calculating the amount
or
l’eau au cours de1 1 +
+leur
δ AAtrajet naturel. Par exemple, l’abondance bien local que
2
de régional. 18
H et O dans les précipitations peut
ou δ A / r les différents composants de l’hydrogramme de crue. Cette application
1 + séparer of tracer in the different compartments of the lo-
++ δδAA // rr '' =
+
11appliquée // rr
être 1 ==pour
1 + δ cal or regional water budget.
la Part.3.1, nous avons défini, par exemple, la concentration isotopique de l’18
δ AA/ /r r' de +δ rrδA''// rrr '/lar quantité de traceur dansDans
'
111+
permet 1 +alors = calculer les différents compartiments du bilan en eau, aussi
+ δ Aque + rA'// rr que: In Sect. 3.1 we have defined the isotope concen-
bien
1local / r ' =régional.
Et
Et donc,
donc, 1 + δ r '/ r tration of, for instance, 18O in water as:
EtEtdonc,
donc, Dansfollows la Part.3.1, nous avons défini, par exemple, la concentration isotopique quantité de l’18 deOHdans
18 l’eau tel 18 18
δ AA // rr − δ rr ''// rr 18 2 O H2 O R (H 2 O)
Et donc, que: δ = − [H O] = (4.6) = = ≈ 18
= 2
quantité (4.6)
d'eau 16
H 2 O+ H 2 O
18
1 + 18
R (H O)
δδ1 + −δ−δ δ
A /
A/ r'r '

δ AA//rr' ' == 1A A/+r/ r rr ''// rr '/ rr '/ r

2
(4.6) (4.6) (4.6)
δ −δ
δ A / r ' = 1A1/+r 18+δ δr '/ rr ''// rr quantité de H 2 O
18
H2 O
18 18
R (H 2 O) (4.6)
18
Cette équation est
Cette équation est également [H
également O] =
1 +2 δ r '/ rutile pour faire la conversion16entre deux
utile pour faire la conversion = et dans
entre la
deux =
18 phases δ:
notation
phases ou
18 entre
ou entre deux deux R (H 2 O) (4.10)
≈ composés
composés (4.10)
This equation is also quantité
useful d'eaufor H 2 O+ be-
converting H2 O 1 + R (H 2 O)
A
A et
Cetteet B:
Cette B:équation est
équation est également
également utile pour faire la conversion entre entre deux phases ou entreoudeux composés
tween two phasesutile pour
or compounds faire la conversion
A and B: deux18 phases 18 18
entre deux 18
composés18 18
Cette
A et B:équation est également utile pour faire la conversion entre deux phases [H
and O]
2 inou = R {
entrernotation:
the δ R(H 2O) / Rr} = Rr {1 + δ}
deux composés
A et B: et dans la notation − δ B/A δ:
A et B: δ A/BA/B =
= − B/A ≈
≈− −δ B/A (4.7) (4.7)
18 (4.7)
11−++ δδB/A B/A
Maintenant, l’isotope [H218O] = rare 18
Ren r {tantR(H que2O) tel/ 18
neRpeut,
r} = seul,
18
Rr {1servir
+ 18δ}de traceur. Ceci appar
δ A/B = [H − δ18
B/A
B/A ≈ − 18δ 18 18
B/A{ R(H O) / R } = R {1 + δ} 18 18
(4.11) (4.7)
δδ A/B
A/B = =1−to +δδ2 B/A O]
B/A ≈ ≈
B/A =
−δ−B/A
R δr B/A 2 r nous
r analysons le cas d’un hydrogramme de
(4.7)
(4.11)
(4.7)crue. Si, pendant un épisode pluvieux, l
similar 1 + the Eq. 3.6
δ for ε. Values of R and α are
de
de façon
façon similaire
similaire + δ B/A
àà1l’équation
l’équation 3.6
3.6 pour pourδεε..and Les
Les εvaleurs
valeurs de se R et α
α sont
R produisent multiplicatives,
avec the rare
une valeur 18
tandis que
δ égale les
à cellecandunotflux de base (= eaux souterraines
valuesdeare etonly sont Now
multiplicatives, tandis que les
B/A
multiplicative, whereas isotope as such simply serve
valeurs Maintenant,
de δ et ε l’isotopeseulement
peuvent rare en tantε
et que tel ne peut,
approximativement seul,
changement α servir
s’additionner.de
dans traceur.
le En Ceci tandis
ruissellement,
d’autres apparaît et
termes, clairement
donc le nous sine sommes pas en mesure de rec
de façon similaire
valeurs de δapproximately à l’équation
et ε peuvent seulement 3.6
additive. In pour . Les valeurs
other words, the frac-
et approximativement de R et sont
s’additionner.as the tracer.
multiplicatives,En d’autres Thistermes,
becomes
que le clear if we consider
les
dede façon nous
similaireanalysons à le cas
l’équation d’un 3.6 hydrogramme
pour ε . Les de3.5,crue.
valeurs Si,de pendant
R et α un épisode
sont pluvieux,
multiplicatives, les précipitations
tandis
façon similaire
fractionnement
valeurs de δ tionation
et ε ε, à tel l’équation
peuvent ε,
que as defined
défini
seulement 3.6 pour
par by ε . Les
Eq. 3.5,
l’équation
et
fractionnement ε, tel que défini par 18l’équation 3.5, est presque équivalent à la différence de valeurs
is
approximativement almostde
est R
apportéeet
equal
presqueα sont
par the case
multiplicatives,
les
équivalent
s’additionner. En of
précipitations à the runoff
la
d’autres tandis
dans
différence que
le
termes, le que les
hydrograph
les
ruissellement
de analysis.
total. LesIfpluies
dur- ne peuvent être «
valeurs de
valeurs
compositionse produisent
toet etthe difference
de δisotopique
fractionnement
composition isotopique εε,ε tel peuvent avec
peuvent entre
que
une
entredéfini seulement
deux
deux
valeur
in isotopic
seulement par et
phases:
phases:
δ égale
composition à
approximativement
et
l’équation
celle
approximativement
3.5, est
du flux
between
il est de
possiblebase
s’additionner.
presque ing (=
de eaux
a storm
les
s’additionner.
équivalent
souterraines),
distinguer
En àd’autres rain would il
isotopiquement
termes, de
laEndifférence
d’autres n’y
fall le a
withaucun
du
termes, le a  18
fluxδ value
de base.equal
Ainsi, la concentration
changement
twoε,phases: dans le ruissellement, et donc nous ne
êtrepresquesommes
définie to
pas thaten
commeéquivalent of
mesurethe 
la déviation base
de flow
reconnaître ( = groundwater),
la part there
fractionnement
composition isotopique
fractionnement ε, tel tel que quedéfini
entre deuxdéfini parpar
phases: l’équation
l’équation 3.5, 3.5,est est équivalent
presquewould be
à la différence
no isotopic àdelala change
concentration
de
différence in deen isotope rare à partir d’un nivea
the runoff and so
apportée
composition isotopique
isotopique par les précipitations R
RBB phases: dans
R le
/ R ruissellement
RBB / Rrr − 1 = 1 + qui 1 + δ total.
B // rr est,
Lesdanspluiesnotre ne peuvent être
cas, la teneur(4.8) « tracées
18 » que si
en δ du flux de base (= moyenne des eaux s
composition ε BB // AA = = α BB //entre −
entre 1 deux
= deux − 1 =
phases: B
− 1 ≈ δ
≈ BB //we − δ
rr − would not be able
il est possible deAA les − 1distinguer
=
R
−1 =
RBAA − 1 =isotopiquement
R
RBAA // R
− 1 = du flux −
Rrr − 1 = 1 1+ + δconcentrationde1base. Ainsi, A //la
A
du traceur
rr
concentration
est alors définie
(4.8)entotraceur
recognise the precipita-
comme:doit
ε = α − 1 = A // rr − 1 ≈ δ tion
A
B
− δ in the runoff. The precipitation
(4.8) can only be
être définie comme la déviation R de
R la// R concentration 11 ++ δδ BAen isotopeBrare à Apartir d’un niveau de base donné,
B/ A B/ A /r /r
ε B / A = α B / A − 1 = RBAR−B 1 = RBA R R rr
/ R
− 1 = 1 +
// rr
δ
− 1 ≈ δ − δ (4.8)
Pour
Pour la qui est,
la réaction
réaction ε B / A→B,A = α Bε
dans notre
A→B, ε/B/AA − 1 =R Ala teneur
cas,
correspond
correspond − au
au enB 18δ rdu−11
1R=changement
A / Rr
changement de
de+=δcomposition
flux de base
composition
A/ r
B / r (=
−B1[H 2δ O]
/ r 18 A / r
≈moyenne
isotopique
isotopique B / r −−[H δ(égal
des 18 eaux souterraines).
2A / rObase
(égal au = 18Rr {18(4.8)
au ]"nouveau"
"nouveau" δ − 18δLa base}
concentration
34 A→B, δδ;; cf.du
B/A
traceur estR alors R
définie / R
comme: 1 + δ
δδ moins
Pour
moins l’
l’ "ancien"
la réaction
"ancien" cf.εB/A Part.
Part. 3.3).
correspond
3.3). A A r A / r
au changement de composition isotopique (égal au "nouveau"
Pour
δ moinsla réaction
l’ "ancien" A→B, δ; cf.18B/Aε correspond
Part.strictes 3.3). gouvernent au changement de Ici nous avons
composition inséré 18R(égal
isotopique r en tant que valeur 18R de la référence internationale (i.e. no
au "nouveau"
Du fait
Du fait que des
que des conventionsconventions strictes l’utilisation des références, nous allons généralement
Pour
δ moinsla réaction
l’ "ancien" A→B, δ;[H cf.2 εPart.
O] [H2 Ogouvernent
B/A −correspond
3.3).
18
base] =au R
18 l’utilisation de
18
r { δ − δbase
changement
18 descomposition
qui} sera
références, nous
introduite dans
allons généralement
isotopique
le chapitre (égal (4.12)
7). au "nouveau"
supprimer
Du fait quel’indice
supprimer des conventions
l’indice rr etet désigner
désigner strictes l’échantillon
gouvernent
l’échantillon par
par un indice δδAA des
indice
l’utilisation
un ou δδréférences,
ou (A)
(A) àà lala place
place nous de δδAA // rr et
de allons δδrr(A).
etgénéralement
(A).
δ moins l’ "ancien" δ; cf. Part. 3.3). Si la comparaison entre le taux de ruissellement et la hauteur de précipitations, com
 18 quantité de H 2 O H O R (H 2 O) 18
[H 2 O] = = 16 2 18
= 18
≈ R (H 2 O) (4.10)
quantité d'eau H 2 O+ H 2 O 1 + R (H 2 O)

et dans la notation δ:
ABUNDANCE VARIATIONS by NATURAL PROCESSEs

[H218O] = 18Rr {18R(H2O) / 18Rr} = 18Rr {1 + 18δ} (4.11)

‘traced’ if it can be distinguished isotopically 4.3. Mixing of reservoirs
from the 
Maintenant, l’isotope base
rare flow.queTherefore,
en tant tel ne peut,the  tracer
seul, de traceur. Ceciwith
servir con- different
apparaît clairement si isotopic
centration
nous analysons hashydrogramme
le cas d’un to be defined as the 
de crue. Si,deviation composition
pendant unofépisode pluvieux, les précipitations
se produisentthe rare
avec uneisotope
valeur concentration
18
δ égale à cellefrom a certain
du flux base
de base (= eaux souterraines), il n’y a aucun
4.3.1. Mixing of reservoirs of
changement danslevel,leinruissellement,
our case the  18
δ value
et donc nousofnethe  base flow
sommes pas en mesure dethe same
reconnaître lacompound
part
( = average groundwater). The concentration of
apportée par les précipitations dans le ruissellement total. Les pluies ne peuvent être « tracées » que si
il est possiblethe tracer defined as: du flux de base. Ainsi, laIfconcentration
is thenisotopiquement
de les distinguer
two (or more) quantities of a certain compound
en traceur doit
with different δ values are being mixed (for in-
être définie comme la déviation de la concentration en isotope rare à partir d’un niveau de base donné,
[H218O] − [H218Obase] = 1818Rr {18δ − 18δbase} (4.12) Fig.4.1 Représentation 2 in the air of
stance, the COschématique de two
(A):different origins,
le mélange de deux quantités d’un
qui est, dans notre cas, la teneur en δ du flux de base (= moyenne des
suchdeuxeaux souterraines).
as marine La
and biospheric), the δ value of le mélange et la
avec compositions isotopiques différentes, et (B):
concentrationHere
du traceur
we haveest alors définie 18
inserted Rr as the 18R value of composés
comme: the mixture can be ou
différents calculated from a mass
deux phases du même bal-composé avec de
the international reference (i.e. standard, to be in- isotopiques ance equation (Fig. 4.1A).
différentes qui seront sujet à des échanges isotopiques et
18 18
[H 2 O] − [H
troduced
18
Obase] = 7).
in2Chapter Rr {18δ − 18δbase} (4.12)
N1 molecules
dernier offacteur
ressort un a certain compound with
de fractionnement (α).an iso-
If a comparison is required of, as in our present tope ratio R1 contain N1/(1 + R1) molecules of
Ici nous avons inséré 18Rr en tant que valeur 18R de la référence internationale (i.e. notion de standard,
case, the amount of runoff and the amount of pre- the abundant, R1N1/(1 + R1) molecules of the rare
qui sera introduite dans le chapitre 7). N1 molécules isotopic species
d’un composé donné (cf.avec Eq. 
un3.3).If
rapportthis quantity
isotopique is
R1 contiennent N1/(1 +
cipitation, we have to introduce the amount of
tracer, defined as:
Si la comparaison entre le taux de ruissellement et la l’isotope
hauteur de mixed
abondant, with
et
précipitations, R Nanother
comme
1 1 /(1 +
dansR 1 )quantity
lemolécules
cas N 2de(with isotopic
l’espèce isotopique rare (cf. E
quantité
présent, est nécessaire, nous devons introduire le taux de traceur, composition
est mélangée
défini tel que: avec une R ), a simple mass balance gives
2 autre quantité N2 du même composé (avec une compo
18
Rr {18δ − 18δbase} W = 18Rr ∆18δ W ), un simplethe isotope
R2(4.13) ratiodonne
bilan de masse of the mixture:
alors le rapport isotopique du mélange tel que:
18 18 18 18 18
Rr { δ − δbase} × W = Rr × Δ δ × W (4.13)
where W denotes the amount of water. RN RN R N
= 1 1 + 2 2 or RN ≈ R1 N1 + R2 N 2
Comparing specifically the  amount of runoff Q 1 + R 1 + R1 1 + R2
ou W correspond à la quantité d’eau. En comparant spécifiquement la quantité de ruissellement Q et la
and the amount of precipitation, P now comes to (4.15)
hauteur de précipitations, P permet alors de calculer le rapport:
avec N = N1 + N2. L’approximation est valable pour R ≈ R1 ≈ R2 (notons que les vale
calculating the ratio:
négligées parwhere N=N
comparaison N2. The approximation is valid
1 + l’unité).
avec
∑i (Δ δ Q × Q )i
18

En remplaçant
for R ≈ R1 ≈ R2 (note that the R values have not
les valeurs de Rinpar Rr (1 + δ) ettoen1).
indiquant les contributions fraction
(4.14) been neglected comparison
(4.14)
∑j (Δ δ P × P ) j
18
par f1 (= N1/N) et f2 (= N2/N), ou f1 + f2 = 1, la valeur de δ du mélange est:
Replacing the R values by Rr (1 + δ) and denot-

ing the fractional contributions to the mixture by
for a number of time periods i and j, respectively f1 (= N1/N) and f2 (= N2/N), where 1 + f2 = 1, the δ
52 (i may equal j, depending on the question). value of the mixture is:

Fig. 4.1.  Schematic representation of (A): the mixing of two quantities of one compound with different isotopic
compositions, and (B): the mixing and reaction of two different compounds or two phases of the same compound
with different isotopic composition that will be subjected to isotope exchange and will ultimately become a frac-
tionation factor (a) apart.

35
 INTRODUCTION

2 Noraor + Nadaad = (Nor + Nad)amix (4.18a)

seawater
0 and
δ (‰)

-2
NorCor + NadCad = (NVariations
or + Nad)Cd’abondances
mix (4.18b) isotopiques
18

-4
where the subscripts or, add’abondances
Variations and mix isotopiques
refer to
-6
river water
the original
et material, the added material and
the mixture, respectively. N is the respective
-8 et N orCor + NadCad = (Nor + Nad)Cmix
quantity, C the concentration, A the amount of
0 5 10 15 20
Cl (g/L) où les radioactivity
N
indices, C
or,
or or +
ad N
et
ad Cadand
mix a the specific
or + Nad)C
=se(Nréfèrent activity.auHere
respectivement
mix we d’origine, au mat
matériel
Fig. 4.2.  Linear relation between the Chlorinity briefly
N estor, mention a few examples.
mélange.
où les indices, la ad
quantité se réfèrent Crespectivement
et mixrespective, la concentration, A le taux
au matériel de radioactivit
d’origine, au mat
(Cl concentration) and 18δ of water in the  estuary of
spécifique.
mélange. NNous
est laallons
Example mentionner ici quelques
1. Determination
quantité respective, ofexemples.
an unknown
C la concentration, A le taux de radioactivit
the Western Scheldt, where water from the Belgian riv-
er Scheldt (Cl = 0‰ ( = g/kg); δ = –6.5‰)Exemple
18
. 1. Détermination de la quantité d’un produitinac-
spécifique. Nous allons quantity/concentration
mentionner ici quelques of
exemples. inactif en quantité e
Chapitre 4
inconnues tiveajout
par compound
d’une by adding
quantité a known
connue du même
Exemple 1. Détermination de la quantité
amount of the samed’un produit
compoundinactif en composé
quantité av
e
spécifique connue.
inconnues par ajout d’une quantité connue du même composé av
with a known specific activity
f1δ 1 [1 + Rr (1 + δ 2 )] + f 2δ 2 [1 + Rr (1 + δ 1 )] spécifique connue.
δ= aor = 0
aor = 0 (4.16)
1 + Rr [ f1 (1 + δ 2 ) + f 2 (1 + δ 1 )] N et a sont connues
aorad= 0 adNad and aad are known
L’activité
N spécifique
Specific amix doit
activity amixêtre
is tomesurée
be measured
ad et aad osont connues
(4.16)
Pour les abondances isotopiques naturelles dans une gamme δNordeest100 N /oroois
inconnue , cette
unknown
et équation
recherchéeand peut
wanted
(Eq. être (Eq. 4.16a):
4.16a):
L’activité spécifique amix doit être mesurée
approchée (à For
± 0.03‰)
natural par:abundances of isotopes within a δ
Nor est inconnue et recherchée (Eq. 4.16a):
range of 100‰ this equation can be approximat- ⎛a ⎞
N or = ⎜⎜ ad − 1⎟⎟ × N ad (4.19)
δed= (to
f1δ1within
+ f2δ2 ± 0.03‰) by: ⎛⎝ aamix ⎞
⎠ (4.17)

N or = ⎜⎜ ad − 1⎟⎟ × N ad
δ = f1δ1 + f2δ2 la solutionIfradioactive
Si(4.17) ⎝ a mix ajoutée
the added ⎠ est sanssolution
radioactive is carrier
support, i.e. Nad = 0,free,
et que donc son activ
ce qui signifie qu’on peut additionner les valeurs δ avec une très bonne approximation. La Fig. 4.2
tend vers i.e.
∞, nous N  = 0
devons
ad and
écrire: thus the specific activity a is ∞,
whichd’un
montre l’exemple means thatentre
mélange to a very
eau degood Si
mer etapproximation
eau douce la dans
solution
un we radioactive
estuaire. ajoutée est sans support, i.e. Nad =ad0, et que donc son activ
have Le fait
to write: d’additionner
additivity
est valable aussi bien pour applies to δ en
les teneurs values.
chloruresFig. de4.2 shows
tend
l’eau vers ∞, nous
(traceur devons écrire:
conservatif) que pour 18δ. La
A = A = N × a = Nor × amix
relation entrethe example
les deux est enofconséquence
mixing seawater une ligneand river water Aad = Amix = Nmixmix × mix
ad mix
droite. amix = Nor × amix
in an estuary. Additivity is valid for the Chloride Aad = Amix = Nmix × amix = Nor × amix
content of the water (conservative tracer)ainsi: as well and
N thus: Nor = Aad / amix
or = Aad / amix

as for δ. The relation between the two isainsi:

18
conse- N or = Aad / a2. Determination
Example mix of an unknown
quently a straight line.
amount of (human or animal)
Example 2. Détermination d’une quantité inconnue de fluide corporel (humain
body fluid by adding deuterium
Example 2. ajout d’eau enriched
Détermination enrichie
d’uneen deutérium
water
quantité inconnue de fluide corporel (humain
4.3.1.1. Isotopic dilution analysis
A practical application of the previous sectionCoris est connue, Cajout d’eau
mais doitenrichie en deutérium
être calculée à partir de 2R ou2 2δ de l’eau du fluide
or is known; has to be calculated from the  R or
the so-called Isotopic Dilution Analysis, a method (sang),
Cor est connue,
2
δ water
parce of the 
qu’utiliser
mais doit êtreδ2original
2
àbody
en tant que
calculée fluid
de 2R(blood),
concentration
partir ou(cf.
2 Eq. 4.17) n’est pas a
δ de l’eau du fluide
used in radiochemistry. By this method an amount Nad est connue because
mais peutusing
être δ as
2négligée a concentration (cf.
(sang), parce qu’utiliser δ en tant que concentration (cf. Eq. 4.17) n’est pas a
of radioactive material can be determined without Cad est connue Eq. 4.17) is not accurate enough
N est connue
N is mais peut
known butêtre
may négligée
be negligibly small
the chemical separation procedures being com- C
ad
doit ad
être mesurée
plete. For instance, if small traces of radioactivity C mix
ad est connue
C ad is known
N est inconnue toetbe
recherchée (à partir de l’équation 4.18b):
are to be quantified, a known amount of the same, mix doitCêtre
Cor mix is mesurée measured
but inactive compound is added and the chemical Nor is unknown
Nor est inconnue et recherchéeand wanted
(à partir (from Eq. 4.18b):
de l’équation 4.18b):
⎛ C ad ⎞
separation procedure is carried out (not necessar- N or = ⎜ ⎜ ⎟
− 1⎟ × N ad
Fig.4.2 Relation linéaire entre concentration en Cl et 18δ de l’eau dans l’estuaire
⎝⎛ CCmix de⎞la « Western
ily quantitative). From the  final specific activity ad 18 ⎠ (4.20)
Scheldt », quand l’eau de la rivière N = ⎜ − δ1⎟⎟=×−6.5‰)
N ad
of the compound the quantity of belge Scheldt ra-
the original (Cl = 0‰or(= g/kg); ⎜C
⎝ ⎠
se
mix
dioactiveavec
mélange compound
les eaux de canla then
Mer dube Nord
calculated. 19,36‰;3.18δ =Détermination
(Cl =Example 0‰). d’une radioactivité sans support inconnue (Aor) p
In general, the conservation of mass Example during 3. Example 3. Determination
quantité connue
Détermination du produit
d’une of an
inactif
radioactivité (N ad)unknown
sans support inconnue (Aor) p
the addition of material requires (cf. Eq. 4.15): carrier-free radioactivity (Aor) by
quantité
Ici l’activité totale, connue
avant du produit
et après inactif
l’ajout, est (Nad) (Amix = Aor), tandis que la q
la même
adding a known quantity of the in-
Aor + Aad = Amix or mélange (Nmixtotale,
) est égale
avantà la quantité
active ajoutéeest
aprèscompound (Nlaad):même
(N
Ici l’activité et l’ajout, ad) (Amix = Aor), tandis que la q
4.4.1.1 ANALYSES DE DILUTION ISOTOPIQUE mélange (NmixA)orest
= Négale à la quantité ajoutée (Nad):
ad × amix

Une application
36 pratique de la partie précédente est, ce qu’on appelle, × amix de Dilution
Aor = Nadl’Analyse
Isotopique, une méthode utilisée en radiochimie. Par cette méthode, une quantité de matériel radioactif
peut être déterminée sans que les procédures de séparation chimique soient complètes. Par exemple, si
des traces de radioactivité doivent être quantifiées, une quantité connue d’un produit identique mais
 ABUNDANCE VARIATIONS by NATURAL PROCESSEs

Here the total amount of activity before and after 4.4. Isotopic changes in Rayleigh
the addition is the same (Amix = Aor), while the fi- processesVariations d’abondances isotopiques
nal quantity of mixture (Nmix) is equal to the quan- It is common in isotope Variations
studiesd’abondances isotopiques
to be concerned
tity added (Nad): with the change in isotopic composition of a res-
4.5.1 RESERVOIR AVEC UNE FUITE
4.5.1 RESERVOIR AVEC UNE FUITEof an increasing
ervoir because of the removal
Aor = Nad amix (4.21) Un modèle àfraction une boîteof noire
its décrivant
contents un réservoir avecbyune
accompanied seule fuite est présenté e
isotope
Un
N modèle
est le àfractionation.
nombreune boîte total noire
de décrivant
We
molécules, will un
et réservoir
discuss
R est avec unedeseule
the process
le rapport un- fuite est
l’isotope rareprésenté
par rape
This method is known as the Reverse Isotope
Dilution Analysis. N est le
abondant, tel que der
nombre two
total conditions,
de molécules, (i) removal
et R est leof a compound
rapport de l’isotope rare par rap
abondant, tel que (= sink) from a reservoir without an additional
N/(1+R) est le nombrefrom
input (evaporation de molécules
a  confined avec l’isotope
water basin abondant et
N/(1+R)
for example); est le nombre de molécules avec l’isotope abondant et
4.3.2. Mixing of reservoirs of RN/(1+R) est le (ii) removal
nombre accompanied
de molécules by a con-
avec l’isotope rare
different compounds Chapitre
Chapitre 4 4 stant input
RN/(1+R) est(= source)
le nombre de(such moléculesas evaporation
avec l’isotope fromrare
a lake with a river input).
If the mixing process includesChapitre chemically differ-
Chapitre
Chapitre444
Cette
Cette méthode
méthode est estconnueconnue comme comme
ent but reactive compounds of quantities l’Analyse
l’Analyse Réversible
Réversible dede Dilution
Dilution
N1 and Isotopique.
Isotopique.
N2 with different isotopic compositions R1 and 4.4.1. Reservoir with one sink
Cette
Cette méthode
méthode estest connue
connue comme
comme l’Analyse
l’Analyse Réversible
Réversible
Réversible de
de
de Dilution
Dilution Isotopique.
Isotopique.
Cette méthode
4.4.2
4.4.2 MELANGE R2est
MELANGE , the  connue finalDE
comme
DE stage
RESERVOIRS
l’Analyse
is characterised
RESERVOIRS AVECAVEC by a Dilution
DIFFERENTSfraction-Isotopique.
DIFFERENTS A simple box model describing a reservoir with
COMPOSES
COMPOSES
ation between the compounds. During there ac- only one sink. is presented by Fig. 4.3. Here N is
Si4.4.2
Si
le le
4.4.2 processus
processus dede
MELANGE
MELANGE mélange
mélange implique
DEDE implique desdescomposés
composés réactifs
réactifs maismais chimiquement
chimiquement différents
différents enen quantité
quantité
4.4.2 tion a chemical
MELANGE DE RESERVOIRS
RESERVOIRS
shift between the two
RESERVOIRS AVEC
AVEC
AVEC DIFFERENTS
DIFFERENTS
compounds COMPOSES
DIFFERENTS COMPOSES
the total
COMPOSES number of molecules, and R is the ratio
N1Net1 etN2Net2 et avec avec desdes compositions
compositions isotopiques
isotopiques différentes
différentes R1Ret1 et
R2R , 2le, le stadestade
of final
final
the rareest estcaractérisé
caractérisé
to abundant parparunun
molecular concentrations,
Si
Si le
le processus
processus will de
de often
mélange
mélange occur. implique
implique The quantities
des
des composés
composés change
réactifs
réactifs into
mais
mais Nchimiquement
1’
chimiquement différents
différents en
en quantité
quantité
Si le processus
fractionnement
fractionnement entre de
entre mélange
cesces composés. implique
composés. des
Durant
Durant composés
cettecette réactifs
opération,
opération, mais
unun chimiquement
déplacement
déplacement so chimique
that différents
chimique entre
entreen quantité
leslesdeux
deux
NN anddes N ’compositions
with isotopic compositions of R1RR’11and R ’le stade
composés et NN
N111 et
et
composés N222 et et
et avec
avec
avec des
interviendra
interviendra des2compositions
compositions
souvent.
souvent. Les
isotopiques
isotopiques
isotopiques
Les quantités
quantités
différentes
différentes
différentes
évoluent
évoluent R et RR
et
et
Fig.4.3
vers
1vers RN
22,,,2le
21N ' le
1et
stade final
' stade 2N
final est
' 2final
etNReprésentation
avec
' avec
est
est caractérisé
caractérisé
caractérisé
desdes schématique
compositions
par
par
par un
compositions
un
undu processus de Rayleigh. N est le nombre d
fractionnement
fractionnement where entre
entre the latter
ces
ces composés.
composés. values are a fractionation
Durant
Durant cette
cette opération,
opération, factor
un
un déplacement
déplacement N/(1+R) chimique
chimiqueis the number
entre
entre les
les of abundant isotopic mol-
deux
deux
fractionnement
isotopiquesR1R
isotopiques entre
' etR2R
' α apart. ces composés. Durant cette opération, un
Fig.4.3 déplacement l’isotope chimique
Représentation abondant entre
schématique
(≈
α αprès. les deux
nombre du total
processus de Rayleigh.
de molécules), N est
R est le lerapport
nombreisod
1et ', 2ces',Ancesdernièresdernièresvaleurs
example isvaleurs étant
the exchange étantdéfinies
définies
between auaufacteur
facteur
gas- dedefractionnement
fractionnement
ecules and près. UneUne
composés
composés
composés interviendra
interviendra
interviendra souvent.
souvent.
souvent. Les
Les
Lesunun quantités
quantités
quantités évoluent
évoluent vers
vers N N ' ' et
et
N1' etfacteur NN ' '
N2' avec avec
avec des
des compositions
compositions
etévoluent vers bicarbonatée, l’isotope despar
abondant compositions
(≈exemple,
nombre total(àdel’équilibre
molécules), R est le rapport iso
11 22
idée
idée dede cece mélange
mélangeeous estCO est l’échange
l’échange entreentre CO CO 2 gaz gaz et
une une solution
as,solution in-bicarbonatée, decomme,
comme, fractionnement
par
exemple, impliqué ou cinétique).
isotopiques
isotopiques R R ' ' et
et R R ',', 2 and
ces
ces dernières
dernières
a bicarbonate valeurs
valeurs
2solution
étant
étant définies
définies au
forfacteur
au facteur de
de RN/(1+R)
fractionnement
fractionnement is the number
α
α près.
près. Une
Une of rare isotopic mol-
isotopiques
l’eau
l’eau d’un d’unlaclac Rstance,
1 1
1et' etetle R 2
leCO2',CO
2 ces dernières
2 atmosphérique,
between 2 atmosphérique, lake water valeurs ouétant
ouand définiesd’une
le lemélange
mélange
atmospheric au
d’unefacteur
CO eau eaudouce de
douce fractionnement
facteur ded’une
et etd’une eaueauαdeprès.
fractionnement demermerUne
impliqué
à à (à l’équilibre ou cinétique).
2, ecules
idée
idée
idée de
de
de cece
ce mélange
mélange
mélange est
est
est l’échange
l’échange
l’échange entre
entre
entre un
un
un CO
CO
CO 22 gaz
gaz
gaz et
et
et une
une
une solution
solution
solution bicarbonatée,
bicarbonatée,
bicarbonatée, comme,
comme,
comme, par
par
par exemple,
exemple,
exemple,
différents
différents pH.pH.or the mixing of fresh and seawater 2 with different
l’eau
l’eau
l’eau d’un d’un
d’un lac lac
lac et
et
et lele
le CO
CO
CO 22 atmosphérique,
atmosphérique,
atmosphérique, ou
ou
ou le
le
le mélange
mélange
mélange d’une
d’une
d’unedeeau
Lors eau douce
la perte
eau douce
Forde
douce et
et
etdNd’une
d’une
the removal
d’une eau
moléculeseau
eauofde dedNmer
avec
de mer
mer unàààfacteur de
molecules with an accom- associé α, le bila
fractionnement
Un Unbilan
bilan de de
masse
pH.identique
masse identique
2
pour pour l’isotope
l’isotope rarerare peutpeut être
être
écritécrit(Fig.
(Fig. 4.1B): 4.1B):
différents
différents
différents pH. pH.
pH. Lors de larare
l’isotope panying
perte de dNfractionation
donne: molécules avecfactor α , the mass
un facteur balance associé α, le bila
de fractionnement
A similar mass balance for the rare isotopel’isotope can be rarefor donne:the rare isotope gives:
Un
Un
Un bilan
bilan
bilan de deR
de 1R
masse
masse
masse 'N
written1 ' 1N ' R2R' N
' identique
1identique
identique
+ 2 ' 2N
+(Fig. 4.1B): 2 ' Rl’isotope
'pour
pour
pour R
N11N1 Rrare
l’isotope
= = 1l’isotope
RN2 2Npeut
rare
+ + 2rare
peut
peut
2 être
être
être écrit
écrit
écrit (Fig.
(Fig.
(Fig. 4.1B): 4.1B):
4.1B):
1 +1 + R1R' 1 ' 1 +1 + R2R' 2 ' 1 +1 + R1R1 1 +1 + R2R2 R R+dR αR
RR R11'''NN N11''' RR R22'''NN N22''' RR R11NN
N11 RR R22NN N22 N= (N + d N ) − dN
1 1 + + 2 2 ==
+ = 1 1 ++ + 2 2  or 1 + R N = 1 + R + d R ( N + d N ) − 1 +αα
R R + d R RR
dN
111++ + RR R11''' 111++ + RR R22''' 11 1 + RR
++ R11 11 1 +++ RR
R22 1 + R 1 + R + d R 1 + α R
ouou R1R 'N11'N ' +1' R 1+2R 'N22'N' ≈2' R ≈1R 2 N11N+1 R +2R N22N2
1 2    To a good approximation (4.22)
(4.22) we will furthermore
Pour une bonne take approximation,
the total nous considérerons,
number of molecules pourequal
la suitetodu paragraphe, que
ou
ou RR R11'N ’N
1'N ' '1++’R +R22R 'N
'N 2’N' ' ≈
≈ 2R ’R≈ N NR +
1+NRR1 +NN R 2N2 (4.22)
Pour une bonne approximation, (4.22)
(4.22)
nous considérerons, pour la suiteinduen
paragraphe, que
ou N1N ' +1' N + 2N ' =2R' 1N ='N1N1+'1 +N
11
+R 'N2les
22 ' ≈les R1mêmes
1 1 N1 + R
11 22 N2
22 de molécules estdans égal
the number au nombre de
of abundant molécules
(4.22) pourisotopic de l’isotope
molecules:abondant: fait, pour cett
avec
avec 2N,2et
2, et mêmes approximations
2approximations queque celles
celles appliquées
appliquées dans l’équation
l’équation 4.154.15 pour
where N1’ + N2’ = N1 + N2, and the same approxi- de moléculesfact, est égal forau nombre de molécules alldedenominators
l’isotope
qui neabondant:are en pasfait,
aupour cett
la la
gamme
gamme desdes valeursvaleurs dede δ de δ de tous tous lesles échantillons
échantillons naturels. tous les dénominateurs
naturels. this seront égaux
approximation à 1+R (ce revient même
avec
avec NN ' ' +
+ N N ' mation
' == NN + + N applies
N ,, et
avec N1' + N2' = N1 + N2, et les mêmes approximations que celles
11 22 1 1 22 et les
les as
mêmes
mêmes in Eq. 4.15
approximations
approximations for the range
que
que celles
celles
tous ofles
complètement δ
appliquées
appliquées
appliquées taken
dénominateurs dans
R!).dansdans
Le l’équation
equall’équation
bilan 1+R
seront
de masse
l’équation 4.15
4.15
(which
égaux pour
4.15pourpour
à
pourisl’isotope
not the same
1+R (ce qui ne
rare devient as ne-
revient pas
maintenant: au même
Ceci
Ceci
la
la conduit
gamme
gammeconduit à: values
des
des à:
valeurs
valeurs of de
de all
δ δ denatural
de tous
tous lessamples.
les échantillons
échantillons naturels.
naturels. complètement glecting
R!). Le R
bilan completely!).
de masse pour The mass
l’isotope rarebalance
devient for
maintenant:
la gamme des valeurs de δ de tous les échantillons naturels. RN = (R +isotope dR)(N +now − αRdN
dN)becomes:
the rare
Ceci
Ceci
Ceci conduit
conduit
conduit à:à: R1results
This RN N+ R +in: RN N RN = (R + dR)(N +(4.23) dN) − αRdN
R2à: R' =2 ' = 11 1 2 2 2 2 et et R1R' =1 'α =Rα2R' 2 ' et, en négligeant RN les = (R produits
+ dR)(N +(4.23)
de l’équation
dN) − αRdN différentielle:
αNα1N'+1 'N+ 2N' 2 '
RRR11NN N11 ++ + RR R22NN N22 et, en négligeant les produits de l’équation différentielle:
ouou
RRR22'''==
2 = α
1 1
αNN N11'+ '+NN22''
2 2 et
et
et RR
and =αα
R111'''== αRRR222''' (4.23) and neglecting
dR/R = (α − 1)dN/N
(4.23)
(4.23)
the products
(4.23) of differentials:
α 1 '+ N 2 '
dR/R==(α
dR/R (α−−1)dN/N
1)dN/N
L’intégration et l’application des conditions aux limites: R = Ro at N = No (rien n’a été
ou
ou
ou or
f δf δ+ +f δf δ− −f 'fε ' ε Integration anddes applying
(4.24) the boundary condition:
L’intégration et l’application conditions aux limites: R = Ro at N = No (rien n’a été
δ 2δ' ≈2 ' ≈1 1 1 2 22 2 1 1 and et et δ 1δ' ≈1 'δ≈2δ'+2 ε'+ε présent) (4.24) donnent: (4.24)
1 +1 +f1 'fε1 ' ε présent)
donnent: R = Ro at N = No (nothing has been neglected yet)
fff11δδδ11 ++ ff22δδ22 −− ff11''εε
δδδ22'''≈≈ 1 1 + f 2δ 2 − f 1 ' ε et
et δδ ' ≈
' ≈ δδ '+'+ ε
ε gives: α −1 (4.24)
(4.24)
2 ≈ f = N 1111+/(N
+ ''εεε 2), et cetera.
fff11' + N et δ111 ' ≈ δ222 '+ε R ⎛ N ⎞α −1 (4.24)
with 1  + = ⎜ ⎟
avec
avec f1 =f1 N= 1N /(N /(N + N+ N ), et
), et
cetera.
cetera. RR0 = ⎛⎜⎝⎜ NN0 ⎞⎟⎠⎟
1
1 1 1 2 2
These equations are applied to the indirect18 deter- (4.25a)
CesCes
avec
avecéquations
équations
ff == NN /(N sont
/(N sont
+ + appliquées
N N appliquées
),
), et
et 18 à la
cetera.
cetera. à ladétermination
détermination indirecte
indirecte 18
dede δ d’unδ d’un R0 ⎜⎝ d’eau,
échantillon
échantillon
⎟
N d’eau,
0 ⎠ via via
la lamesure
mesure
avec f1 = N1/(N
11 11 mination
1
1 + N2), et
1 2 2 ofcetera. δ of a water sample, viz. by measur-
18 18
dudu δ du
δ du CO CO2 équilibrant
2ing équilibrant δ of avec
CO avec l’eau l’eau plutôt
plutôtque que viavia l’eaul’eauelle-même
elle-même
ou,18
18avec (Sect.(Sect. 10.2.1.1
or10.2.1.1
les valeurs etpar
in δ δvalues et
11.2.3.4).
11.2.3.4).
rapport aux références standardisées: ref-
2 equilibrated with the water rather
18
Ces
Ces 18δδ d’un with respect to the standardised
Ces équations
équations
équations sont sont
sont appliquéesappliquées
appliquées ààà la
la
la détermination
détermination
détermination indirecte indirecte
indirecte de de
de
ou, δ
avec
d’un
d’un les
échantillon
échantillon
échantillon
valeurs δ
d’eau,
d’eau,
d’eau,
par
via
rapport
via
via lala
la
aux
mesure
mesure
mesure
références standardisées:
du 1818
du 18δδ dudu CO COthan équilibrant
équilibrant the water avecitself
avec l’eau(Sect. 10.2.1.1
l’eau plutôt
plutôt que
du δ du CO222 équilibrant avec l’eau plutôt que via l’eau elle-même (Sect. 10.2.1.1 et 11.2.3.4). que via via l’eauandelle-même
l’eau 11.2.3.4).(Sect.
elle-même (Sect.erence:
10.2.1.1
10.2.1.1 et et 11.2.3.4).
11.2.3.4).
4.54.5 CHANGEMENTS
CHANGEMENTS ISOTOPIQUES
ISOTOPIQUES DANS
DANS LELE PROCESSUS
PROCESSUS DEDERAYLEIGH
RAYLEIGH
Il 4.5
Ilestestcourant
4.5 courant dans
dansleslesétudes
CHANGEMENTS
CHANGEMENTS étudesisotopiques
isotopiquesd’être
d’êtreconfronté
confrontéà àdesdeschangements
changements dedecomposition
composition
4.5 CHANGEMENTS ISOTOPIQUES ISOTOPIQUES
ISOTOPIQUES DANS DANS
DANS LE LE
LE PROCESSUS
PROCESSUS
PROCESSUS DE DE
DE RAYLEIGH
RAYLEIGH
RAYLEIGH 37
isotopique
isotopiquedans dansununréservoir
réservoirenenraison
raisondedela laperte
perted’une
d’unepartie
partiecroissante
croissantededesonsoncontenu,
contenu,perte
perte
IlIl
Il est
est
est courant
courant
courant dans
dans
dans les
les
les études
études
études isotopiques
isotopiques
isotopiques d’être
d’être
d’être confronté
confronté
confronté ààà des
des
des changements
changements
changements de
de
de composition
composition
composition
accompagnée
accompagnée parparununfractionnement
fractionnement isotopique.
isotopique. Nous
Nous allons
allonsdiscuter
discuterdedececeprocessus
processus sous
sousdeux
deux
isotopique
isotopique
isotopique dans
dans
dans un
un
un réservoir
réservoir
réservoir en
en
en raison
raison
raison de
de
de la
la
la perte
perte
perte d’une
d’une
d’une partie
partie
partie croissante
croissante
croissante de
de
de son
son
son contenu,
contenu,
contenu, perte
perte
perte
conditions,
conditions, (i)(i)
la la
perte
perte
d’un
d’uncomposé
composé (=(=fuite)
fuite)
depuis
depuisunun
réservoir
réservoir
sans
sans
apport
apport
additionnel
additionnel (évaporation
(évaporation
accompagnée
accompagnée par par un
un fractionnement
fractionnement isotopique.
isotopique. Nous
Nous allons
allons discuter
discuter de
de ce
ce processus
processus sous
sous deux
deux
 ou R est donné = l’équation α3.25a.
RΣpar
N0 − N ∫
R d NL’intégration
=
N
de N dN
α −1cette équation donne:
N0 − N N ∫
N

α
1 − (N / N )
α
N ⎛ N ⎞ N
ou R est donné
RΣpar
= l’équation
0
⎜
R03.25a. ⎟
L’intégration
0
= R0 de cette équation
⎜N ⎟
0 donne:
INTRODUCTION N 0 − N ⎝ 0⎠
N
1− N / N0
α
1 − (N / N 0 )
α
N0 ⎛ N ⎞ N0
ou RΣ = R0 ⎜⎜ ⎟⎟ = R0
δ = (1 + δ0)(N/N0)ε − 1 (4.25b) or N 0 − N ⎝ N0 ⎠
N
1− N / N0

1 − (N / N 0 )
α
where N/No represents the remaining fraction of
ou
the original reservoir; Ro and δ0 refer to the origi- δ Σ = (1 + δ 0 ) −1 (4.27)
1− N / N0
nal isotopic composition. Once more we have to
remind the reader that ε (= α –1) is a small num- (
The resulting1 −change
(
δFig. 4.4 )
δ 0de
N / N 0in) δe (for δ0  =  0) is shown in
α

Le changement
ber, for instance −0.004 if the fractionation is = 1 +by
Σ résultant the lower = −0)1est montré sur la Fig. 4.4 par la courbe infé
δe (pour δline.
1 − N / N 00
−4‰.
4.5.2 RESERVOIR AVEC DEUX FUITES Chapitre 4
The increase in 18O/16O of a  confinedLe water
changement 4.4.2.
résultantReservoir
de δe (pour δ0 with two
montrésinks
= 0) estChapitre 4sur la Fig. 4.4 par la courbe infé
body by evaporation with α < 1 (Fig. 4.4: up-
Un phénomène légèrementmore plus compliqué, quoique
per curve) serves as an example of thisretirent A slightly
simplesimultanément complicated, but tout à fait réaliste, se produit si
nevertheless
4.5.2 by deux
realistic phenomenon
RESERVOIR composés
AVEC DEUX différents
occurs if two processes si-considéré (Fig. 4.5
FUITES au réservoir
Rayleigh process. Another case is presented
multaneously
intervient quand, withdrawdes
lors de la croissance twoalgues
different compounds
à la surface de l’eau, le pH de ladit
the 13C/12C increase in lake-water bicarbonate Un due
phénomène légèrement plus compliqué, quoique tout deux
à occurs
faitprocessus
réaliste, seimpliquent
produit si
provoquant from
la the reservoir
formation de (Fig. 4.5).
carbonate de This process
calcium. Les
to the growth of plankton. retirent simultanément deux composés
facteurs de when, through
fractionnement growth
du carbone of différents au(spécifiques).
algae in surface
caractéristiques réservoir
water,considéré (Fig. 4.5
We have now focussed our attention on intervient
the iso- quand, the pHlorsofde the water
la croissanceincreases causing
des algues the forma-
à la surface de l’eau, le pH de ladit
Le
topic change of the reservoir. It is also relevant bilan de masse
provoquant lation pour l’isotopie
of calcium
formation rare donne
carbonate.
de carbonate donc:
Both processes
de calcium. Les deuxhave processus impliquent
to calculate the isotopic composition of the com- characteristicdu carbon
facteurs de fractionnement isotope fractionation
carbone caractéristiques in-
(spécifiques).
pound which is gradually built up by the  infini- RN = (R + dR)(N + dN) − α1Rf1dN − α2Rf2dN
volved.
tesimal increments dN. This is not a simple Le addi-
bilan de masse pour l’isotopie rare donne donc:
The rare isotope mass balance now gives:
tive procedure, because the isotopic composition
Ici f1 + f2 = 1: une quantité totale dN de l’élément considéré est prélevée du réservoir.
of the reservoir changes during the process and RN
cas précédents, + dR)(N + dN) − α Rf dN − α Rf dN
= (Ravons:
RNnous= (R + dR) (N + dN) −1 α11R f1 dN2 − 2α2R f2 dN
thus also that of the increments dN. An example
is found in the formation ofd’abondances
a carbonateisotopiques
deposit
Fig.4.5
Ici f1 + f2 = 1:Représentation
Here schématique
f1 + f2 =totale
1: a total du processus
amount de Rayleigh
dNconsidéré
of the element dansdulequel deux
Variations dune
R quantité dN de dNl’élément est prélevée réservoir.
from a groundwaterVariations
mass whichd’abondances
looses CO Fig.4.5
isotopiques
when under =
prélevés (
Représentation
α f + α
consideration
cas précédents, nous avons:
2 du
1 1 f
réservoir
2 2 − 1 )
schématique
is
avec du processus
removed
différents from de Rayleigh(αdans
the reser-
fractionnements 1 et lequel
α 2 ); f deux
1 et f2
exposed to the atmosphere. R
voir. As du
prélevés with the previous
réservoir N
avecpar case, weau
différents have:
fractionnements et α
(α1 (f 2); f1 et f2
contributions fractionnées rapport prélèvement total 1 + f2 = 1).
La composition isotopique moyenne du composé formé (= somme (Σ)contributions
des incréments) à un temps
fractionnées
The average
La composition isotopique isotopic
moyenne composition of the formed
du composé formé (= somme (Σ)ddes R incréments) d par
à un tempsN rapport au prélèvement total (f1 + f2 = 1).
donné est: = α 1 f1 + α 2 f 2 − 1)
(
donné est: compound (= of the sum (S) of the increments) at R N
a certain timeNis: N
ce qui, après intégration, donne:
1 N 00 1 αR0 N 00 αce−1 qui, après which
intégration,
afterdonne:
integration gives:
RΣ = N 0 − N N∫∫ αR d N = N 0 − N N αα −−011 ∫∫ NN α
RΣ = 1 αR d N = 1 αR ⎛ N ⎞
−1 dN α1 f1 +α 2 f 2 −1
dN
N0 − N N N0 − N N N R = R0 ⎜⎜⎛ N ⎟⎟⎞α1 f1 +α 2 f 2 −1
N
R = R0 ⎜⎝⎜ N 0 ⎟⎠⎟ (4.28a)
where
ou R est donné R is given
par l’équation by Eq. 3.25a.
3.25a. Integration
L’intégration of thisdonne:
de cette équation
⎝ N0 ⎠
ou R est donné par l’équation 3.25a. L’intégration de cette ou
équation donne:
equation gives: ou or
α
1 − (N / N )
α
N ⎛ N ⎞α N
RΣ = N 00 R0 ⎜⎛⎜ N ⎟⎞⎟ NN 00 = R0 1 − ( N / N 00 )α δ = (1 + δ 0 )(N / N 0 )εε(4.26)1 f1 +ε 2 f 2
(4.28b)
RΣ = N 0 − N R0 ⎜⎝⎜ N 0 ⎟⎠⎟ N = R0 1 − N / N 0 δ = (1 + δ 0 )(N / N 0 )(4.26) 1 f1 +ε 2 f 2

N0 − N ⎝ N0 ⎠ 1 − N / N 0 This reduces to the simple case of one sink

(4.26) Cette solution(Eqs réduit le problème
4.25a and 4.25b) à un cas if f2simple de prélèvement
 = 0, while the expo- unique (Eqs. 4.25a
ou Cette solution
cas ou f2 = 0,nent réduit
tandis le problème
que la fonction à un cas simple de prélèvement
à ε1f1 siunique (Eqs. 4.25a
ou reduces to ε1f1 ifenthe removalexposant se réduitof the second le prélèvement du
cas ou f = 0, tandis que la fonction
compound occurs without fractionation.
se fait sans fractionnement.
2 en exposant se réduit à ε1 f 1 si le prélèvement du
1 − (N / N ) se fait sans fractionnement.
α
δ Σ = (1 + δ 0 )1 − (N / N 00 )α − 1 (4.27)
δ Σ = (1 + δ 0 ) 1 − N / N 0 − 1 4.5.3 RESERVOIR
4.4.3. AVEC
Reservoir (4.27)
UNE with SOURCEone ET sourceUNE FUITE, FONCTION D
1− N / N0 4.5.3 RESERVOIR AVEC UNE SOURCE ET UNE FUITE, FONCTION D
and one sink, as a function
Bien que les paragraphes précédents présentent des exemples pratiques du processus
Le changement résultant de δe (pour δ0 = 0) est montré sur la Bien
Fig. que
4.4 lespar paragraphes
la courbe of time présentent des exemples pratiques du processus
précédents
inférieure.
Le changement résultant de δe (pour δ0 = 0) est montré sur la cas général
Fig. 4.4 parinclus l’existence
la courbe inférieure.d’une seule source et d’un seule fuite. Ils sont représe
cas général
d’apport inclus l’existence
Although
i (en quantité d’unede
the previous
par unité seuleare source
temps) et et
practical pard’unun seule
examples
taux de fuite. Ils sont
of perte représe
u (Fig. 4.6A
4.5.2 RESERVOIR AVEC DEUX FUITES d’apport i Rayleigh
(en quantité processes,
par unité de the general
temps)
fractionnement à l’apport, αi, n’est pas nécessairement égal à l’unité. et case
par un includes
taux de perte u (Fig. 4.6A
4.5.2 RESERVOIR AVECrepresentation
Fig. 4.3.  Schematic DEUX FUITES of the  Rayleigh the existence of a source as well as a sink. These
fractionnement à l’apport, αi, n’est pas nécessairement égal à l’unité.
Un phénomène légèrement plusnumber
compliqué, quoique tout àLefait réaliste, se represented
produit si deux rareprocessus
réaliste,are by a supply rate i (in quantity per
process. N is the  of abundant isotopic bilan de masse de l’isotope est:
Un phénomène légèrement plus compliqué, quoique tout à faitmol- se produit si deux processus
retirent simultanément deuxnumber
ecules (≈ total composés Le bilanconsidéré
différents Rauis réservoir
of molecules), the isotope de masse de
unit (Fig.l’isotope
time) 4.5).andCe rare est: rate u (Fig. 4.6A), while
processus
a loss
retirent simultanément deux composés différents au réservoir considéré
ratio,lors
intervient quand, α  is
de the  (equilibrium
la croissance des or kinetic)
algues
RN +(Fig.
α Ri4.5).
surface de l’eau, the fractionation
à la fractionation le pH dei ladite
Ce
i d t =eau(Rwith
processus
+
augmente,
)[N + α(ii,−isu )not
d Rinput, d t ] necessarily
+ αRu d t
intervient quand, lors de la croissance des algues à la surface de l’eau, le RNpH+ α
equal dei Rladite
i
to unity.
i d t =
eau( R + d
augmente,R ) [N + (i − u ) d t ] + αRu d t
provoquant lafactor involved.
formation de carbonate de calcium. Les deux à processus
partir duquel impliquent
nous avons, par
par ailleurs desdes variables (avec α − 1 = ε):
séparation
provoquant la formation de carbonate de calcium. Les deux processus impliquent par ailleurs des
à partir duquel nous avons, par séparation des variables (avec α − 1 = ε):
facteurs de fractionnement du carbone caractéristiques (spécifiques).
facteurs de fractionnement du carbone caractéristiques (spécifiques).
38 pour l’isotopie rare donne donc:
Le bilan de masse dR dt
Le bilan de masse pour l’isotopie rare donne donc: =
(i + εu )R − α i Ri i = N 0 + (i −d ut )(t − t 0 )
d R
RN = (R + dR)(N + dN) − α1Rf1dN − α2Rf2dN (i + εu )R − α i Ri i N 0 + (i − u )(t − t 0 )
RN = (R + dR)(N + dN) − α1Rf1dN − α2Rf2dN
ou N au temps t a été remplacé par le dénominateur à droite (N = N0 à t = t0).
 Fig.4.5 Représentation schématique du processus de Rayleigh dans lequel deux composés sont
Fig.4.5 Représentation schématique du processus de Rayleigh dans lequel deux composés sont
prélevés du réservoir avec différents fractionnements (α1 et α2); f1 et f2 se réfèrent aux
prélevés du réservoir avec différents fractionnements (α1 et α2); f1 et f2 se réfèrent aux
contributions fractionnées par rapport au prélèvement total (f1 + f2 = 1).
contributions fractionnées par rapport au prélèvement total (f1 + f2 = 1).
ABUNDANCE VARIATIONS by NATURAL PROCESSEs

ce qui, après intégration, donne:

ce qui, après intégration, donne:
α1 f1 +α 2 f 2 −1
⎛ N ⎞α1 f1 +α 2 f 2 −1
R = R ⎛⎜ N ⎞⎟ (4.28a)
R = R00 ⎜⎜⎝ N 0 ⎟⎟⎠ (4.28a)
⎝ N0 ⎠
ou
ou

δ = (1 + δ )(N / N )ε 1 f1 +ε 2 f 2
(4.28b)
δ = (1 + δ 00 )(N / N 00 )ε 1 f1 +ε 2 f 2
(4.28b)

Cette solution réduit le problème à un cas simple de prélèvement unique (Eqs. 4.25a et 4.25b) dans le
Cette solution réduit le problème à un cas simple de prélèvement uniqueFig. 4.5. 
(Eqs. Schematic
4.25a et 4.25b)representation
dans le of the  Rayleigh
cas ou f2 = 0, tandis que la fonction en exposant se réduit à ε1f1 si le prélèvement du
process where second composé
two compounds
cas ou f2 = 0, tandis que la fonction en exposant se réduit à ε1f1 si le prélèvement du second composé are being removed from
se fait sans fractionnement. the reservoir with different fractionation (α1 and α2); f1
se fait sans fractionnement.
Fig. 4.4.  he  enrichment of a  rare heavy isotope in and f2 refer to the fractional contributions to the total
a  reservoir by the  Rayleigh process as a  function of sink (f1 + f2 = 1).
4.5.3 RESERVOIR AVEC UNE SOURCE ET UNE FUITE, FONCTION DU TEMPS
4.5.3 the  fraction removed.
RESERVOIR AVEC UNE The SOURCE
preferential
ET removal
UNE FUITE, of FONCTION DU TEMPS
Bien que les the  light isotopic
paragraphes speciesprésentent
précédents is accompanied by a  frac-
des exemples pratiques du processus de Rayleigh, le
Bien que les paragraphes précédents présentent des exemples pratiques du processus de Rayleigh, le
tionation
cas général inclus of α  < d’une
l’existence 1. The  lower
seule line present
source the  aver-
et d’un seule fuite. Ils sont représentés par un taux
cas général inclus
age l’existenceisotopic
cumulative d’une seule source et
composition of d’un seule fuite. Ils sont représentés par un taux
the compound
d’apport i (en quantité par unité de temps) et par un taux de perte u (Fig. 4.6A), alors que le
d’apport i (en quantité
formed par unité de
by the process, temps) et par un taux de perte u (Fig. 4.6A), alors que le
δS (Eq. 4.26).
fractionnement à l’apport, αi, n’est pas nécessairement égal à l’unité.
fractionnement à l’apport, αi, n’est pas nécessairement égal à l’unité.
The rare
Le bilan de masse isotoperare
de l’isotope mass
est:balance is:
Le bilan de masse de l’isotope rare est:
RN + α R i d t = (R + d R )[N + (i − u )d t ] + αRu d t
RN + α ii Rii i d t = (R + d R )[N + (i − u )d t ] + αRu d t
à partir duquel nous avons, we
from par séparation des variables (avec α − 1 = ε):
à partir duquel nouswhich have by separation
avons, par séparation des variablesof(avec
variables
α − 1 = ε):
(with α - 1 = ε):
dR dt
dR = dt
((ii ++ εεuu ))RR −− αα ii RRii ii N
= N 0 + (i − u )(t − t 0 )
0 + (i − u )(t − t 0 )

t a étéNremplacé
ou N au tempswhere at a timepart lehas been replaced
dénominateur by (N
à droite the de-
= N0 à t = t0).
ou N au temps t a été remplacé par le dénominateur à droite (N = N0 à t = t0).
nominator on the right (N = N
Variations 0 at t = t
d’abondances 0).isotopiques Fig. 4.6.  Schematic representation Chapitre 4 Rayleigh
of the 
60
60 process with one source and one sink (A ) as a func-
Integration and applying the boundary condition
L’intégrationthat
et l’application
R = R0 at tdes = tconditions
0 results in:
aux limites telles que R = R0tion à t =of
αt0itime with n and
Rconduisent
⎡ αà:i Rm denoting the input and output
i ⎤ −α (i / N 0 )(t −t0 )
Variations d’abondances isotopiques R = i
+
rates respectively,R −
⎢ 0 and ⎥ e as a function of the quanti-
(B)
−
i + uε α ⎣ α
ties of in- and outflow with ⎦ determining the  relation
α i Ri ⎡ α i Ri ⎤ ⎡ i − u ⎤ i −u between input and output rates.
R= + ⎢ R0 − ⎥⎢ 1 + (t − t )
0 ⎥ (4.29)
des conditions aux limites u / i )εque⎣R = R10 +à (t u=/ti0)εconduisent
1 + (telles ⎦ ⎣ N 0à:Comme⎦ t → ∞, une situation d’équilibre est atteinte avec:
i + uε
−
⎡ dans leαcas ou⎤i ⎡≠ u. i − u ⎤
+ ⎢ R0 − i Ri
×⎥ ⎢1 + (t − t 0 )⎥
i −u
(4.29)
(4.29) R=
α i Ri
ou δ=
(1 + ε i ) (1 + δ i )
)ε ⎦ ⎣de masse (4.31)
⎣ Si i1=+u,(ule/ ibilan N 0 est: ⎦
α 1+ ε
for0 the case
RN + αiRiidt where i ≠ u.0 + αRudt
= (R + dR)N
which is approximated by
ce qui peut être approché par: δ = δi + (εi − ε)
: If i = u, the mass balance is: δ = δi se
Une telle situation + (ε i − ε) (4.32)
produit quand l’évaporation du lac est contrebalancée par l’appo

RN0 + αiRiidt = (R + dR)N0 + αRudt

(R + dR)N0 + αRudt une rivière (Mer
SuchMorte, Lac Titicaca,
a situation occursLacwhere
Tchad). Dans ce cas, αi = 1 parce que l’
the evaporation
Chapitre 4 sans fractionnement.
of a lakeLa signification
is balanced by et α doivent
la valeurofdewater
the inflow from être considérées
from which we can similarly derive: processus décrit également le phénomène de dissolution
a river (Dead Sea, Lake Titicaca, Lake Chad). In incongruente qui se produ
systèmes d’eaux
this souterraines. Le résultat
case αi = 1 because est compris
the inflow simplement
occurs withouten notant qu’un ré
α i Ri ⎡ αR⎤
R= + ⎢ R0 − i i ⎥ e −α (i / N 0 )(t −t0 )
(4.30)
nécessite desfractionation. (4.30)
The meaning
apports isotopiquement and value
équivalents (Ri = α
of α has
aux pertes toR).
α ⎣ α ⎦
be considered separately. It also describes the in-
Un autre exemple important est fourni par l’évapotranspiration (eau du sol prélevée p
As t → ∞, a steady-state situation is reached with: congruent dissolution process which occurs in
Comme t → ∞, une situation d’équilibre est atteinte avec: travers de l’action capillaire des ses vaisseaux, et subséquemment évaporée au niveau
feuilles) qui provoque le transport de l’eau par la plante depuis le sol jusque
αR
R = i i ou δ =
(1 + ε i ) (1 + δ i ) fractionnement isotopique net. Ce processus est démontré en Fig. 39
(4.31)
4.7.
α 1+ ε Le faible diamètre des capillaires implique un flux relativement élevé. Ceci est esse
empêche l’eau isotopiquement lourde des feuilles de diffuser vers le bas.
ce qui peut être approché par: δ = δi + (εi − ε) (4.32)
 Ceci conduit à une équation différentielle:
RN + αiRi(1 − f)dN = (R + dR)(N + dN) − αRfdN
d R différentielle:
Ceci conduit à une équation dN
=
(αf − 1)R + (1 − f )α i Ri N
INTRODUCTION dR dN
=
L’intégration (et − 1)R + (1 − des
αfl’application f )αconditions
N aux limites avec R = Ro quand N = No con
i Ri

some groundwater systems. The result isL’intégration

simply et l’application des conditions aux limites avecαfR−1 = Ro quand N = No con
understood by noting that steady state requires R=
(1 − f )α i R + ⎡ R − (1 − f )α i R ⎤ ⎛⎜ N ⎞⎟
1 − αf
i ⎢ 0 1− f
i⎥ ⎜ ⎟
the input to be isotopically equal to the output ⎣ ⎦ ⎝ N 0 ⎠αf −1
R=
(1 − f )α i R + ⎡ R − (1 − f )α i R ⎤ ⎜ N ⎞⎟
⎛
(Ri = αR). (4.33) i ⎢ 0 i⎥ ⎜ ⎟
1 − αf 1− f
⎣ du réservoir ⎦ ⎝ N 0 Un
⎠ exemple courant de ce p
ou N/N0 indique la fraction restante originel.
Another important example is the fact that evapo- where N/N0 denotes the remaining fraction of
nature est représenté par l’évaporation à partir d’un réservoir d’eau isolé. Avec une ta
transpiration (the phenomenon that water from the original reservoir. A common example of this
ou N/N
de ce 0 indiqueRlaapproche:
réservoir, fraction restante du réservoir originel. Un exemple courant de ce p
the soil is taken up by a plant through capillary process in nature is represented by the evapora-
nature est représenté par l’évaporation à partir d’un réservoir d’eau isolé. Avec une ta
action of the plant vessels, and subsequently tion of an isolated water body. With decreasing
size (1 − f )α i
de ce réservoir, R approche:
evaporates from the leaf surface) causes water to R∞ =of the reservoir N, R approaches:
be transported by a plant from the soil to the air 1 − αf
with no net isotope fractionation. The process is R∞ =
(1 − f )α i
(4.34)
demonstrated by Fig. 4.7. 1 − αf
4.5.5 RESERVOIR AVEC DEUX SOURCES ET DEUX FUITES, AVEC E
The small diameter of the capillary results in
a  relatively high flow rate. This is essential,
4.5.5
be- FRACTIONNEMENT
4.4.5. Reservoir
RESERVOIR AVEC DEUX with two sources
SOURCES ET DEUX FUITES, AVEC E
cause it prevents the isotopically heavy leaf water
Enfin, nous allons traiter
anddes conditions
two en étatwith
sinks, stationnaire,
and i.e. situation dans laquell
FRACTIONNEMENT
to diffuse downward. et sortant d’un réservoirwithout
bien mélangéfractionation
sont équilibrés de telle façon que la compositi
Enfin, nous allons traiter des conditions en état
4.8).stationnaire,
Un exemplei.e. situation
de dans laquelle
If there is no source, i = 0 and Eq. 4.29 réservoir
reduces resteFinally
constante dans le temps (Fig.
we will treat the conditions at
pratique
a station-
ce modèle
et
unesortant
rivièred’un réservoir
en région bien mélangé
tropicale, sont équilibrés
où l’évaporation de telle façon
est significative que la une
et produit compositi
augme
to Eq. 4.25a, the simple case with only one sink. ary state, i.e. a situation in which in- and outflow
réservoir reste constante
des teneurs en H 2 18 dans le temps (Fig. 4.8). Un exemple pratique de ce modèle e
et O le longreservoir
de son cours; α représente l’évaporation et l’échang
If the sink is absent, the isotopic composition
une ap- enofrégion
rivière
a well-mixed
tropicale, où
are balanced
l’évaporation est
such that
significative et produit une augme
atmosphérique; I0 est le fluxcomposition
the isotopic d’eau originelleofà the reservoir
la source de la rivière.
com-
proaches for t → ∞ to R = αiRi. 2 18
des teneurs en H et O le long de son cours; α représente l’évaporation et l’échang
poundnécessite
L’état stationnaire has become
que les constant
fuites et lesinapports
time (Fig. 
soient4.8).
équilibrés, aussi bien p
In the general cases where i ≠ u, (for instance,
atmosphérique; I0 est le flux d’eau originelle à la source de la rivière.
rares que pourA practical
les isotopes example
abondants. ofCette
thiscondition
model is est presented
mathématiquement représen
slowly increasing or decreasing surface water
by a river
L’état stationnaire in a tropical
nécessite region
que les fuites et leswhere
apportsevaporation
soient équilibrés, aussi bien p
bodies in which cases αi = 1), the resulting iso-
rares que pourisles
significant, resultingCette
isotopes abondants. in gradually
conditionincreasing δ
est mathématiquement
2
représen
topic composition Variations d’abondances
of the reservoir isotopiques
depends on
the competition between sink and source. If and 18
δ values along the course of the river; α rep-
u < i and for t schématique
→ ∞, R approaches resents the evaporation and exchange with atmo-
αiRid’évapotranspiration.
[1 + (u/i)ε],
Fig.4.7 Représentation du processus Le flux capillaire de l’eau
while in the opposite case (u > i):
18 R → 2 ∞, as spheric vapour; I0 is the original water flow rate at
du sol, de rapport isotopique Ri (for O or H), se produit sans fractionnement. A la
with the simple Rayleigh process discussed in the river source.
surface de la feuille, l’évaporation est accompagnée d’un fractionnement Av/l (Table 7.3
Sect. 4.4.1.
ou 7.4). En état stationnaire, la vapeur d’eau qui s’échappe devrait avoir la même valeur
R que l’eau transpirée. Le résultat est que l’eau de la feuille (supposée bien mélangée) est
4.4.4. enReservoir
enrichie 18
O et 2H par αwith
v/l. one source
and one sink, s a function
of mass

4.5.4 If the Rayleigh
RESERVOIR process
AVEC UNEinvolves
SOURCE one
ETsource and FONCTION DE LA MASSE
UN FUITE,
one sink there is an alternative mathematical ap-
Si le processus de Rayleigh
proach in whichmet en jeu unecomposition
the isotopic source et uneisfuite,
con- on a une approche mathématique
alternative dans laquelle la composition isotopique est considérée
sidered to be a function of changes in quantity N, comme une fonction du changement
de quantité Nrather than
plus que of time
comme une(Fig. 4.6B). The isotope
fonction du temps massLe bilan de masse isotopique donne
(Fig. 4.6B).
donc: balance now gives:
Fig. 4.7.  Schematic representation of the evapotrans-
RN++ααiRiRi(1
RN − f)dN = (R + dR)(N + dN) − αRfdN
i(1 − f)dN = (R + dR)(N + dN) − αRfdN piration process. The  capillary flow of the  soil water
Ceci conduit à une équation différentielle: with isotope ratio Ri (for 18O or 2H) occurs without
This results in the differential equation: fractionation. At the surface of the plant leaf evapora-
dR dN tion is accompanied by fractionation Av/l (Table 7.3 or
=
(αf − 1)R + (1 − f )α i Ri N 7.4). In a stationary state the escaping vapour should
have the same R value as the transpired water. The re-
L’intégrationIntegration anddes
et l’application application
conditions of
auxthe boundary
limites avec R con- sultN is= N
= Ro quand o conduit
that à:
the  (supposedly well-mixed) leaf water is
dition that R = Ro at N = No results in: enriched in O and H by αv/l.
18 2

αf −1

R=
(1 − f )α i R ⎡
+ ⎢ R0 −
(1 − f )α i R ⎤ ⎛⎜ N ⎞⎟ (4.33)
i i⎥ ⎜ ⎟
40 1 − αf ⎣ 1− f ⎦ ⎝ N0 ⎠

ou N/N0 indique la fraction restante du réservoir originel. Un exemple courant de ce processus dans la
nature est représenté par l’évaporation à partir d’un réservoir d’eau isolé. Avec une taille décroissante
 ABUNDANCE VARIATIONS by NATURAL PROCESSEs
Chapitre 4

f 1
I +dI + dI = dI +I
1− f 1− f

et

f 1
(R + d R )( I + d I ) + α i Ri d I = αu R d I + RI
1− f 1− f

ou

⎛ εu + f α f ⎞
⎜⎜ R − i Ri ⎟⎟ d I = I d R Variations d’abondances isotopiques
⎝ 1− f 1− f ⎠
Fig. 4.8.  Model representing a well-mixed reservoir with ε u + fsimple in- and outflow as well as with a source and sink

affecting the isotopicαcomposition
f ⎡ α f ⎤ ⎛ I ⎞ 1− f
R = i Ri + ⎢ R0 − i Ri ⎥⎜⎜ ⎟⎟ instance, during an infinitesimal time period
of the reservoir. For
(4.35)
dI has escaped
εu + f
from the (river) water into the air
⎣ ε u + f ⎦⎝ I 0 ⎠
through evaporation and exchange with the ambient vapour.

Chapitre 4
ou
Chapitre 4
The stationary f 1
I +dI + d Istate
= requires d I + I that the sinks and εu + f

sources are f
1 − balanced α1i f−for ⎡
f the abundant as αwell
i f as ⎤⎛ I ⎞ 1− f
f δ= 1 (1 + δ i ) + ⎢1 + δ 0 − (1 + δ i × 
)⎥⎜⎜ ⎟⎟ −1 (4.36) (4.36)
for
I + dthe rare
I+ isotope.
dI = ε u +This
f d Icondition is 4mathemati-
+ I Chapitre
⎣ εu + f ⎦ ⎝ I0 ⎠
1 − f by:1 − f
cally presented
The result of the last model calculation is shown
et f 1
I +dI + dI = dI +I in Fig. 4.9 for δ and ε values as indicated in
1 −duf dernier1 −modèle
Le résultat f f est indiqué sur1 la Fig. 4.9 pour des valeurs
the graph. de δ et ε telles
In the case qu’indiquées
of flowing river water that
et (dans )( I + d IDans
R + dleRgraphe.
and ) + α ileRicas d’une = α u R pouvant
d I rivière d I être
+ RIsoumise à l’évaporation, la valeur de f dépend
is subjected to evaporation, the value of f depends
1− f 1− f
Fig.4.8 Modèle représentant unPourréservoir bien
f le calcul mélangé
1Fig. 4.9,avec un arbitrairement
flux entrant etfixée sortant simple,
(ainsi
R + d R )( I + d I ) + α i Ri
de l’humidité relative.
qu’avec une source 1et−une
de
d I = αu R la f
d I + RI a été on the relative humidity. à 0,5. For the calculation of
ou f fuite affectant
1 − f la composition isotopique du réservoir. Par
et La différence avec l’évaporation simple, uni-directionelle Fig. 4.9, de la Fig.f4.4 hasestarbitrarily
évidente: been
tandischosen 0.5.
que, dans
exemple, pendant une période de temps infinitésimale, dI s’échappe de l’eau (de la
ou or⎛leε ucas α f la valeur
+ fprécédent, ⎞ de δ de l’eau restante tend vers l’infini, ici la valeur de δ augmente très
rivière)
⎜⎜ R −l’airi viaRl’évaporation
vers i⎟ d I =f I d R et l’échange
1 avec la vapeur ambiante.
(⎝régulièrement.
R1+−dfR )( I +1d−ILe ⎟
α⎠i Ri le dplus
)f + résultat I =α uR
important ddeI +comparaison
RI des tendances pour 18δ et 2δ avec
⎛ εu + f αi f ⎞ 1− f 1− f
⎜⎜l’augmentation
R − duRrapport i⎟⎟ d I =I/I
I d0 sera
R discuté en Sect. 7.5.
Integration
⎝ 1− f 1and
− f applying
⎠ the boundary condition
ou
L’intégration et l’application des conditions aux limites, i.e. R = R0 avec I = I0, conduit à:
R = R0 at I = I0 results in:
⎛ εu + f α f ⎞
⎜⎜ ⎡ ε u + Rf − i α i R
f i ⎟⎟ d⎤I = I d R
⎝ 1⎢− f R1−− f R⎠ i ⎥
⎣ 1− f 1− f ⎦ εu + f I
ln = ln
⎡ε u + f α i f Variations f I0
⎤ 1 −d’abondances isotopiques
⎢ 1 − f R0 − 1 − f Ri ⎥
⎣ ⎦
Variations d’abondances isotopiques
Finally, after some rearrangement: ε u + f
α f ⎡ α f ⎤⎛ I ⎞ 1− f
R = i Ri + ⎢ R0 − i Ri ⎥⎜⎜ ⎟⎟ ε u + f (4.35)
Finalement, après εquelques
u +f f
α ⎣⎡ εαu +f f
réarrangements: ⎦⎤⎝⎛ II0 ⎠⎞ 1− f Fig. 4.9.  Result of the  model of Fig. 4.8, represent-
R = i Ri + ⎢ R0 − i Ri ⎥⎜⎜ ⎟⎟ (4.35) ing, for instance, a  river (4.35)which evaporates continu-
εu + f ⎣ ε u + f ⎦⎝ I 0 ⎠
ously during its course (Eq. 4.36). The value of f has
ou
or been chosen 0.5. The δ and ε values can be realistic.
ou
Fig.4.8 Modèle représentant un réservoir bien mélangé avecε +un The shape
flux entrantof etthe curve is almost a straight line, con-
sortant simple,
u f
64 trary
ainsi qu’avec
α f une source ⎡ et une fuite
α i f affectant la ⎤⎛ composition
I ⎞ 1− f isotopique du réservoir. Par presented in Fig. 4.4.
to the simple evaporation
Fig.4.8 δ
Modèle
exemple,
(
= ireprésentant1 + δ i ) +un⎢1réservoir
pendant
+ δ 0 − bien
une périodeε de+ temps
(1 + δ i )⎥avec
mélangé ⎜⎜ ⎟⎟un
infinitésimale,
−A similar
ε u + fflux
dI
1entrant curve
s’échappe
can simple,
et sortant
de
be
l’eau
calculated for 2δ. The ratio be-
(4.36)
(de la
εα + f α
⎡⎣ et une fuite f I
⎤⎝⎛ I0 ⎠⎞ 1− f tween
i affectant la ⎦composition
u f u f thesedu two curves will
Par be discussed in Sect. 7.5.
vers (l’air )
ainsi
δ = qu’aveci
1une
+ δsource+ 1 + δ − (1 + δ ) ⎜ ⎟ − isotopique
1 réservoir.
(4.36)
rivière) via
i l’évaporation
⎢ 0 et l’échange i ⎥⎜avec ⎟la vapeur ambiante.
ε u + pendant
exemple, f une ⎣période de ε u +temps
f infinitésimale,
⎦⎝ I 0 ⎠ dI s’échappe de l’eau (de la
Fig.4.8 rivière)
Fig.4.9vers
Modèle l’air via l’évaporation
représentant
Résultat un modèleetde
duréservoir l’échange
bienla mélangé
Fig.4.8,avecreprésentant,
la vapeur
avec un flux ambiante.
entrant
par et sortant
exemple, simple,qui s’évapore
une rivière 41
Le résultat duainsi
L’intégration qu’avec
etdernier
l’application
modèleune source
des
est et une
conditions
indiqué
continuellement surfuite
aux
la au
tout affectant
limites,
Fig.long i.e.
4.9 de laRcomposition
pour
son R0valeurs
=cours
des avec (Eq.4.36).isotopique
I =de I0δ, conduit du
à: réservoir.
etLaε valeur
telles de f a étéPar
qu’indiquées fixée à 0.5. Les
dans exemple,
le graphe. Dans le pendant
casvaleurs
d’une unerivière
période de temps
pouvant être infinitésimale,
soumise à valeurs dI s’échappe
l’évaporation, de l’eau
laε telles
valeur de (de la
f dépend
Le résultat duetdernier modèle de δ et sur
estconditions
indiqué ε semblent
lalimites,
Fig. réalistes.
4.9 pour La
des forme de de la courbe
δ et estqu’indiquées
presque une ligne droite,
L’intégration l’application
rivière) vers l’airdes
via l’évaporationaux et l’échangei.e. R = R avec
avec la vapeur I = I , conduit
ambiante. à:
de l’humidité ⎡ ε
relative.+ f
Pour leα f
calcul
contrairement ⎤
de la Fig.
au 4.9,
modèle f a été
0
arbitrairement
d’évaporation simple
0
fixée
présentéà 0,5. en Fig.4.4. Une courbe similaire
dans le graphe. Dans le cas
u
R − d’une Rrivière pouvant être soumise à l’évaporation, la valeur de f dépend
i
 INTRODUCTION

The difference between the simple, one-direc- very regular. The important result of comparing

tional evaporation of Fig. 4.4 is obvious: while in the trends for 18δ and 2δ with increasing I/I0 will
the former case the remaining δ of the remaining be discussed in Sect. 7.5.
water approaches infinity, here the  δ increase is

42
5. rADIOnuclide DECAY and production
This section contains a brief review of relevant
facts about radioactivity, i.e. the phenomenon
of nuclear decay, and about nuclear reactions,
the production of nuclides. For full details
the reader is referred to textbooks on nuclear
physics and radiochemistry, and on the applica-
tion of radioactivity in the earth sciences (cited in
the list of references).
5.1. Nuclear instability
If a nucleus contains too great an excess of neu-
trons or protons, it will sooner or later disin-
tegrate to form a stable nucleus. The different
modes of radioactive decay will be discussed
briefly. The various changes that can take place in
the nucleus are shown in Fig. 5.1. In transforming
into a more stable nucleus, the unstable nucleus
looses potential energy, part of its binding en-
ergy. This energy Q is emitted as kinetic energy
and is shared by the particles formed according to
the laws of conservation of energy and momen-
tum (see Sect. 5.3).
The energy released during nuclear decay can be
calculated from the mass budget of the decay re-
action, using the equivalence of mass and energy,
discussed in Sect. 2.4. The atomic mass determi-
nations have been made very accurately and pre-
cisely by mass spectrometric measurement:
E = [Mparent − Mdaughter] mc2 (5.1)
with
1 uma ≡ 931.5 MeV (5.2))
Disintegration of a parent nucleus produces
a daughter nucleus which generally is in an excit-
ed state. After an extremely short time the daugh-
ter nucleus looses the excitation energy through
the  emittance of one or more γ (gamma) rays,
electromagnetic radiation with a very short wave-
length, similar to the emission of light (also elec-
tromagnetic radiation , but with a longer wave-
length) by atoms which have been brought into
an excited state. In some cases, however, ß decay
is directly to the ground state of the daughter nu-
cleus, without the emission of γ radiation. Fig. 5.2
shows the various decay schemes of some famil-
iar nuclides.
5.2. Nuclear decay and radiation
In the now following sections the various types
of spontaneous nuclear disintegration will be dis-
cussed.
5.2.1. Negatron (β−) decay
The most abundant decay mode is ß- decay, in-
volving the emission of a negative electron,
a  negatron or β− (beta) particle because of
a transformation inside the nucleus of a neutron
into a proton:
n → p+ + β− +ν + Q (5.3)
This results in a daughter nucleus with equal
A and a change in atomic number Z to Z+1, and
the emission of an electron and an anti-neutrino.
A (anti)neutrino is a particle with mainly a rela-
tivistic mass, i.e. mass because of its motion.
(Neutrino’s and negatrons have their spin anti-
parallel to their direction of motion and anti-neu-
trino’s and positrons parallel).
The total reaction energy Q is shared between
the  β particle and the (anti)neutrino. The conse-
quence is that, although Q is a specific amount of
energy, the energy spectrum of the ß− particles is
continuous from zero to a certain maximum en-
ergy at Eßmax = Q. The energy distribution is such
that the maximum in this distribution is at an en-
ergy about one third of the maximum energy.
As mentioned above, in some cases the result-
ing daughter nucleus is not in an excited state, so
that no γ radiation is emitted. This happens to be
the case with the two isotopes that are relevant in
isotope hydrology, viz. 3H and 14C.
5.2.2. Positron (β+) decay
This type of nuclear transformation involves
the emission of a positron or ß+ (beta plus) parti-
cle as the result of a transformation inside the nu-
cleus of a proton into a neutron:
p+ → n + e+ + ν + Q (5.4)
and, because after slowing down the positron re-
acts fast with an electron anywhere present:
 INTRODUCTION

e+ + e− → 2γ (5.5)
Here two electron masses are transformed into
energy. The process is called annihilation, the en-
ergy released annihilation energy. With the mass
of the electron

me = 5.4858026 × 10−4 (5.6)
the resulting energy is 1.022 MeV, which is rep-
resented by two oppositely directed g particles of
511 keV each. This type of decay is, for instance,
known from naturally occurring 40K (Fig. 5.2).

5.2.3. Electron capture (EC)

The nucleus may pick up one electron from
the atomic electrons circling the nucleus in con- Fig. 5.1.  Different modes of radioactive decay visual-
secutive shells. In that case the following reaction ised on one spot of the chart of nuclides (cf. Fig. 1.2).
takes place: N is the number of neutrons, Z the number of protons.

p+ + e− → n + ν + Q (5.7)
to the ground state by emitting short-wave elec-
Depending on from which atomic shell the elec-
tromagnetic radiation, viz. low-energy g rays or
tron is caught by the nucleus, electron capture is
called K capture, L capture, and so on. β+ decay X rays. As in the previous decay modes, the ex-
and EC leave the mass number A of the nucleus
cited state of the nucleus causes the emission of
unchanged, while Z becomes Z–1 (Fig. 5.1).
The atom is left in an excited state and returns one or more g rays.

Fig. 5.2.  Decay schemes for some nuclides obeying β-, β+ or EC decay, the latter example of 40K in branching
decay, and the consecutive g radiation by the excited daughter nucleus as well as the formation of 2 g by annihila-
tion of an emitted β+ particle.

44
 rADIOnuclide DECAY and production

5.2.4. Alpha (α) decay

α (alpha) decay involves the emission of an
α particle (a 4He nucleus):
A
Z X → A −4
Z−2 Y + 4
2 He Fig.(5.8)
5.3. Après la désintégration radioactive, le noyau fils M et la plus petite particu
exemple, une particule α) se déplacent en directions opposées, portant en
This type of decay occurs primarily within de désintégration en tant qu’énergie cinétique.
the heavy elements such as in the uranium and Fig. 5.3.  After radioactive decay the daughter nucleus
thorium series. The emission of the heavy α par- M and the smaller emitted particle m (for instance, an
ticle practically coincides with the emission of movedeinl’impulsion
opposite direction,
α particle)
Le principe de conservation nécessite:together carry-
relatively large-energy g rays. ing the decay energy as the respective kinetic energies.
Because as in all cases the reaction energy Q MV + mv = 0 ou M2V2 = m2v2
is shared by the atoms Y and He according to
the two conservation laws, the case of α emission
tandis que le whileprincipe de conservation de l’énergie nécessite quere-
l’énergie de désintég
the principle of conservation of energy
is special. As with a gun shot, where the rifleman
à la somme des deuxthe decay
énergies cinétiques:
quires energy to be equal to the sum of
feels a large momentum against his shoulder,
the two kinetic energies:
the daughter nucleus receives a relatively large
Edésintégration = ½ MV2 + ½ mv2 = EM + Em
so-called recoil. This is particularly important Edecay = ½ MV 2 + ½ mv 2 = EM + Em (5.10)
where the recoil energy is large enough to loose
the daughter nucleus from its chemical bond. A partir
Thisde l’Eq.From 5.9,Eq. 5.9
nous avons:
we have:
phenomenon is the basis for studying the natural 1 1 1 m
abundance of the decay nuclides of uranium and E M = MV 2 = M 2V 2 = m 2v 2 = E
2 2M Chapter 52M Chapter 5 M m
thorium. In Sect. 5.3 we will deal with recoil en-
ergy quantitatively. (5.11) Chapter 5
Avec l’Eq. 5.10:
 With m Eq. 5.10:
  m
Edecay = 1E +decay =Em1 +  Em
5.2.5. Spontaneous and induced  M   m M
⎛  m⎞
E désintégra
E =  1
tion += ⎜1+E ⎟ E m
fission, neutron emission decay
 M ⎝  M m ⎠

Nuclides of the heavy elements so havethatthe possibil-

thesotwo thatparticle
the twoenergies
particleare, energies
respectively:
are, respectively:
so that the two particle energies are, respectively:
ity of breaking up into two relatively largesodaugh-
that the two particle energies are, respectively:
ter nuclei together with the emission of a number M M m m
Em = Em E=decay Edecay
and and and EM = EM E=decay Edecay (5
of neutrons. This decay may occur spontane- M + m MM+ m M + m Mm+ m
ously as well as induced by the bombardment Em = Edecay and EM = (5.12)Edecay
of the parent nucleus by a neutron from else- M + m238 238
M +m
In the case In ofthethecaseα of decaythe of α decay U with of a Udecay with energy
a decayofenergy about 4.2 of about
MeV,4.2 theMe da
where, for instance from a neighbouring nucleus.
234 234In the case of the α decay of 238
U with a decay
This is the dominant process innucleus,
nuclear In nucleus,
Th,
the receives
reactors Th,
case energy
of theareceives
recoil
α decay energy
a recoil ofU
of 238 energy
[4/(234+4)]
with of × 4.2
[4/(234+4)]
a decay MeV
energy × 4.2= 71 MeVkeV,= mo 71
of about 4.2 MeV, the daughter nucleus,of about 4.2 Me
(Sect. 5.4.2; Chapter 12). enough tonucleus,
enough
break the to
234break
chemical the chemical
bond between
bond the
between
Th
Th,
234
Th,receives
receives a recoil
a recoilenergy of atom
energy the[4/(234+4)]
and
Th atom
[4/(234+4)]
of the ×surrounding
and
4.2 the
MeVsurround
=atoms
71
mineral (see mineral
Sect.12.14
(see × Sect.12.14
and
4.2 Volume
MeV  and
=  4
71Volume
on Groundwater)
keV, 4 on
more Groundwater)
than
enough to break the chemical bond between the Th atom and the surroundi for a discussion
enough fortoa discussion
of the consequ
of th
5.3. Recoil by radioactive decay break the chemical bond between the Th atom
mineral (see Sect.12.14 and Volume 4 on Groundwater) for a discussion of the
and the surrounding atoms in the mineral (see
5.4
In the preceding chapter we mentioned 5.4NUCLEAR
the phe- NUCLEAR
Sect. 12.14REACTIONS and REACTIONS
Volume 4 on Groundwater) for
nomenon of the recoil momentum and ener- a discussion of the consequences.
gy which any decaying nucleus The overall 5.4
The
experiences. overallNUCLEAR
principle of a nuclear
principle REACTIONS
of areaction
nuclear isreaction
that a nucleus
is that aisnucleus
bombarded is bombarded
by a particleby
However, in the case of a heavyinparticle
the firstThesuch
in as
instance
the firsttaken
overall instance up by
principle taken
ofthe up
nucleus
by the
a nuclear tonucleus
form aisto
reaction compound
form
that a compound
nucleus
a nucleus nucleus
. This
is bombarded does. by
Th
no
the α particle leaving the nucleus, the effect
in a stable is
inthe not
particle.
a stable 5.4.
Within Nuclear
particle.taken
anWithin
extremely reactions
anthe
extremely
short timeto
short
the compound
time the compound
nucleus will
nucleulo
in
negligibly small. We will now calculate the recoil first instance up by nucleus form a compound nucleus . Thi
excess energy
excess by The overall oneprinciple oneof ora nuclear reaction is
energy by considering the classical in
mechanics ofenergy
a stablethe particle.
release
that
by the ofWithin
a nucleus
releaseoran
is
of
more particles,
extremely
bombarded
more
by
ultimately
particles,
short time the
a particle
ultimately
forming
that
compound
is
aforming
newnucleu
nuclid
an
this process (Fig. 5.3). bombarding bombarding
excessparticles
energy may
particles
be "man-made"
may beof"man-made"and originate
and from
originatea nuclear
from aparticle
nuclearacce
apan
in bythe thefirstrelease
instanceone takenor more
up byparticles,
the  nucleus ultimately
to forming
The  principle of conservation of (electrically
momentum (electrically
charged
re- particles)
bombarding charged
form particles)
or
a compound
particles may a nuclear or areactor
be nucleus. nuclear
"man-made" This(high-
reactor
does
and or
notlow-energy
(high- or
in low-energy
resultfrom
originate neutrons),
a nuclear neu or
par
quires: from natural from origin.
naturala stable
(electrically origin. particle.
charged particles)Within an extremely
or a nuclear reactor short(high-time
or low-energy neut
the compound nucleus will loose the excess en-
2 from natural origin.
MV + mv = 0 or M 2V 2A= few
m 2v examples
A few
(5.9) examples
may ergy
serve may
to the release
by show
servethe to convention
show
of one theorconvention
of writing
more of
nuclear
particles,writing
ulti-reactions:
nuclear reaction
A few
36
examples36
may serve to show the convention of writing nuclear reaction
Ar + n → p ++36nCl→ p + 36
Ar orCl 36
Ar(n,p)3636Cl
or Ar(n,p)36Cl
36
45
Ar + n → p + 36Cl or 36
Ar(n,p)36Cl
40 40
Ca + n → α ++37nAr
Ca → α + 37
orAr 40
Ca(n.α)37
or 40
Ca(n.α)37Ar
Ar (5
40 37 40 37
Ca + n → α + Ar or Ca(n.α) Ar
 INTRODUCTION
mately forming a new nuclide. The bombarding
particles may be ‘man-made’ and originate from
a nuclear particle accelerator (electrically charged
particles) or a nuclear reactor (high- or low-ener-
gy neutrons), or may be from natural origin.
A few examples may serve to show the conven-
tion of writing nuclear reactions:
36
Ar + n → p + 36Cl or 36
Ar(n,p)36Cl
40
Ca + n → α + 37Ar or 40
Ca(n.α)37Ar
40
Ar + n → 2n + 39Ar or 40
Ar(n,2n)39Ar
(5.13)
5.4.1. Natural production
Nature is constantly and intensively performing
nuclear reactions. The bombarding particles orig-
inate from two sources:
(1) From cosmic radiation, an avalanche of
fragments of atmospheric nuclei, a wide
range of particles from photons and electrons
to neutrons and mesons. These are primarily
produced as secondary and tertiary particles
in the upper atmosphere in a process called
spallation, by very-high-energy cosmic
protons and a smaller percentage of helium
nuclei from the sun, from further away in
our Galaxy and probably from extragalac-
tic space. Mesons reaching the earth surface
have a very high penetrating power and can
be observed at great depth below the ground
or water surface.
Variations in cosmic radiation occur because
the origin is to be found in events such as
solar flares and supernova explosions. Also
indirectly does the sun influence the cosmic
ray flux in the  atmosphere. The  fact is that
part of the incoming primary particles are
deflected away from the  earth by the  earth’
magnetic field, which has not been entirely
constant through geologic times. The vari-
able magnetic field of the  sun now adds to
the variations in the earth’ magnetic field and
thus in the shielding capacity of the earth
against cosmic particles.
Cosmic radiation produces radioactive nu-
clei in the atmosphere primarily through two
different types of reactions:
(a) high-energy reactions by the second-
ary particles such as protons, neutrons
46
and He nuclei bombarding atmospheric
nuclei (N, O, Ar); these reactions are
the origin of the atmospheric abundance
of nuclides such as 3H, 7Be, 26Al, 32Si,
39
Ar and 85Kr;
(b) low-energy reactions by thermal neu-
trons, of which the production of 14C in
the air is the best known example.
These reactions will be discussed later to-
gether with the specific treatment of the vari-
ous isotopes (Chapters 8 and 12).
(2) From nuclear decay particles, primarily
neutrons from spontaneous decay of nuclides
of the uranium, actinium and thorium decay
series. These processes occur underground
depending on the U or Th content of the soil
minerals (Chapter 12).
5.4.2. Anthropogenic releases of
radionuclides
Also man has become able to produce nuclei and
even elements, presently unknown in nature, on
a small scale in the laboratory, but also on a large
scale in the natural environment by the test explo-
sion of nuclear weapons.
The anthropogenic releases of radioactivity are
related to these nuclear weapons testings as well
as to the regular or incidental releases by nuclear
(power) industries.
The release of radioactivity related to the testing
of nuclear weapons has two main causes, viz.:
(1) Fission bombs, based on the neutron-in-
duced fission reaction of uranium or pluto-
nium:
235
U + n → nucleus
with A ≈ 85−100 + nucleus
with A ≈ 130 – 145 + neutrons
and likewise
239
Pu + n → nucleus
with A  ≈ 95 – 105 + nucleus
with A ≈ 132 – 142 + neutrons
Well-known examples of radioactive nu-
clides as products of the asymmetrical mass
distribution of the  long-living fission prod-
ucts are 93Zr and 99Tc on the one hand, and
129
I and 137Cs on the other. Industrial activi-
ties concerning nuclear power production
and fuel reprocessing may bring on a small
scale nuclear waste materials in the environ-
 rADIOnuclide DECAY and production

ment, similar to those that are being pro- is sufficiently high to produce radioactive
duced by the bomb explosions. nuclides that are also being made by nature
itself:
A special case of nuclear waste release is
the occurrence of nuclear reactor incidents. 14
N + n → 12
C + 3H or 14N(n,3H)12C
In some cases (Chernobyl in 1986) sufficient a n d
radioactivity was injected into the environ- 14
N + n → 14C + 1H or 14N(n,p)14C
ment to detect certain isotopes in nature, for 3
H (tritium) and 14C (radiocarbon), and other
instance in sediments and ice cores.
cosmogenically as well as anthropogenically
(2) During the nuclear explosions especially produced isotopes will be discussed in detail
the neutron density in the surrounding air in Chapter 8 and 12.

47
 6. EQUATIONS OF RADIOACTIVE DECAY AND GROWTH

6
The mathematical expressions presented in this 1000

EQUATIONS DE DESINTEGRATION ET
chapter are generally applicable to all those pro-
cesses in which the transition of the parent nucle- 800 A0

CROISSANCE RADIOACTIVE
us to a daughter nucleus, i.e. the process of ra-
dioactive decay, is governed by statistical chance.
T 1/2
2T 1/2
600
This chance of decay is equivalent to the degree

A
of instability of the parent nucleus. Each radioac- 1/2 A 0
400
tive nuclide has its specific degree of instability
which, as we will see, is going to be expressed by
200 1/4 A 0
the half-life
Les expressions assigned
mathématiques to this dans
présentées nuclide.
ce chapitre sont généralement applicables à tous les
processus dans lesquels la transition
The radioactivity du noyauis père
of a sample noyau fils, i.e. le processus de décroissance
moreaucomplicat- 0
radioactive, est
ed if it consists of two or more components,chance
gouverné par des chances statistiques. Cette such de désintégration
0
est équivalente
10 20 30 40 50 60 70 80 90 100
as: (i) in du
au degré d’instabilité the case
noyau of a mixture
père. Chaque of independent
nucléide ac-a son degré spécifique d’instabilité
radioactif time in hours
tivities, (ii) if one specific type of nuclide shows
qui, comme nous allons le voir, est exprimé par la demi-vie associée à ce nucléide.
two modes of decay, so-called branching decay, Fig. 6.1.  The  ratecomposants,
of radioactive decay. After each
La radioactivité
and d’un
(iii) échantillon
if we are est plus compliquée
dealing si il comporte
with a nuclear decay deux ou plusieurs
subsequent half-life of 20 hours the  number of ra-
coe: (i) dansseries
le casind’un
whichmélange d’activités indépendantes,
also the daughter nuclides are(ii)
ra- si undioactive
type spécifique de nucléide
nuclei and the original radioactivity of 800
montre deuxdioactive.
modes de All décroissance, appelés décroissance
these phenomena multidirectionnelle, et (iii) si nous nous
will be discussed units are divided into half.
intéressons àseparately.
une série de désintégration radioactive dans laquelle les noyaux fils sont radioactifs.
Tous ces phénomènes seront discutés séparément.
ln(N/N0) = −λt (6.4)
6.1. Law of radioactive decay
6.1 LOI DE DÉCROISSANCE RADIOACTIVE and subsequently the equation of exponential de-
The fundamental law of radioactive decay is cay:
based ondethe fact
La loi fondamentale that the decay,
décroissance radioactive i.e. the transi-
est basée sur le fait que la décroissance, i.e. la
tionnoyau
transition d’un of a parent
père à un nucleus
noyau to
filsa daughter nucleus
est un processus is
purement Nstatistique.
= N 0e−λt La probabilité de (6.5)
désintégrationa purely statistical
(décroissance) est uneprocess.
propriétéThe disintegration
fondamentale du noyau atomique et reste équivalente
dans le temps.(decay) probability cette
Mathématiquement, is a fundamental property
loi s’exprime ainsi: or using Eq. 6.3:
of an atomic nucleus and remains equal in time.
Mathematically this law is expressed as: A = A0e−λt (6.6)
dN = λN dt (6.1)
dN = λN dt (6.1) The time during which A0 decreased to
et A (= the age of the material) is:
and
(− d N / d t ) T = (1/λ)ln(A/A0) (6.7)
λ= (6.2) (6.2)
N The relations of Eqs.6.5 and 6.6 indicate the rate
where N is the number of radioactive nuclei, –dN/ at which the original number of radioactive nuclei
ou N est le nombre de noyaux radioactifs, -dN/dt la décroissance
dt the decrease (negative) of this number per unit (N 0)deand
(négative) the original
ce nombre radioactivity
par unité de (A0) decrease
temps, et λ est
of donc
time laand
probabilité
λ is thusdethe probability
désintégration par noyau per
of decay in time
et par unité (Fig. 6.1).
de temps. Cette constante
nucleus
de désintégration λ estper unit of pour
spécifique This decay
time.chaque mode deconstant λ is de chaque nucléide.
désintégration
specific for each decay mode of each nuclide. 6.2. Half-life and mean life
La radioactivité ou taux de désintégration est définie comme le nombre de désintégration par unité de
temps: The  radioactivity or decay rate is defined as It is a common practice to use the half-life (T1/2)
the number of disintegrations per unit of time:
instead of the decay constant (λ) for indicating
A = −dN/dt = λN the degree of instability
(6.3) or the decay rate of a ra-
A = −dN/dt = λN (6.3)
dioactive nuclide. This is defined as the  period
By integration of this relation and applying of time in which half of the radioactivity has dis-
the boundary conditions that at in the beginning appeared (half of the nuclei have disintegrated,
t = 0 and N = N0 we obtain: Fig. 6.1):
75
 Il est de pratique courante d’utiliser la demi-vie (T1/2) à la place de la constante de décroissance
Il est de pratique
radioactive (λ) pourcourante
indiquerd’utiliser demi-vie (T
le degré lad’instabilité ) à ladeplace
ou1/2taux de la constante
décroissance de décroissance
d’un nucléide radioactif.
VIE MOYENNE
6.2radioactive
Celle λ) pourcomme
ci estDEMI-VIE
(définie ET VIE
indiquer
la leMOYENNE
degréde
période d’instabilité ou taux
temps au bout de décroissance
duquel la moitié de lad’un nucléide radioactif.
radioactivité a disparue
Celle ci demi-vie
(la moitié
d’utiliser estdes
définie(Tcomme
nucléides laplace
période
sed’utiliser
sont de temps
désintégrés, Fig.au bout décroissance
6.1): duquel la moitié de la radioactivité a disparue
Il est dela pratique 1/2) à la
courante de
la la constante
demi-vie (T1/2de
) à la place de la constante de décroissance
(la moitié
r leradioactive des
degré d’instabiliténucléides se sont désintégrés, Fig. 6.1): INTRODUCTION
(λ) pour ou taux de
indiquer le décroissance d’un nucléide
degré d’instabilité ou taux deradioactif.
décroissance d’un nucléide radioactif.
a période T1/2
au = λ)ln(1/2)
(−1/duquel (6.8)
Celle cideesttemps
définie bout
comme la moitié
la période de la radioactivité
de temps au bout duquel a disparue
la moitié de la radioactivité a disparue
T1/2 = (−1/λ)ln(1/2) (6.8)
ont (la
désintégrés,
moitié desFig. T1/2
6.1):
= (−1/λ)ln(1/2)
nucléides
se sont désintégrés, Fig. 6.1): (6.8) where:
A partir de quoi : λ = (ln2)/T1/2 = (ln2)/12.43 a (1 year = 3.16 × 107 s)
A partir de quoifrom: which:
N = 2 × 10 – 18 (G/M)
1/2) T1/2 = (−1/λ)ln(1/2) (6.8) (6.8)× A (G/M = number of
ln 2 0,693 moles)
λ= = (6.9) (6.9)
ln
T 22 0T,693 A = Avogadro’s number = 6.02 × 1023/mol
A partir de quoiλ: = 1 / = 1/ 2 (6.9)
T1 / 2 T1 / 2 M = molecular weight = 18.0
The mean life of a nuclide is the sum of the life pCi = pico-Curie = 10  – 12
Curie = 3.7 × 10 – 2 dps
93 La vie moyenne lnd’un
times 2 of nucléide
,693 estnumber
0a certain la somme des temps de demi-vie d’un
of nuclei (before they nombre de noyaux donnés
La λ = d’un= nucléide est la somme des temps de(6.9)
vie qu’ils
moyenne demi-vie = 0.037
d’un nombre Bq (6.9) donnés
de noyaux
2
(avant neTse all
have soientT1 /tous désintégrés)
disintegrated) divisée
divided by par le nombre
the number ofdesdits noyaux. Pendant l’intervalle
1/ 2 2
(avant
de tempsqu’ils ne
un se
dt, nuclei. soient
nombre tous
dN de désintégrés)
noyaux se divisée
désintègre.
During the time interval dt a number ofpar le
Ils nombre
ont « desdits
existé » noyaux.
pendant Pendant
The numerical
une l’intervalle
result
période t, for
ce qui water with 1 TU of tri-
estdelatemps
correspond dt,àdes
un nombre
dN nuclei
temps dedN de noyaux
disintegrate.
vie global, senombre
These
pour désintègre.
dN ‘lived’ during existé » tium
Ils ont donnés
«a pe- is: une période t, ce qui
pendant
de La vie somme
moyenne temps
d’un de
nucléide demi-vie
est d’un
la somme desnoyaux,
temps de:
de noyaux
de demi-vie d’un nombre de noyaux donnés
correspond
us désintégrés) à riod
un t,
temps which
de vie amounts
global, to
pour a total
dN life
noyaux, time
de: for dN
(avant qu’ilsdivisée par letous
ne se soient nombre desdits noyaux.
désintégrés) Pendant
divisée par l’intervalle
le nombre desdits noyaux. Pendant
Aspec = 0.118 l’intervalle
Bq/L = 3.19 pCi/L (6.11)
nuclei
tdN = tλof Ndt(cf. Eq. 6.3):
dede
noyaux
tempssedt,désintègre.
un nombreIlsdNont
de«noyaux
existé »sependant Ils ont «t,existé
une période
désintègre. ce qui» pendant une période t, ce qui
tdN = tλNdt As another example we can calculate the 14C
e global, pour dN noyaux,
correspond à untdN temps de:
de vie global, pour dN noyaux, de:
= tλNdt
L’intégration pour tous les noyaux (N) donne la période de demi-vie (temps): concentration in carbon, which has a  specific
L’intégrationIntegrating
pour tous lesover
noyaux
all (N) donne
nuclei (N)lagives
période de demi-vie
the mean life (temps):
14
C activity of 13.56 dpm per gram of carbon
tdN = tλNdt
(time): 1
∞ ∞
⎧ t ∞ 1 (in
∞
the year
⎫ AD 1950) (see 14C standard activity,
τ = 0 ∞∫ tλN d t = λ∞∫ t ⋅ e −λt d t = λ⎧⎨− e −λt 0 + ∞∫ e Chapter − λt
d t⎫⎬ 8):
oyaux (N) donnepour
L’intégration N1 les
laτ période
=tous denoyaux
demi-vie
N d t =(N) λ(temps):
0 donne
t ⋅ e −λt la d tpériode
= λ ⎨⎩− de λt edemi-vie
− λt ∞ 1λ −λt
+(temps):
0 ∫ ∫ ∫00 e 14 Cd t ⎬⎭⎭13.56 × 5730(6.10)
0 tλ
N 0 ⎩ λ 0
λ × (3.16 × 10 7 ) × 12
⎧ 1 ⎛ 1 − λt ∞ ⎞ ⎫ 1
0
= (6.10) = 1.2 × 10 −12
∞ =⎧λ∞⎨t0 + ⎜ − ∞e ∞
1 ⎟⎫⎬ = ⎫ ⎧ ∞
C ⎫ 60 × ln 2 × ( 6. 02 × 10 23
)
1 ⎧ −1 1 1 t 1
d t = λ ∫ t ⋅ e dτt == λ=⎨0λ−∫⎨⎩t0λ+eN λd t⎛⎜⎝−= λ et−λ⋅tee−λt ⎞⎟⎠dd⎭tt=⎬= λλ − e −λt
∞ 0
∫
− λt λ t −∞λ t ∞
0 λ∫
+ ⎬ ⎨ + ∫ e − λt d t ⎬
N⎩ 0⎩λ λ ⎝ λ 0λ 0 0
⎠⎭ ⎭ λ ⎩ λ
0
λ (6.12)
0
(6.10) 0 ⎭ (6.10)
⎫ 1 ⎧ la vie
1 A−λttitre∞ ⎞d’exemple, 1 ⎛ 1
moyenne d’un
∞ ⎞ ⎫ noyau 1 de 14
C avec T 1/2 = 5730 ans est de 8267 ans. Ainsi λ =
− e ⎟⎬ = = λ ⎨0 + ⎜ − e −λt 0 ⎟⎬ =
λ A titre
1/8267, 0 d’exemple,
⎠⎭ λ ⎩
ce qui la
signifie vie que
λ⎝ λ moyenne
l’activité d’und’un noyau de
échantillon
⎠⎭ λ (6.10)
14
C avec
décroît T de
1/2 = 5730
1‰ en 6.4.
ans est
environ Mixture
de 8 8267
ans; ans. of
Ainsi
l’activité independent
λ=
d’un
1/8267,
échantillon ce qui
de signifie
3
H (T1/2 =que 12,43 l’activité
a), quantd’un échantillon
à elle, diminuedécroîtde 5,6% depar1‰an. radioactivities
en environ 8 ans; l’activité d’un
échantillon deAs3 an example, the mean life of a 14C nucleus with
H 14(T1/2 = 12,43 a), quant à elle, diminue de 5,6% par an.
yenne d’un noyau de laCvie avec T1/2 = 5730 ans estde λ = ansFig.  6.28267 shows ans. a semi-logarithmic decay curve
years.deThen 8267 ans.T1/2Ainsi
14
A titre d’exemple, T1/2 = 5730 moyenne a is d’un
8267noyau C avec = 5730
λ = 1/8267, est de Ainsi λ =
6.3 d’un
’activité
1/8267, ce qui ACTIVITE,
échantillon
signifie
which que décroît
means ACTIVITE
de
l’activité 1‰d’un
that en SPECIFIQUE
environ
a sample échantillon 8 ans;
activity ET CONCENTRATION
l’activité
décroît de 1‰
decreases d’un of a mixture
en environ 8 ans; of two
EN l’activité d’un activities that are completely
43 a), 6.3
quant à elle, de 3ACTIVITE,
RADIONUCLEIDES
diminue ACTIVITE à SPECIFIQUE deET par an. independent,
CONCENTRATION EN a composite decay curve. If the half-
échantillon by
H (T1‰1/2 = dein 5,6%
12,43 abouta),par 8an.
quant years;elle, a  H sample
diminue 5,6% activity
3

RADIONUCLEIDES
(T1/2  = 12.43 a ) decreases by 5.6% life values are sufficiently apart, it is seen to be
L’activité d’un échantillon donné est le nombre de per year.
désintégrations radioactives
possible par secondethe two
to unravel pour cetseparate decay curves,
CTIVITE SPECIFIQUE
6.3L’activité d’un
ACTIVITE, ET
échantillon CONCENTRATION
ACTIVITEdonné est le nombre
SPECIFIQUE EN
échantillon dans son ensemble. L’activité spécifique, d’un autre côté, eststarting de désintégrations
ET CONCENTRATION radioactives EN
définie commepar secondele nombrecet
pour de side of the curve,
at the right-hand
EIDES échantillon
désintégrations dans
6.3. sonActivity,
RADIONUCLEIDES
par ensemble.
unité de poids L’activité
specific
ou de volume spécifique,
activity d’un autre
d’échantillon and côté,
(voir act.estspéc.
définie
du comme
14
C et 3
H,le nombre
Chapitre de
8).
where the one activity has already disappeared.
désintégrations
L’unité de par unité
radioactivité de
radionuclide
est poids
le ou de
Becquerel volume
concentration
(Bq), d’échantillon
qui est défini (voir
commeact. spéc. du 14de
le taux
Subtracting C et 3
H, Chapitre par
désintégration
the straight 8).
donné est le nombre
L’activité de désintégrations
d’un échantillon donné estradioactives
le nombre de pardésintégrations
seconde pour cet radioactives par seconde pour cet semi-logarithmic curve
L’unité
seconde de radioactivitéd’un est Becquerel
le.échantillon
L’activité (dps) ou, aujourd’hui
dansThe activity
spécifique,
son ensemble. ofleL’activité
autre obsolète,
a certain
côté, le (Bq),
Curiecomme
sample
est spécifique,
définie qui
(Ci)
is est
qui défini
étaitcôté,
the number
d’un leautre
nombre comme
défini
ofdeestcomme le taux
from
définie
de désintégration
lethe composite
taux
comme curve
deledésintégration
nombre
par
de gives the straight line
poids seconde
de
ou3,7 (dps)
10 ou, aujourd’hui obsolète, le Curie
× 10 a radioactive
de volume dps.
d’échantillon disintegrations
(voir spéc. duper 14 (Ci)
Csec
et 3H,qui était
forChapitre
the sam-défini for the shorter-lived
comme le taux de nuclide.
désintégration
désintégrations 10
par unité de poids ouact.
de volume d’échantillon (voir act. 8). spéc. du 14C et 3H, Chapitre 8).
de 3,7
Becquerel
le L’unité × 10(Bq), dps.
plequias est
a whole.
défini The specific
comme activity, est on the other
A titreded’exemple
radioactivité de la estrelation entre lel’activité
le Becquerel taux
(Bq), despécifique
qui désintégration
défini comme
d’un par le taux et
échantillon de ladésintégration
concentrationpar d’un
hand, is defined as the number of disintegrations
ui obsolète,
seconde
A titre le
(dps) Curie
ou,
d’exemple
noyau radioactif, (Ci) de qui
aujourd’huila
nousweightétait
relation défini
obsolète,
allons calculer comme
entre le Curie
l’activitéle
l’activité taux
(Ci) de
qui désintégration
spécifiqueétait
spécifique défini
d’un comme
échantillon 6.5. Branching
3 le taux
et la de désintégration
concentration decay
d’un
103
per unit or volume of sample (see en tritium ( H) d’une eau contenant un
spec.
18 allons calculer l’activité spécifique en tritium (3H) d’une eau contenant un
denoyau
3,7 × 10
atome radioactif,
de dps.
H pour nous
10 14 atomes 3d’hydrogène (équivalent à 1 UT = Unité Tritium — cf. Chapitre 8):
act. of 18 C and H, Chapter 8). The unit of radio- Also in nature radioactive nuclides exist that
atome de 3H pour activity10 is atomes d’hydrogène
the Becquerel (équivalent
(Bq), which à is
1 UT = d’un
defined Unité Tritiumshow — cf.
two Chapitremodes
different 8):
tion entre l’activité spécifique d’un échantillon et la
A titre d’exemple de la relation entre l’activité spécifique d’un échantillon et la concentration concentration d’un 77of decay. One example
ns noyau
calculerradioactif, as
l’activité nous a decay
spécifique rate
allons en
of
calculer
one disintegration
3
( H) d’une
tritiuml’activité per
eau contenant
spécifique
second
en tritium un ( H) d’une eau contenant uncan
3 is presented by 40
K that 77 decay with the emis-
s d’hydrogène
(dps) or the now obsolete Curie (Ci) which was sion of a β or a β particle (Fig. 5.1).
- +
atome de 3H (équivalent
pour 1018 atomes à 1 UTd’hydrogène
= Unité Tritium — cf. Chapitre
(équivalent à 1 UT =8): Unité Tritium — cf. Chapitre 8):
defined as a decay rate of 3.7 × 1010 dps.
77 Each decay mode has 77 its specific decay constant
As an example of the relation between the specif- or half-life. The total decay is simply the sum of
ic activity of a sample and the actual concentra- both single chances and is thus given by:
tion of the radioactive nuclide, we will calculate
the specific tritium (3H) activity of water contain- λtotal = λ1 + λ2 (6.13)
ing one 3H atom per 1018 hydrogen atoms (equiv-
alent to 1 TU = Tritium Unit (Chapter 8): and the total half-life consequently by:

Aspec = λN (par litre) (1/T1/2)total = (1/T1/2)1 + (1/T1/2)2 (6.14)

50
 celle des séries de U et Th (Part.12.14-12.16).

Dans ce contexte, nous pouvons nous limiter à un seul élément de cette chaîne
multiple:
Dans la relationnous
ce contexte, entre pouvons
une activité
nouspère et fils.à Les
limiter relations
un seul d’un de
élément deuxième et plu
cette chaîne
EQUATIONS OFété traitéeslapar
multiple:
RADIOACTIVE ailleurs
relation
DECAY (voir
entre
ANDunelesactivité
livres de
GROWTH Friedlander
père et fils. Leset relations
al. et de Faure).
d’un deuxième et plu
été traitéespère
Le noyau par ailleurs
décroît (voir les livres
en accord avecdelesFriedlander
équations et
deal.
la et de Faure). radioactive tr
décroissance
6.6. Radioactive decay seriespartie:
Le noyau père décroît en accord avec les équations de la décroissance radioactive tr
partie:
If a radioactive nuclide is situated in the Chart ofZ
Nuclides far from the stability line (for the light d N1
A1 = − = λ1 N 1
elements at Z = N), the daughter nucleus after ddNt 1
A1 = − = λ1 N 1
radioactive decay may be radioactive as well. dt
α decay
In nature this occurs with the heavy nuclides et in
the uranium and thorium decay series (Chapter et
12). Here the original decay of 238U or 232Th is fol- N 1 = N 10 e − λ1t and A1 = A10 e − λ1t β decay
lowed by a series of radioactive decay products.
Fig.6.3. Représentation schématique d’une hypothétique courbe de décroissance e − λ1t and
N 1 = N 10 multiple, 0 −λ t
NA =à A e 1
analogue
Fig. 6.3 shows schematically how the elements of 1 1
celle Fig. 6.3.  multiple,
Schematic representation
à deux of a  hypothetical
suchdes séries
Fig.6.3. Représentation
decay de Uare
et Th
schématique
series (Part.12.14-12.16).
d’une La quantité
hypothétique courbe
related. de noyaux
de décroissance fils est fonction
analogue de processus: (i) la décroissance radio
celle des séries de U et Th (Part.12.14-12.16). croissance multiple
La quantitéradioactive
de noyaux decay
par curve, analogous
filsdécroissance
est fonctiondes to the decay
denoyaux
deux curves
(i) laof décroissance radio
pères, respectivement:
processus:
In this context we can restrict ourselves to one el- the U and Th decay series (Sect. 12.14 – 12.16).
croissance radioactive par décroissance des noyaux pères, respectivement:
ementnous
Dans ce contexte, frompouvons
the multiple
nous decay
limiter chain: the relation
à un seul élément de dcette
between a parent and a daughter activity. The re- N 2 chaîne de décroissance
multiple: la relationnous
Dans ce contexte, entre pouvons
une activité
nouspère et fils.à Les
limiter relations
un seul d’un deuxième=
élément et−λplus + λ1niveau
2 N 2haut N1 on
lations in a second and higher degree have been de dcette
dNt 2 chaîne de décroissance
= − λ N + λ N (6.17)
été traitéeslapar
multiple: ailleurs
relation (voir
entre lesactivité
une livres de Friedlander
père et fils. Leset relations
al. et de Faure).
d’un deuxième et plus 2 2haut 1niveau
1 on
treated elsewhere (see textbooks by Friedlander dt
été traitéespère
Le noyau par
etailleurs
al. and(voir
décroît les livres
byaccord
en Faure). avecdelesFriedlander
équations et
deal.
la et
Ladesolution
Faure).deradioactive
décroissance cette équation différentielle
traitées dans cetteest:
The solution of this differential equation is:
partie:
Le noyau père décroît en nucleus
The parent accord avec les équations
decays La solution deradioactive
accordingdetolathe equa-
décroissance cette équation différentielle
traitées dans cetteest:
λ1
N 1 (e −λ1t − e −λ2t ) + N 2 e −λ2t
0 0
partie: tions of radioactive decay which we have treated N2 = (6.18)
λ λ− λ
N 2 = 2 1 1 N 1 (eEquations − e −λ2tde) +Décroissance
N 2 e −λ2t Radioactive
0 − λ1t 0
d N1
in this section:
A1 = − = λ1 N 1 λat2 zero (6.15)
− λ1 activity
ddNt 1 while et
tandis qu’à activité temps zéro (N20at= zero
0): time (N2  = 0):
0

A1 = − = λ1 N 1 (6.15) (6.15)
λ2 (N20 =0 0):−λ1t −λ2t
A1 (e − e )
dt tandis qu’à activité et temps zéro
et 80 A 2 = λ 2 N 2 = (6.19)
and λ2 − λEquations
1 de Décroissance
Radioactive
et 80
The last term represents Equations de Décroissance Radioactive
N 1 = N 10 e − λ1t and A1 = A10 e − λ1t (6.16) the decay of the amount
Le(6.16)
dernier terme représentenuclide
of daughter la décroissance despresent
quantités at de noyaux fils présents au te
λ2 that 0 was the time
N = N 0 − λ1t
e and A = A 0 − λ1t
The amount of daughter nuclei is determined by
1 1 1 1 e évident que le A = λ
rapport
t =  N =
entre
2 0. 2It 2is obvious λ et (6.16)
λ
λ21λ−2 λet
A
est
2 that
1 (
e
le
− λ1t
−
facteur e )
− λ2 t
the ratio betweendétermine
principal qui λ1 l’évolution
La quantité de noyaux fils est fonction de
two processes: (i) radioactive decay anddansdeux processus: (i) la décroissance
(ii) lera-temps.and radioactive
λ2 2allons
2 = λ
ANous is
N 2the dominating
=maintenant
1 (ii)
(
0 la
e factor
− λ1t
A1 brièvement )
− e that
− λ2 t
rappelerdetermines
les trois différents cas relat
croissance
La quantitéradioactive
de noyauxpar
dioactive décroissance
growth
fils by decay
est fonction desdenoyaux
of
deux pères, respectivement:
the parent
processus: nuclei, the course
(i) la décroissance ofλthe daughter
radioactive2 − λet 1 (ii) la activity in time. We

respectively:
croissance radioactive Le dernier terme
par décroissance des noyaux pères, respectivement: shallreprésente
now briefly la décroissance
mention the 3 des different
quantités de noyaux
cases for fils présents au te
6.6.1 EQUILIBRE SECULAIRE
d N2 évident que lethis ratio.
rapport entre λ
Le dernier terme représente la1 décroissance et λ 2 est le facteur principal qui détermine
des quantités de noyaux fils présents l’évolution
au te
= −λ 2 N 2 + λ1 N 1 Ce type de relation entre activité (6.17)
père et fils intervient quand la demi vie du noyau pè
d
d N2t dans le temps. Nous allons maintenant brièvement rappeler
évident que le rapport entre λ1 et λ2 est le facteur principal qui détermine l’évolution les trois différents cas relat
1000 = −λ 2 N 2 + λ1 N 1 plus grande que celle du noyau fils. (6.17) On peut citer les exemples des relations entre le
dt dans le temps.6.6.1. Nous allons maintenant
Secular brièvement
equilibrium
238 235
rappeler les trois différents cas relat
232
La solution de cette équation différentielle est: longue,
6.6.1 de l’uranium et du
EQUILIBRE SECULAIRE thorium, U, U et Th, et leurs produits de décroissanc
12): This type of relation between parent and daugh-
La solution de cette équation
λ1 différentielle est: 6.6.1 EQUILIBRE
Ce type de relationter activity
entre activitéSECULAIRE
occurs whenetthe half-life
père fils intervientofquand the parent
la demi vie du noyau pè
N 100
2 =
0
( ) 0
N 1 e −λ1t − e −λ2t + N 2 e −λ2t
plus grande λnuclide
que << λ
1 celle 2 is duinfinitely
noyau fils.
(6.18)
larger than thatlesofexemples
the daugh-
λ 2 λ−1 λ1 0 −λ1t −λ2t pèreOn peut citer des relations entre pè
le
N2 = ( ) 0 Ce type de relation
N 1 e −T 1/2e = 10 hrs+ N 2 e −λ2t longue, de l’uranium
entre
ter nuclide.
activité
Examples
etdudunoyau
thorium, (6.18)
et fils intervient
238 are235the relations
U,père Uau 232
et coursTh,
quand la demi
between
et temps,
leurs produits
vie du noyau
de décroissanc
ln A

λ − λ1 zéro (N 0 = 0): L’Eq. 6.16 décrit

plus grande correctement
que celle l’activité
fils. On peut citer les du
exemples vu
desque l’Eq.
relations 6.19
entreselet
tandis qu’à activité et2temps 2 12):
the long-living isotopes 238
of235
uranium 232
and thorium,
longue, de l’uranium
238
U, 235U et duandthorium,
232
Th, andU,theirU decay et Th, et leurs produits
products (see de décroissanc
( )
10
tandis qu’à activité et temps zéro (N20 = 0): 0 − λ1t − λ2 t
80
12): A12<<
= λA21 12):
λChapter e −e
T 1/2 = 2 hrs
80 L’Eq. 6.16 décrit λ1 << λλ22
<<correctement l’activité père au cours du temps, vu que l’Eq. 6.19 se t
1 ou pour λ1 = 0,
L’Eq.26.16 Eq. 6.16
décrit properlyl’activité
correctement describes pèrethe parent
au cours duactivity
temps, vu in que l’Eq. 6.19 se t
10 (e e − λ2t ) turns into:
0 10 time in hours 0
time, whereas
A2 = A
0 − λ1t
−Eq. 6.19
A2 = A1 0(1 −− λet − λ2t )− λ t
Fig. 6.2.  Semi-logarithmic plot of a  composite decay A2 = A1 (e 1 − e 2 ) (6.20)
ou
curve for a  mixture of two independent radioactivepour λ1 = 0,
décrivant la or croissance
for λ1 = de
0, l’activité fille au cours du temps si nous prenons au dé
compounds with half-lives of 2 and 10 hours. ou The lon-
pour λ1 = 0,
Fig. 6.4 montre l’évolution
ger-lived activity can be subtracted from the sum curve A2 = A10 1 − e − λ2t ( (6.21) )
des deux activités. Enfin, (pour t → ∞ avec λ2t → ∞
(heavy line) to produce the  semi-logarithmicl’activité
straight fille atteint une valeur de:
decay curve for the shorter-lived nuclide.
0
A2 = A1 1 − e − λ2 t
( )
décrivant la croissance de l’activité fille au cours du temps si nous prenons au dé
A2 = A10 e − λ1t = A1
Fig. 6.4 montre
décrivant l’évolution
la croissance des deuxfille
de l’activité activités. Enfin,
au cours temps tsi→nous
du (pour ∞ avec λ2t →
prenons au ∞
dé
l’activité
Fig. 6.4 fille atteint
montre une valeur
l’évolution des de:
deux activités. Enfin, (pour t →51∞ avec λ2t → ∞
en d’autres termes, les activités mère et fille, deviennent équivalentes.
l’activité fille atteint une valeur de:
Le fait qu’uneAactivité 0 fille
− λ1t de vie courte puisse augmenter dans un échantillon conten
2 = A1 e = A1
vie longue0 −a λ1t été utilisé, par exemple dans les cas ou la mesure de la
A =A e =A
 0
(
A2 = A1 e − λ1t − e − λ2t ) (6.20)

ou pour λ1 = 0,
INTRODUCTION
0
A2 = A 1 − e
1 ( − λ2 t
) (6.21)
describing the growth of the daughter activity in 1000
décrivant la time if wedetake
croissance A2 = 0fille
l’activité in the beginning. Fig. 6.4
au cours du temps si nous prenons au départ
T =∞
A2 = 0. La
1/2

Fig. 6.4 montre shows the courses

l’évolution of both
des deux activities.
activités. Enfin, Finally
(pour t →(at∞ avec λ2t → ∞ dans l’Eq. 6.20)

ln A
l’activité fillet atteint
→ ∞ with λ2t →de:
une valeur ∞ in Eq. 6.20) the daughter ac-
tivity reaches a value of: T 1/2 = 0.8 hrs
100
A2 = A10 e − λ1t = A1 (6.22) (6.22)

in other words, parent and daughter activity be-

en d’autres termes, les activités mère et fille, deviennent équivalentes.
come equal.
Le fait qu’une activité fille de vie courte
The phenomenon that puisse augmentercontain-
inde a sample dans un échantillon
10 contenant un noyau de
Equations Décroissance Radioactive
vie longue a été utilisé, par exemple
ing a long-living nuclide a short-living daugh- dans les cas ou la mesure 0 de la radioactivité
5
timedu
in hours
10 15

noyau fils est may

ter activity plus facile
growque celle du noyau
is applied, père. Ce in
for instance Fig. 6.4.  àRelation
cas correspond betweende the  radioactivities of
la détermination
Chapitre 6
cases where
l’activité the radioactivity
de 32Si d’une demi vie de measurement
140 ans, quiofdécroîta  parent (straight line) and
par l’intermédiaire d’unea  daughter nuclide when
Chapitre 6
the daughter βnuclide the  parent nuclide decays infinitely slow as com-
décroissance −
basseis— easier thanvers
énergie that of
32 the par-
P d’une demi vie de 14,3 jours et une
ent activity. Such case is the activity determina- pared to the daughter nuclide (half-lives of ∞ and 0.8
décroissance β− haute — énergie. L’Eq. 6.21 montre querespectively),
hours, après avoiri.e.séparé
the  case of secular equilib-
tion of Si with a half-life of about 140 years,
32
chimiquement un 32Si pur, l’activité 32P augmente dans l‘échantillon
rium. à unline
The upper tauxrepresents
tel que the sum of parent and
which decays through a  low- energetic β decay -
après
to 32Pune
withdemi vie fille, of
a half-life l’activité fille s’est
14.3 days élevée à 50% dedaughter
and a high-en- sa valeuractivity.
maximum A1:
ergetic β- decay. Eq. 6.21 shows that after sepa- 1000
rating chemically a pure 32Si activity 32P is grow-
ing into this sample at a rate such that after one T 1/2 = 8 hrs

daughter half-life the daughter activity has in-

ln A

creased to 50% of its maximum value of A1: T 1/2 = 0.8 hrs

A2 = 1/2 A1 after one T1/2 100

A2 = 3/4 A1 after two T1/2 81

A3 = 7/8 A1 after three T1/2 , and so on.
This consideration gives the time required to gain
sufficient daughter activity for a proper measure- 10
0 5 10 15
ment after chemical separation of the parent and time in hours
daughter nuclides.
Fig. 6.5.  Relation between the  radioactivities of
a  parent and a  daughter nuclide, when the  half-life
6.6.2. Transient equilibrium
Fig. 6.5. Relation entre les radioactivités d’un nucléide parent of the parent
et d’un nucléide is larger (but not infinitely) than that of
Fig.6.6 Relationfils, quand
entre la demi-vie
les radioactivités d’un nucléide père et d’un nucléide fils
In the daughter (half-lives of 8 and 0.8 hours, respective-
du this
parentcase, the half-life
est plus of the parent
grande (mais pas infinie)nuclide
que celleisde l’élément-fils
Fig.6.6 Relation
vie du entre(demi-vie
les de 8 et
radioactivitésque d’un
cellenucléide père et d’un(demi-vie
nucléide de
fils
still larger than that of the daughter nuclide but ly): the fils
caseest
of plus grande
transient equilibrium. de l’élément-père
The  heavy line
0,8 heures, respectivement): cas de l’équilibre transitoire. vieLaduligne
respectivement)épaisse
fils est plus
cas dumontre
grande la
queand
celle de ligne
l’élément-père (demi-vie
fonction de
shows the sum activity ofnon-équilibre.
parent La
daughter. droite est la sem
not
somme infinitely:
des activités parents/fils. respectivement)
de l’activité de l’élément-père. La courbe supérieure correspond à sem
cas du non-équilibre. La ligne droite est la fonction l’a
λ 1 < λ2 de l’activité de l’élément-père. La courbe supérieure correspond à l’a
mélange.
λ 1 > λ2
Growth of the daughter after zero activity at zero mélange.
La croissance de l’élément-fils après une activité nulle au temps zéro The daughterse produit maintenant
activitysuivant
is growing in the sample
time now occurs according to Eq. 6.19. A sta-
l’équation 6.19. Un état stationnaire est atteint après un temps according to Eq. 6.19 (Fig. 6.6).
tionary state is reached after sufficient Finalement, time suffisant
in pendant
après lequelsuffisamment
un temps l’activité de long, seule l’activité de l’élément-fils
l’élément-filswhich
est plus importante que celle de l’élément père,
the daughter activity is larger than l’activité comme
Finalement, on peut
après s’y
un
the par- de l’élément-père attendre.
temps Laàfigure
suffisamment
Finally, after disparaît
sufficiently un taux
longlong,
plus seule
onlyl’activité
élevé:
time, daugh- de l’élément-fils
6.5 montre l’évolution de chacune
ent activity, as is todes
bedeux activités.
expected. Fig. 6.5l’activité
shows de l’élément-père
ter activity will disparaît
be left,à un tauxthe parent
since plus élevé:activity is
the course of both activities: disappearing
λ2 at0 a higher rate:
λ2 λ2 A2 = A1 e −λ2t
λ
A2 = A10 e −λ1t = A1 (6.23) A2 = λ1 −2 λ 2 A10 e −λ(6.23)
2t
(6.24)
λ2 − λ1 λ2 − λ1 λ1 − λ 2
Après un période tmax l’activité
Afterdea period of tmaxdethe daughter
l’élément-filsactivity
atteindrareaches
une valeur maximale pou
6.6.3. No-equilibrium Après un période de tmax l’activité
a maximum de l’élément-fils atteindra une valeur maximale pou
value for:
6.6.3 NON-EQUILIBRE 2
Here the half-life of the daughter nuclide is larger d A2 − λ1λ 2 0 −λ1tmax λ2
=0= A1 e + 2 A10 e −λ2tmax
dAt2 = 0: =
Ici, le temps de demi-vie de l’élément-fils est supérieur à celui de l’élément-père
than that of the parent: d − λ λ λ
λ2 −1 λ21 A 0 e −λ1tmax + λ 2 −2 λ1 A 0 e −λ2tmax
1 1
λ1 > λ2 dt λ2 − λ1 λ 2 − λ1
ou
L’activité de 52
l’élément-fils croît dans l’échantillon suivant l’équation 6.19 (Fig. 6.6).
ou
λ1 e − λ t 1 max
= λ 2 e − λ2tmax
λ1 e − λ t 1 max
= λ 2 e − λ2tmax
Après un période de tmax l’activité de l’élément-fils atteindra une valeur maximale pour:
Après un période de tmax l’activité de l’élément-fils atteindra une valeur maximale pour:
2
d A2 − λ1λ 2 0 −λ1tmax λ2
d A2 = 0 = − λ1λ 2 A10 e −λ1tmax + λ22 A100 e −−λλ22ttmax
dt = 0 = λ λ 1 A e + λ λ A1 e max
dt λ22 −
− λ11 λ 2 −
2 − λ
EQUATIONS
1
1 OF RADIOACTIVE DECAY AND GROWTH

ou
ou
or 1000
− λ1t max
λ
λ11 ee − λ1t max = λ e − λ2tmax
= λ 22 e − λ2tmax (6.25)
(6.25)
(6.25)
100
The maximum
La valeur maximale value
pour l’activité de of the daughter
l’élément-fils activity
est alors is à:
atteinte
La valeur maximale pour l’activité de l’élément-fils est alors atteinte à:

ln A
thus reached at: T 1/2 = 8 hrs

1 λ
t max = 1 ln λ22 (6.26) 10
(6.26)
t max = λ − λ ln λ (6.26)
λ22 − λ11 λ11 T 1/2 = 0.8 hrs

84 Inserting Eq. 6.25 in Eq. 6.19 shows that at 1

84 the time this maximum is reached, the parent and 0 5 10 15
time in hours
daughter activity are equal (Fig. 6.6).
Fig. 6.6.  Relation between the  radioactivities of
a parent and a daughter nuclide, when the half-life of
6.7. Accumulation of stable the  daughter exceeds that of the  parent (half-lives of
Equations de Décroissance Radioactive
daughter product 8 and 0.8 hours, respectively): the case of no-equilib-
rium. The straight line is the semi-logarithmic plot of
A special case of ‘no-equilibrium’ as discussed
L’insertion de l’équation 6.25 dans l’équation 6.19 montre qu’au moment the parent activity. The upper
où ce maximum est atteint,curve is the total activity
in the preceding paragraph occurs if the daughter of the mixture.
les éléments père et fils sont équivalents (Fig. 6.6).
product is not radioactive, in other words:

6.7 λ2 = 0
ACCUMULATION DE PRODUITS-FILS STABLES The period of time elapsed since time zero
(the ‘age’ T) is:
Un cas spécialThisde can
"non-équilibre",
be illustrated comme
by twodiscuté dans le paragraphe
examples, (i) précédent, se produit si
l’élément-filsthe accumulation
n’est pas radioactif;ofen40d’autres termes:
Ar during the decay of K 40
(6.28)
in rock
λ2 = 0 (Fig. 6.2) and the accumulation of 3
He in
water during the decay of 3H. We will take the lat-
40 This dating method — especially applied in
Ceci peut être terillustré
process parasdeux exemples,to(i)calculate
an example l’accumulation
the age de of Ar lors de la décroissance de 40K
oceanography, but recently also in hydrology
dans les rochesa sample
(Fig. 6.2)from
et (ii)the remaining de 3He activity
l’accumulationparent pendant la décroissance de 3H. Nous
dans l’eauand
[29] — makes a very strong appeal to the ex-
prendrons cethe accumulated
dernier processusamount commeofexemple
daughterpourproduct.
calculer l’âgeperimental
de l’échantillon
(massà partir de
spectrometric) technique, as
l’activité résiduelle de l’élément-père et le taux d’accumulation
Starting from the general relation of Eq. 6.18 or du produit-fils.
the amount of He produced is extremely small.
3

En partant de6.19 we can simplydecorrect for λ6.18 This is shown here by an example of one litres of
la relation générale l’équation 2 = 0ouand the ab-
6.19, nous pouvons simplement corriger pour3
sence ofd’une
λ2 = 0 et l’absence an original
quantitéquantity of de
originelle daughter (a hard(une water
l’élément-fils
with a present-day H activity of 100 TU
condition
condition for méthodes
a successful application of the dat- which overdifficile
a period pour
of une
20 years has accumulat-
application avec succès des de datation mentionnées): ed of 5.1 × 10  mL STP (0°C and 1033 hPa) of
 – 10
ing methods mentioned): 3
He.
0 − λ1t
N 2 = N 1 (1 − e ) (6.27) (6.27)

where the amount of gas accumulated (V in litres 6.8. Radioactive growth

Chapitre 6
où la quantité de gaz accumulée (V en litres STP) est reliée au nombre d’atomes N2 par:
STP) is related to the number of atoms N2 by: For the sake of completeness we will mention
6.8 here the production
CROISSANCE of radionuclides by nuclear
RADIOACTIVE
NN22 22.4 L
VV == 6 × 10 23 22,4 L reactions, because this phenomenon is, from
Pour compléter cette étude, nous mentionnerons ici la production de radionucléid
6 × 10 23 a mathematical point of view, very similar to
Since, instead of the original 3H activity,nucléaires,
the ac- parce que ce
the case of phénomène est, d’un point
secular equilibrium de vue mathématique,
as discussed in très sim
Puisque, à lativity
place after the unknown
de l’activité period
originelle 3
de H,ofl’activité d’équilibre
time is known séculaire tel
Sect. 6.6.1,
après une période que discuté en
if the production
de temps Part. 6.6.1, si le
inconnue est rate (P) is constant. taux de production (P) e
connue (doit (toêtre be measured),
mesurée), N10l’Eq.
N10 dans in Eq. 6.27
6.27 doit has
être toréactions
be re-par
remplacé NThe reactions
peuvent may dans
prendre place take place
1, et subséquemment, N1 par
in a nuclear
un accélérateur de particle
particules nucléaires ou d
l’activité (A1 =placed N1, and
bytelle
λN1), de sortesubsequently
que: nucléaire.
N1 by the activity Le accelerator
taux de or
production in a nuclear
du reactor.
radionucléide est: The produc-
(A1 = λN1), so that: tion rate of the radionuclide is:
dN
6 × 10 23 λT − λT A1 + λT − λT A1 λT = P − λN (6.29)
V = N 1 e (1 − e ) = e (1 − e ) = (ed t − 1)
22,4 λ λ
where N is the number of radioactive nuclei and λ
is the decay
ou N est le nombre constant.
de noyaux Similaret to
radioactifs, λ Eq. 6.21,
la constante the so-
de désintégration. De f
La période de temps écoulée depuis le temps zéro (l’ « âge » T) est:
l’Eq. 6.21, la lution
solutionforpour
the activity produced
l’activité produite est:is:
1 ⎛ λ ⎞
T= ln⎜⎜ 2,7 × 10 22 V + 1⎟⎟ (6.28)
λ ⎝ A1 ⎠ λN = A = P(1 − e − λt )
53
Cette méthode de datation — spécialement appliquée enQuand océanographie, mais plusderécemment
le temps approche l’infini, unenétat stationnaire est atteint dans lequel la
hydrologie (Schlosser et al., 1998) — fait très fortement appel aux techniques expérimentales
décroissance du radionucléide sont équivalentes. Ainsi, à t = ∞:
(spectrométrie de masse), puisque la quantité de 3He produite est extrêmement faible. Ceci est montré
 dN
= P − λN (6.29)
dt

ou N est le nombre de noyaux radioactifs, et λ la constante de désintégration. De façon similaire à

INTRODUCTION
l’Eq. 6.21, la solution pour l’activité produite est:

λN = A = P(1 − e − λt ) (6.30) 1000 (6.30)

A max = production rate

At time approaches infinity, a stationary is being 1/2 A max 3/4 A max

Quand le temps approche de l’infini, un état stationnaire est atteint dans lequel la production et la
reached in which the radionuclide production and 100

Activity (Bq)
décroissance decay
du radionucléide
are equal.sont at t = ∞: Ainsi, à t = ∞:
équivalentes.
Thus,
T 1/2 2T 1/2
Amax
A max = P (6.31)
=P 10 (6.31)

This is shown in Fig. 6.7, representing the course

Ceci est montré en Fig. 6.7, qui représente l’évolution de la radioactivité dans le temps, de la même
of the radioactivity in time, comparably to
façon qu’en Fig. 6.4.
Fig. 6.4. 1
0 2 4 6 8 10
Le temps nécessaire
The time pour produire
required certaines
to produce fractions
certain de l’activité
fractions of maximale atteignabletime est(hrs)
maintenant: the maximum attainable activity is now:
Fig. 6.7.  Growth of radioactivity by a  constant pro-
A =
A 1/2PP = 1/2
= 1/2 Amax
= 1/2 Amax after
après uneone half-life
demi-vie duction rate P of 400 nuclides/sec, resulting in a maxi-
A = 3/4 P after a period of time = 2T1/2 mum activity of 400 Bq. The half-life of the produced
A = 3/4 P après une période de temps = 2T
A = 7/8 P after 3T1/2, and so on. 1/2
nuclide is 2 hours.
A
This P aprèsthat
= 7/8means 3T1/2after
, et ainsi de suite. the maximum
3 half-lives
Ceci signifie attainable activity de
qu’après 3 périodes hasdemi-vie,
practically been maximale
l’activité reached. est pratiquement atteinte.

86

54
7. natural abundance of the stable isotopes of C, O
and H

This chapter is concerned with the natural con-
centrations of the stable isotopes of hydrogen,
carbon and oxygen, with particular attention paid
to those compounds relevant in the hydrological
cycle. For each isotope separately, we discuss
the natural fractionation effects, internationally
agreed definitions, standards, and reference ma-
terials, and variations in the natural abundances.
In order to help the reader to appreciate isotopic
abundance values as they occur in nature, Fig. 7.1
shows some actual isotope ratios and fraction-
ations in a choice of equilibrium systems. Surveys
of some practical data of all isotopes concerned
are given in the respective Sections.
7.1. Table carbon isotopes
processes, kinetic as well as equilibrium, the iso-
tope ratio shows a natural variation of almost
100‰.
Fig. 7.2 presents a broad survey of natural abun-
dances of various compounds, at the low-13C end
bacterial methane (marsh-gas), at the high end
the bicarbonate fraction of groundwater under
special conditions. In the carbonic acid system
variations up to 30‰ are normally observed.
Wider variations occur in systems in which car-
bon oxidation or reduction reactions take place,
such as the CO2 (carbonate) - CH4 (methane) or
the CO2 - (CH2O)x (carbohydrate) systems.
7.1.2. Carbon isotope
fractionations

7.1.1. The natural abundance It will later be shown that the presence of dis-

The chemical element carbon has two stable
isotopes, 12C and 13C. Their abundance is about
98.9% and 1.1%, so that the 13C/12C ratio is about
0.011 [30]. As a result of several fractionation
solved inorganic carbon (DIC) in sea-, ground-,
and surface water presents the possibility of
studying gas-water exchange processes and of
measuring water transport rates in oceans and

2 18
R = 0.00014354 R = 0.00198567
H 2O ( vapour) H 2O ( vapour)

2 18
εv/l = −78.4‰ εv/l = −9.74‰

H 2O ( liquid) at 20 oC H 2O ( liquid) at 20 oC
2 18
R = 0.00015575 R = 0.00200520

13 18
R = 0.0111421 R = 0.00200520
CO 2 (gas) H 2O ( liquid) at 20 oC

13 18
εg/b = −8.46‰ εs/l = +30.42‰

HCO −3 (bicarbonate) at 20oC CaCO 3 (solid calcite)

13 18
R = 0.0112372 R = 0.00206620

Fig. 7.1.  Examples of isotope ratios of compounds in isotopic equilibrium and the re-
spective isotope fractionations, as defined in Sect. 3.3. As an example may serve
the  calculation of 13εg/b as 13αg/b 13εg/b as 13αg/b – 1 with 13αg/bb = 0.0111421/0.0112372 
= 0.99154.
 INTRODUCTION

TABLE 6.1.  The stable and radioactive isotopes of carbon:

practical data for the natural abundance, properties,
analytical techniques and standards.
Further details are given in Sect. 7.1 and 8.1, and in Chapters 10 and 11.

12
C 13
C 14
C
stability stable stable radioactive
natural abundance 0.989 0.011 < 10−12
natural specific activity < 0.25 Bq/gC
decay mode / daughter β− / 14N
half-life (T1/2) 5730 a 
decay constant (l) 1,21 × 10 /a = 1/8267 a −1
−4

max. b energy 156 keV

abundance range
30‰ 0 to 10−12
in hydrological cycle
reported as 13
δ or δ13C 14
A, 14a, 14δ, or 14∆
in ‰ dpm/gC, Bq/gC, %, or ‰
instrument SM CPG, SSL, SMA
CO2, C2H2, CH4,
analytical medium CO2
C6H6, graphite
usual standard deviation 0.03‰ 1‰ to 1% at natural level
international standard VPDB Oxalic acid: Ox1, Ox2
with absolute value 0.0112372 13.56 dpm/gC

Note: MS = mass spectrometry, PGC = proportional gas counting, LSS = liquid scintillation

spectrometry, AMS = accelerator mass spectrometry

in the ground. In connection with studying these
phenomena, the stable and radioactive isotopes
of carbon and their interactions pay an important
contribution, often together with the water chem-
istry.
In nature equilibrium carbon isotope effects oc-
cur specifically between the  phases CO2-H2O-
H2CO3-CaCO3. Values for the fractionations in-
volved only depend on temperature and are ob-
tained from laboratory experiments. A survey is
presented in Fig. 7.3 and Table 7.2.
The kinetic fractionation of specific interest is that
during carbon dioxide assimilation, i.e. the CO2
uptake by plants. The relatively large fraction-
ation (up to about −18‰) is comparable to the ef-
fect observed during absorption of CO2 by an
alkaline solution. A quantitative estimate shows
that the isotope effect as a result of diffusion of
CO2 through air can not explain the fractionation
(Sect. 3.5). The resulting value of 13α is 0.9956,
so that only −4.4‰ of the total assimilation frac-
tionation in favour of 12C can be explained by
the diffusion. The remaining −13.6‰, therefore,
has to be found in the surface of the liquid phase
and in the subsequent biochemical process.
Another kinetic process occurring in the soil is
the bacterial decomposition of organic matter to
form methane (CH4). Here the largest fraction-
ation amounts to about −55‰. In this process CO2
is simultaneously produced with a fractionation
of +25‰, resulting in a 13δ value of about 0‰.
A special problem is the kinetic fractionation dur-
ing uptake and release of CO2 by seawater. This
fractionation is included in calculations on global
13
C modelling.
First we have to emphasise that the difference
in isotopic composition between, for instance,
gaseous CO2 and the dissolved inorganic carbon
content of water can not be addressed by isotope
fractionation between CO2 and DIC.

56
 natural abundance of the stable isotopes of C, O and H

atmospheric CO2
marine HCO 3−
marine carbonate
marine plants
marine plankton
land plants C4 type
land plants C3 type
groundwater HCO −3
fresh-water carbonate
wood
peat
coal
oil
natural gas
bacterial CH4
animal bone
diamond

−80 −60 −40 −20 0 +20

13
δ VPDB (‰)

Fig. 7.2.  General view of C/ C variations in natural compounds. The ranges are indicative for the materials
13 12

shown.

Isotope fractionation is the phenomenon that, due Table 7.2. The chemical fractions are quantita-
to an isotope exchange process, a difference be- tively treated in Chapter 9.
tween the isotopic composition of two compounds Originally 13εk values for the uptake of CO2 by
occurs, while seawater carbon consists of 3 frac- seawater of about −15‰ were assumed, based
tions, i.e. dissolved CO2 (H2CO3 is hardly pres- on experimental results of CO2 absorption by an
ent), dissolved HCO! andd dissolved CO$. All alkaline solution [36]. However, [37] have rea-
these fractions
Isotopesare fractionated
Stables isotopically
de l’Hydrogène, withet du Carbone
de l’Oxygène
respect to each other. The  R value of DIC is:
13
4
13 − 13 2 − 13
ou, en terme
s de l’Hydrogène, de l’Oxygène aqCarbone
de fractionnements
[CO
Isotopes
et 2du RCO respectifs:
] Stables
+ [HCO 3 ] RHCO + [CO 3 ] RCO
de l’Hydrogène, de l’Oxygène et du Carbone
13
RDIC =
2aq 3 3 s/b
CaCO 3
− 2−
[CO 2 aq ] + [HCO ] + [CO ]
ε (‰)

HCO −3
3 3
ou, en terme de
spectifs: 13 a ×13
α
fractionnements + b + c ×13
α
respectifs: 13
0 c/b
RDIC = a / b c / b
Rb (7.7)
13

CO 32−
CT
or in terms of the respective fractionations:
fractionation

+ c ×13 α c / b a ×13 α a / b + b + c ×13 α c / b 13 -4

13
Rb 13 RDIC = Rb
(7.7) (7.7) (7.7)
CT g/b
ou en terme or
dein terms δof: δ values:
valeurs CO 2
a/b
-8
CO2 aq
a ×13 α a / b + b + c ×13 α c / b a ×13 ε a / b + c ×13 ε c / b
ou en terme deδ DIC δb +
13 13
= δ:
valeurs (7.8)
CT CT
-12
+ cα×a 13
+ c ×13 α c / b 13 13 a ×13 ε aa/ b×13 ε+cb/ b + c ×13 α c / b 13 a ×13 ε a / b + c ×13 ε c0/ b 10 20 30 40
+ δ DIC
équationsδ bdans lesquelles
= les/ b parenthèses
(7.8) indiquentδ
(7.8)b + les concentrations respectives, (7.8)quitemperature
sont t ( °C)
C CT CT
aussi identifiées par unT a (acide), b (bicarbonate), et c (ions carbonate), ainsi tels que
Fig. 7.3.  Temperature-dependent equilibrium isotope
a + bindiquent
enthèses + c =dans
équations C T.les
where Les
lesquelles α sont
valeursles
concentrations
the brackets donnéesthe respective
parenthèses
respectives,
indicate dans
quilesont
indiquent Tableau 7.2. Les
les concentrations
con- fractions chimiques
respectives,
fractionation for sont of gaseous CO (g),
qui isotopes
carbon 2
e), b aussi centrations,
quantitativement
identifiées
(bicarbonate), par unwhich
ettraitées
c (ionsdans leare
(acide), also
Chapitre
a carbonate), denoted
9. telsbyque
b (bicarbonate),
ainsi a (acid),
et c (ionsdissolved
carbonate),
CO2 ainsi tels quecarbonate ions (c), and
(a ), dissolved
a + bdans bTableau
+ c =leC (bicarbonate), and données
α sont c (carbonate ions), so solidfractions
carbonate (s) with respect
sont to dissolved HCO 3 (b).
−
données
Originellement, T. Les
les valeurs
7.2. Les
valeurs de fractions
13
ε lors du dans lesont
chimiques
prélèvementTableau
de CO 7.2.par
Lesl’eau de merchimiques
sont estimées
that a + b + c = CT. The α values are given in The actual data and equations are given in Table 7.2. 
k 2
quantitativement
hapitre 9. traitées dans le Chapitre 9.
à environ −15‰, sur la base des résultats expérimentaux d’absorption du CO2 par une
13
lors solution alcalinede
Originellement,
du prélèvement (Baertschi,
les valeurs
CO 1952).
2 par de
l’eau εkdelors
Toutefois,
merdusont Siegenthaler
prélèvement
estimées de CO &2 Münnich
par l’eau de(1981) ont démontré
mer sont estimées
57
àqueenviron
es résultatscet expérimentaux
effet−15‰,
ne s’applique pas à des
sur d’absorption
la base l’action du dissolvante
résultats de l’eau ded’absorption
CO2 expérimentaux
par une mer. Les calculs
du CO effectués par
2 par une
ces auteurs,
solution
). Toutefois, ainsi (Baertschi,
alcaline
Siegenthaler que&par Inoue
1952).
Münnich &(1981)
Sugimura
Toutefois, (1985) et Wanninkhof
Siegenthaler
ont démontré & Münnich (1985) ont montré
(1981) que le
ont démontré
fractionnement
actionque decinétique
cet effet ne
dissolvante s’applique pendant
l’eau de mer.pasLes lecalculs
à l’actionprélèvement de par
dissolvante
effectués CO est de mer. Les calculs effectués par
de 2l’eau
 INTRODUCTION

TABLE 6.2.  TCarbon isotope fractionation in the equilibrium system CO2−

HCO3−CO3−CaCO3.
t 13
εg/b a  13
εa/g b 13
εa/b c 13
εc/b d εs/b e
13
εs/g f
13

(°C) (‰) (‰) (‰) (‰) (‰) (‰)

0 −10.83 −1.18 −12.00 −0.65 −0.39 +10.55
5 −10.20 −1.16 −11.35 −0.60 −0.11 +10.19
10 −9.60 −1.13 −10.72 −0.54 +0.15 +9.85
15 −9.02 −1.11 −10.12 0.49 + 0.41 +9.52
20 −8.46 −1.09 − 9.54 − 0.44 +0.66 +9.20
25 −7.92 −1.06 − 8.97 −0.39 +0.91 +8.86
30 −7.39 −1.04 − 8.42 −0.34 +1.14 +8.60
35 −6.88 −1.02 − 7.90 −0.29 +1.37 +8.31
40 −6.39 −1.00 − 7.39 −0.25 +1.59 +8.03

Note: 13εy/x represents the fractionation of compound y relative to compound x. Values for intermediate temperatures may be
calculated by linear interpolation (see also Fig. 7.3). T = t (°C) + 273.15 K

g = CO2 gaseous, a = dissolved CO2, b = dissolved HCO!, c = dissolved CO $, s = solid calcite.

a 
[31]: εg/b = −9483/T + 23.89‰
13
(7.1)
b
[19]: εa/g = −373/T + 0.19‰
13
(7.2)
c
From a and b: εa/b = −9866/T + 24.12‰
13
(7.3)
d
[32]: εc/b = −867/T + 2.52‰
13
(7.4)
e
Our evaluation of the original data from [33, 34]:
13
εs/b = −4232/T + 15.10‰ (7.5)
f
From a and e): εs/g = +5380/T − 9.15‰
13
(7.6)

soned that this effect does not apply to the dis-
solving action of seawater. Calculations by these
authors as well as by [38] and [39] have shown
the kinetic fractionation during CO2 uptake to be
εk (air ⇒ sea) =  13εk (atm.CO2 to CO2 taken
13
up) = −2.0 ± 0.2‰
This value was confirmed by experiments of
the last author (−2.4 ± 0.8‰).(We have to remind
the reader that these 13εk values as well as those
below are for kinetic fractionations and do not re-
fer to Table 7.2).
The kinetic fractionation during CO2 release by
the ocean reported by [37] needs a correction
[35]. By application of the most recent equilib-
rium fractionations of Table 7.2 the equilibrium
fractionation (13αa/DIC) for dissolved CO2 with re-
spect to total dissolved carbon at 20°C is 0.99055.
This fractionation factor is also determined by
the chemical composition of seawater, which
adds to the overall temperature dependence.
At 20°C the respective relative concentrations in
seawater at pH = 8.20 are: CO2(aq)/CT = 0.006,
HCO!  /CT = 0.893 and CO$/CT = 0.102 where
CT is the total inorganic carbon concentration. By
incorporation of the CO2 + OH- reaction (0.9995),
the resulting 13δ value is −10.1 to −10.6‰, de-
pending on whether the hydration of CO2 to H2O
is to be included.
According to [38] the value is about –10‰, so
that we can conclude to a fractionation of re-
leased CO2 with respect to DIC of:
13
εk (sea ⇒ air) =  13εk (DIC rel. to CO2 re-
leased) = −10.3 ± 0.3‰
Figure 7.4 represents a review of equilibrium and
kinetic fractionations relative to gaseous CO2
(left-hand scale) and the actual 13δ values based

58
 natural abundance of the stable isotopes of C, O and H

pH=8.2
+10 20 ° C
equilibrium kinetic +2
oceanic
HCO 3−
+8 CO2−
3 DIC 0
δ (‰) rel. to air − CO 2

+6
−2

13
+4 13 13 13 13

δ VPDB (‰)
εb/g εc/g εΣ/g ε(sea→air) −4
+2
−6
atmospheric
0 CO 2
13

13
ε(air →sea) CO 2 −8
CO2 (aq)
−2 13
εa-g −10
CO 2 taken up released
−4 −12
by the sea

Fig. 7.4.  Fractionation for the isotopic equilibrium between CO2(gas)-dissolved CO2(aq)-dissolved bicarbonate
(HCO −3  ) – dissolved carbonate (CO$) [35]. The right-hand scale indicates approximate natural 13δ values with
respect to VPDB. The right-hand part shows kinetic fractionations during uptake and release of atmospheric oce-
anic CO2, respectively. DIC is the total dissolved inorganic carbon content (CT).

on 13δ (atm.CO2) = −7.0‰ (right-hand scale). It
is obvious that the isotopic compositions of CO2
released and taken up by the ocean are equal, as
is required by the condition of stationary state of
isotopic equilibrium between ocean and atmo-
sphere.
7.1.3. Reporting 13C variations and
the 13C standard
As described in Sect. 4.1, isotopic composi-
tions expressed as 13δ values are related to those
of specific reference materials. By international
agreement PDB was used as the primary car-
bon reference (standard) material. PDB (Pee
Dee Belemnite) was the carbonate from a cer-
tain (marine) belemnite found in the Cretaceous
Pee Dee formation of North America. This ma-
terial was the original standard sample used in
the early days in Chicago and at CalTech, but has
long been exhausted. The US National Bureau of
Standards therefore distributed another (marine)
limestone of which 13δ had been accurately es-
tablished in relation to PDB. This first standard
available to the community, Solenhofen lime-
stone NBS20, was analysed by [40] and consecu-
tively defined as:
storage, and has been replaced by another lime-
stone, NBS19, of which the 13δ value has been
compared by a number of laboratories with
the previous standard.
Based on this comparison an IAEA panel in 1983
[41] adopted this new standard to define the new
VPDB (Vienna PDB) scale as:
13
δNBS19 / VPDB = +1.95‰ (7.9)
The absolute 13C/12C ratio of PDB was originally
reported as 0.0112372 [40], whereas a slightly
different value of 0.011183 (±0.1‰) was reported
by [42]. The distinction between PDB and VPDB
has been made for formal reasons, but the differ-
ence is negligibly small (< 0.01‰).
Henceforth all 13δ values are reported relative
to VPDB, unless stated otherwise.
More details on measurement and calculation
procedures are given in Chapter 11. A survey of
other reference samples is given in Table 11.2.
7.1.4. Survey of natural 13C
variations

δNBS20 / PDB = −1.06‰

13
In this way the PDB scale was indirectly estab-
lished. Meanwhile NBS20 is considered to be
no longer reliable, probably because of improper
In the other volumes certain aspects of natural 13δ
variations will be discussed in more detail. Here
we will restrict ourselves to a general survey, par-
ticularly with regard to the hydrological cycle
(Fig. 7.5).

59
 INTRODUCTION
7.1.4.1. Atmospheric CO2
The least depleted atmospheric CO2 had origi-
nally 13δ values near –7‰. Since the 19th century
this value has undergone relatively large changes.
In general, high values are observed in oceanic
air far removed from continental influences and
occurs in combination with minimal CO2 con-
centrations. More negative 13δ values are found
in continental air and are due to an admixture
of CO2 of biospheric and anthropogenic origin
(13δ ≈ −25‰), in part from the decay of plant ma-
terial, in part from the combustion of fossil fuels
[43, 44].
7.1.4.2. Seawater and marine carbonate
Atmospheric CO2 appears to be nearly in isotopic
equilibrium with the oceanic dissolved bicarbon-
ate. The 13δ(HCO!  ) values in the ocean are about
+1 to +1.5‰, in agreement with the equilibrium
fractionation εg/b at temperatures between 15 and
20°C (Table 7.2). According to the fractionation
εs/b we should expect calcite slowly precipitat-
ing in equilibrium with oceanic bicarbonate to
have 13δ values of +2.0 to +2.5‰. This is indeed
the normal range found for recent marine car-
bonates. [45] observed this isotopic equilibrium
between marine to brackish-water shells and dis-
solved bicarbonate in the water.
7.1.4.3. Vegetation and soil CO2
Plant carbon has a lower 13C content than the at-
mospheric CO2 from which it was formed.
The fractionation which occurs during CO2 up-
take and photosynthesis depends on the type of
plant and the climatic and ecological conditions.
The dominant modes of photosynthesis give rise
to strongly differing degrees of fractionation [46,
47]. The Hatch-Slack photosynthetic pathway
(C4) results in 13δ figures of −10 to −15‰ and is
primarily represented by certain grains and desert
grasses (sugar reed, corn). In temperate climates
most plants employ the Calvin mechanism (C3),
producing 13δ values in the range of −26 ± 3‰.
A third type of metabolism, the Crassulacean
Acid Metabolism (CAM) produces a large spread
of 13δ values around −17‰ [48].
The CO2 content of the soil atmosphere can be
orders of magnitude larger than that of the free
atmosphere. The additional CO2 is formed in
the soil by decay of plant remains and by root res-
piration and consequently has 13δ values centring
60
around −25‰ in temperate climates where Calvin
plants dominate.
7.1.4.4. Fossil fuel
As complicated biogeochemical processes are in-
volved in the degradation of terrestrial and ma-
rine plant material ultimately into coal, oil, and
natural gas, the range of 13δ values of these fossil
fuels is larger, extending to more negative val-
ues, especially of biogenic methane (Fig. 7.5).
The global average of CO2 from the combustion
of these fuels is estimated to be about −27‰.
7.1.4.5. Global carbon cycle
Biospheric carbon has a  direct influence on 13δ
of atmospheric CO2. The large uptake of CO2 by
the global biosphere during summer and the equal
release of CO2 during winter causes a seasonal
variation in the atmospheric CO2 concentra-
tion as well as in 13δ. The simple mixing of CO2
from these two components, atmospheric CO2
(atm) and biospheric CO2 (bio) is represented by
the equation (cf. Eqs.4.13 and 4.15):
(13δatm + ∆13δ)(Catm + ∆Cbio)= 13δatmCatm + 13δbio∆Cbio
(7.10)
where C stands for the CO2 concentration, DC for
the biospheric addition, and D13δ for the variation
in the δ value.
Numerically this comes to a periodic (seasonal)
variation of
∆ 13δ 13
δ bio − 13δ atm − 25 + 7.85
= = ≈ − 0.05 0 00
∆C bio C atm + ∆C bio 353
per ppm of CO2 (7.11)
Superimposed on this phenomenon is the gradual
increase in the concentration and the accompany-
ing decrease in 13δ by the emission of fossil-fuel
CO2. The trends are shown in Fig. 7.6 and can be
approximated by:
∆13δ / ∆CO2 = −0.015 ‰ / ppm  or   ∆13δ
= −0.025‰ /year (7.12)
at a CO2 concentration of 353 ppm and
δ = −7.85‰ over the Northern Hemisphere,
13
valid for 01/01/1990.
The smaller ‰/ppm value of Eq. 7.12 compared
to Eq. 7.11 shows that the long-term trend is not
due to simple addition and mixing of additional
 natural abundance of the stable isotopes of C, O and H

+5 marine freshwater be caused by isotope exchange with atmospheric

bicarbonate calcite bicarbonate calcite
CO2 (13δ ≈ −7.5‰), ultimately resulting in values
0 of 13δ + 13εb/g = −7.5‰ + 9‰ = +1.5‰, identical
exchange with atmosphere
to oceanic values. Consequently, freshwater car-
−5
atmospheric CO 2
bonate minerals may have “marine” 13δ values. In
these cases the marine character of the carbonate
−10
roundwater HCO −3 25°C
is to be determined by 18δ (Sect. 7.3).
5°C
In addition to HCO!, natural waters contain vari-
δ VPDB (‰)

exchange with soil CO 2

−15
C 4 plants
able concentrations of CO2 with the effect that
the  13δ value of DIC is lower than that of the bi-
13

−20 carbonate fraction alone: in groundwater [18]),

soil CO 2 and in stream and river waters derived from
−25 groundwater (Fig. 7.8) the 13δ(DIC) values are
generally in the range of −12 to −15‰.
C 3 plants
−30
coal oil

7.2. Stable oxygen isotopes

−35
natural gas (CH 4)
7.2.1. The natural abundance
− 40

Fig. 7.5.  Schematic survey of 13δ variations in nature, The chemical element oxygen has three stable iso-
especially of compounds relevant in the  hydrological topes, 16O, 17O and 18O, with abundances of 99.76,
cycle. 0.035 and 0.2%, respectively [30]. Observation
of 17O concentrations provides little information
on the hydrological cycle in the strict sense above
CO2 in the atmosphere. The large oceanic DIC that which can be gained from the more abun-
reservoir is levelling out the purely atmospheric
dant and, consequently, more accurately measur-
mixing effect through isotope exchange.
able 18O variations (Sect. 3.7). We shall, there-
fore, focus our attention here on the 18O/16O ratio
7.1.4.6. Groundwater and riverwater (≈ 0.0020).
Soil CO2 is important in establishing the dis-
solved inorganic carbon content of groundwater. 360
CO 2 concentration (ppm)

After dissolution of this CO2 the infiltrating rain 355

Mauna Loa

water is able to dissolve the soil limestone: 350

345 South Pole
340
CO2 + H2O + CaCO3 → Ca + 2HCO! 2+
(7.13) 335
330
(Fig. 7.7). Because limestone generally is of ma- 1978 1980 1982 1984 1986 1988 1990 1992 1994 1996
rine origin (13δ ≈ +1‰), this process results in -7.4
13
δ of the dissolved bicarbonate of about −11 to -7.5
δ VPDB (‰)

−12‰ (in temperate climates). -7.6 South

In the soil the HCO! first formed exchanges     

  -7.7
13

Mauna Loa
with the often present excess of gaseous CO2, -7.8
Hawaii

ultimately resulting in 13δ(HCO!) = 13δ(soil -7.9

CO2) + 13εb/g ≈ −25‰ + 9‰ = −16‰ (Fig. 7.5). Fig. 7.6.  Trends of the concentration and 13δ of atmo-
Consequently, 13δ(HCO!) values significantly spheric CO2 of air samples collected by C.D.Keeling
outside the range of −11 to −12‰ are observed in on top of the  Mauna Loa volcano at the  Island of
soil water as well as in fresh surface water such as Hawaii and at the  South Pole. The  seasonal varia-
rivers and lakes. In surface waters such as lakes tions have been removed from the original data [49].
13
C enrichment of dissolved inorganic carbon can The dates refer to 1 January of each year.

61
 INTRODUCTION
Values of 18δ show natural variations within
a range of almost 100‰ (Fig. 7.9). 18O is often
enriched in (saline) lakes subjected to a high de-
gree of evaporation, while high-altitude and cold-
climate precipitation, especially in the Antarctic,
is low in 18O. Generally in the hydrological cycle
in temperate climates we are confronted with
a range of 18δ not exceeding 30‰.
7.2.2. Oxygen isotope
fractionations
The isotope effects to be discussed are within
the system H2O (vapour) - H2O (liquid) - CaCO3.
The equilibrium fractionation values have been
determined by laboratory experiments. Fig. 7.1
shows some actual isotope ratios. Fig. 7.10 and
Table 7.4 present a survey of the temperature de-
pendent equilibrium isotope effects.
Equilibrium fractionations determined in the lab-
oratory are also found in nature. The most strik-
ing observation is that the carbonate shells of
many molluscs appear to have been formed in
isotopic equilibrium with seawater. The palaeo-
temperature scale as presented by Eq. 7.18 was
presented by [55] (cf. [53]). This relation is de-
atmosph.CO 2
exchange − 7.5‰
plants / humus
− 25‰
oceanic HCO 3−
+ 1‰
humus CO2
− 25‰
marine CaCO 3
+ 1‰
erosion / sedimentation
Fig. 7.7.  Schematic representation of the formation of dissolved inorganic carbon in groundwater from soil car-
bonate and soil CO2. This is the main process responsible for the carbonate content of groundwater and the con-
secutive components of the water cycle. Generally, dissolved bicarbonate is by far the largest component. The ‰
values referring to the respective 13δ have been kept simple for the sake of clarity. DIC is the dissolved inorganic
carbon content of the water, i.e. HCO !, CO2(aq) and CO$.
62
duced from 18O measurements on carbonate laid
down by marine shell animals at known tempera-
tures and water isotopic compositions. These data
lost the original interpretation of the temperature
dependence of the αs/l by the later realisation
that the major oceanic palaeotemperature effect
is the change in 18δ of seawater — and, conse-
quently of carbonate formed in this water — by
the formation viz. melting of enormous ice caps
on the poles during or after ice ages.
Kinetic effects are observed during the evapora-
tion of ocean water, as oceanic vapour is isoto-
pically lighter than would result from equilib-
rium fractionation alone. The natural isotope ef-
fect for oxygen (≈ –­ 12‰) is smaller than could
be brought about by fractionation by diffusion.
Laboratory measurements resulted in 18εd = –27.3
± 0.7‰ [57] and 18εd = –27.2 ± 0.5‰ (unpubl.).
These experimental values are again smaller
than results from Eq. (3.35) (–31.3‰), which
may be explained by the water molecules form-
ing clusters of larger mass in the vapour phase.
Furthermore, evaporation of ocean water includes
sea spray by which water droplets evaporate
completely without fractionation, thus reducing
the natural isotope effect.
precipitation
soil H 2O
dissolved CO 2
− 25 ± 1‰ groundwater
HCO −3
− 12 ± 1‰
soil CaCO 3
+ 1 ± 1‰
groundwater
DIC
−11 to −16‰
 natural abundance of the stable isotopes of C, O and H

7.2.3. Reporting 18O variations and -6

13
δ (HCO −3 ) (‰)
the 18O standards
-8
Rhine
Originally 18O/16O of an arbitrary water sample
was (indirectly, via a local laboratory reference A -10
sample) compared to that of average seawater. -12
This Standard Mean Ocean Water in reality never Meuse

existed. Measurements on water samples from -14

all oceans by [55] were averaged and referred to 12 2 4 6 8 10 12 2 4 6 8 10 12 2 4 6 8 10 12
1967 1968 1969
a truly existing reference sample, NBS1, that time -6
available at the US National Bureau of Standards 18
δ(H 2O) (‰)
(NBS). In this way the isotope water standard, -7
Meuse
SMOW, became indirectly defined by [58] as: -8
B
δNBS1 / SMOW = −7.94‰
18 -9
Rhine
The International Atomic Energy Agency (IAEA), -10

Section of Isotope Hydrology, in Vienna, Austria -11

and the US National Institute of Standards and
Technology (NIST, the former NBS) have now
available for distribution batches of well pre-
served standard mean ocean water for use as
a standard for 18O as well as for 2H. This standard
material, VSMOW, prepared by H. Craig to equal
the former SMOW as closely as possible both for
18
δ and 2δ, has been decided by an IAEA panel
in 1976 to replace the  original SMOW in fixing
the zero point of the 18δ scale. All water samples
are to be referred to this standard.
From an extensive laboratory intercomparison it
became clear that the difference between the ear-
ly SMOW and the present VSMOW is very small
[59], probably:
δSMOW / VSMOW = +0.05‰
18
(7.20)
At present two standard materials are available
for reporting 18δ values, one for water samples,
one for carbonates. This situation arises from
the practical fact that neither the isotope mea-
surements on water nor those on carbonates are
performed on the original material itself, but are
made on gaseous CO2 reacted with or derived
from the sample.
The laboratory analysis of O/ O in water is
18 16
performed by equilibrating a water sample with
CO2 of known isotopic composition at 25°C
(Sect. 10.2.1), followed by mass spectrometric
analysis of this equilibrated CO2 (Sect. 11.1).
This equilibration is generally carried out on
batches of water samples, consisting of the un-
known samples (x) and the standard or one or
more reference samples. After the correction dis-
cussed in Sect. 11.2.3.4 is made, it is irrelevant
Fig. 7.8.  A  three-year observation of the  isotopic
composition of water from the  N.W. European rivers
Rhine and Meuse [50]:
A  . 13δ values of the  dissolved bicarbonate fraction,
showing normal values during winter and relatively
high values in summer, probably because of isotopic
exchange of the surface water bicarbonate with atmo-
spheric CO2.
B. 18δ values, where the  river Meuse is showing
the  average value and the  seasonal variations of 18δ
in the precipitation: high values in summer, low dur-
ing winter; during early spring and summer the Rhine
receives meltwater from the Swiss Alps with relatively
low 18δ because of the high-altitude precipitation .
whether the water samples themselves are being
related or the CO2 samples obtained after equili-
bration, provided sample and standard are treated
under equal condition:
18
δx / VSMOW = 18δxg / VSMOWg (7.21)
where g refers to the equilibrated and analysed
CO2.
The absolute 18O/16O ratio of VSMOW is re-
ported as (2005.2 ± 0.45) × 10 – 6 [60]. Reference
and intercomparison samples are available from
the IAEA and the NIST. A survey of the data
is given in Table 11.2. In order to overcome
small analytical errors, some laboratories pre-
fer to fix their VSMOW scale by two extreme

63
 INTRODUCTION

TABLE 6.3.  The stable isotopes of oxygen: practical data

for the natural abundance, properties, analytical
techniques and standards.
O
16
O
17
O
18

stability stable stable stable

natural abundance 0.9976 0.00038 0.00205
abundance range
15‰ 30‰
in hydrological cycle
reported as 17
δ or δ17O 18
δ or δ18O
in ‰ ‰
instrument MS MS
analytical medium O2 CO2 or O2
usual standard deviation 0.05‰
VSMOW for water
international standard .
VPDB for carbonate etc
VSMOW: 0.0020052
with absolute value
VPDB: 0.0020672

Note: MS = mass spectrometry.

Further details are given in Sect. 7.2, and in Chapters 10 and 11.

18
for water δ VSMOW (‰)
18
for carbonate δ VPDB (‰)
−60 − 40 − 20 0 +20

ocean water
arctic sea ice
marine moisture
(sub)tropical precipitation
Dead Sea/Lake Chad
temperate zone precipitation
Alpine glaciers
Greenland glaciers
Antarctic ice
Quatern. marine carbonates
fresh-water carbonates

ocean water
marine carbonates
igneous rocks
marine atmospheric CO 2
atmospheric oxygen
organic matter

−20 0 +20 +40 +60

18
δ VSMOW (‰)

Fig. 7.9.  General view of 18O/16O variations in natural compounds. The ranges are indicative for the majority of
materials shown. The relation between the VPDB and VSMOW scales is given in Sect. 7.2.3 and Fig. 7.11.

64
 natural abundance of the stable isotopes of C, O and H

TABLE 6.4.  Oxygen isotope 18

εsg/s = + 10.25‰
fractionation in the equilibrium 18
εsg/lg = 19 082/T − 65.88‰ (7.19)
system CO2−H2O−CaCO3.
[51]: 18εi/l = + 3.5‰ (0°C); 18εi/v = + 15.2‰ (0°C);
t 18
εv/l
a  18
εs/l
b
εg/l
18 c 18
εg/lg d
εsg/lg
18 e
18
εi/v = + 16.6‰ (−10°C)
(°C) (‰) (‰) (‰) (‰) (‰)
0 −11.55 +34.68 +46.56 +5.19 +3.98
5 −11.07 +33.39 +45.40 +4.08 +2.72
10 −10.60 +32.14 +44.28 +3.01 +1.51 50

15 −10.15 +30.94 +43.20 +1.97 +0.34 CO2 gas

20 −9.71 +29.77 +42.16 +0.97 −0.79 40

g/l

25 −9.29 +28.65 +41.15 0 −1.88 CaCO3 solid

30
30 −8.89 +27.56 +40.18 −0.93 −2.93

ε (‰)
s/l
35 −8.49 +26.51 +39.24 −1.84 −3.96

18
20
40 −8.11 +25.49 +38.33 −2.71 −4.94
fractionation
Note: 18εy/x represents the fractionation of compound y 10
relative to compound x, and is approximately equal
to δy - δx. Values for intermediate temperatures H 2O liquid
may be calculated by linear interpolation (Fig. 7.9). 0
T = t (°C) + 273.15 K
v/l
l = liquid H2O , v = H2O vapour , i = ice , g = gas- -10
eous CO2 , s = solid CaCO3 , lg = CO2 (g) isotopic H 2O vapour
equilibrium with H2O (l) at 25°C , sg = CO2 (g) from
CaCO3 (s) by 95% H3PO4 at 25°C. -20
0 10 20 30 40
a
  [55]: ln18αv/l = −1137/T2 + 0.4156/T + 0.0020667 (7.14a) temperaturet ( ° C)

1/T adjustment:  8εv/l = −7 356/T + 15.38‰ (7.14b) Fig. 7.10.  Temperature dependent equilibrium frac-
Values at higher temperatures can be obtained from tionations for oxygen isotopes of water vapour (v),
[52]. gaseous CO2 (g), and solid calcite (s) with respect to
The fractionation between vapour and liquid water is liquid water (l).
independent of the NaCl concentration of the solu-
tion, contrary to some other salts [53].
b
From c and e and [53]:  18εs/l = 19 668/T − 37.32‰ (7.15)
points (Sect. 11.2.3.5). Using this procedure,
c
[54]: 18εg/l = 17 604/T − 17.89‰ (7.16)
the sample 18δ is located on a linear δ scale be-
d
From c, where lg is obtained from l by applying the 18εg/l tween VSMOW (0‰) and SLAP (Standard Light
value at 25°C (concluded by an IAEA panel to be
+41.2‰
Antarctic Precipitation) with a defined value of
εg/lg = 16 909/T – 56.71‰
18
(7.17) 18
δSLAP / VSMOW  = −55.5‰ (7.22)
This fractionation is independent of the salt content of
the solution δ values of carbonates are given with ref-
18

erence to the same PDB calcite used for 13C

e
[55, 56]:  t(°C) = 16.5 – 4,3(18δs – 18δw) + 0.14(18δs – 18δw)2
(7.18) (Sect. 7.1.3). The zero point of this PDB scale
was fixed by means of the NBS20 reference sam-
where 18δ refers CO2 prepared from solid carbonate
ple (Solenhofen limestone) which originally was
with 95% H3PO4 at 25°C and 18δw to CO2 in isoto-
pic equilibrium with water at 25°C, both relative to defined as [40]:
VPDB-CO2
δNBS20 / PDB = −4.14‰
18

sg is obtained from s by applying the fractionation for

the CO2 production at 25°C The absolute 18O/16O ratio of PDB-CO2 was origi-
nally reported as 0.0020790 [40].

65
 INTRODUCTION
This value, however, does not agree with
Baertschi’s ratio for VSMOW and the accurately
measured difference between the two standards
(Fig. 7.10). At present a value of 0.0020672 is
considered to be more realistic (Table 11.1).
Recently, samples from NBS20 do not always
show the above value. Probably because of ex-
change with atmospheric vapour due to improper
storage, the 18δ value may have shifted to close to
−4.4‰. Therefore, a new set of carbonate refer-
ence materials has been introduced by the IAEA
where NBS19 replaces NBS20. The VPDB
(Vienna PDB) scale has now been defined by us-
ing NBS19:
δNBS19 / VPDB = −2.20‰ (7.23)
18
The carbonate itself is not analysed for 18δ but
rather the CO2 prepared according to a standard
procedure which involves treatment in vacuum
with 95% (or 100%) orthophosphoric acid at
25°C. If samples and reference are treated and
corrected similarly,
δx / VPDB = 18δxg / VPDBg
18
(7.24)
where g refers to the prepared and analysed CO2,
so that neither the fractionation between the car-
bonate and the CO2 prepared from it (Table 7.4)
nor the reaction temperature need to be known.
The relations between the VPDB, VPDB-
CO2 (VPBDg), VSMOW and VSMOW-CO2
(VSMOWg) scales are derived from the equa-
tions given in Table 7.4, according to Eq. 7.24:
δx / VSMOW = 1.03086 18δx / VPDB + 30.86‰ (7.25)
18
δx / VSMOW = 1.04143 18δx / VPDBg + 41.43‰ (7.26)
18
δx / VSMOWg = 1.00027 18δx / VPDBg + 0.27‰ (7.27)
18
The relations are visualised in Fig. 7.11.These are
of interest in isotope studies on silicates, oxides,
carbonates, organic matter, and their correlation
with water.
The conversion equations are in general:
δlower = αi 18δupper + εi
18
(7.28)
where αi = D , D , or α , and ‘lower’ and ‘upper’
refer to the levels in the scheme.
66
Henceforth, all 18δ values of carbonates are
reported relative to VPDB, 18δ of gaseous (at-
mospheric) CO2 relative to VPDB-CO2, and all
18
δ values of water relative to VSMOW, unless
stated otherwise.
More details on the measurement and calculation
procedures are given in Chapter 11.
7.2.4. Survey of natural 18O
variations
δ variations throughout the hydrologic cycle
18
will be discussed in detail in the other volumes.
Here we present only a broad survey (Fig. 7.12).
7.2.4.1. Seawater
The oceans form the largest global water reser-
voir. The 18O content in the surface layer is rather
uniform, varying between +0.5 and −0.5‰ [55].
Only in tropical and polar regions larger devia-
tions are observed. In tropical regions more posi-
tive values are caused by strong evaporation: 18δ
of water in the Mediterranean amounts to +2‰
(2δ = +10‰). In polar regions more negative val-
ues originate from water melting from isotopi-
cally light snow and ice.
If ocean water were evaporating under equilibri-
um conditions, the vapour resulting would be 8 to
10‰ depleted in 18O, depending on temperature.
However, oceanic vapour appears to have an av-
erage 18δ value of –12 to –13‰, which must part-
ly be due to kinetic fractionation. The relative hu-
midity of the air and the evaporation temperature
influence the amount of non-equilibrium fraction-
ation occurring (see Volume 2 on Precipitation).
7.2.4.2. Precipitation
The transformation of atmospheric water vapour
to precipitation depends on so many climato-
logical and local factors, that the 18δ variations
in precipitation over the globe are very large. As
a general rule 18δ becomes more negative the fur-
ther the rain is removed from the main source of
the vapour in the equatorial regions. In the Arctic
and Antarctic, 18δ of the ice can be as low as
–50‰. This gradual 18O depletion model is sche-
matically shown in Fig. 7.13.
 natural abundance of the stable isotopes of C, O and H

In Volume 2 the various effects will be discussed
in detail, causing regional and temporal varia-
tions on 18δ of precipitation.
We can distinguish between:
(1) latitudinal effect with lower 18δ values at in-
creasing latitude
(2) continental effect with more negative
values for precipitation the more inland
(3) altitude effect with decreasing 18δ in precip-
itation at higher altitude
(4) seasonal effect (in regions with temperate
climate) with more negative 18δ values dur-
ing winter
18
δ (5) amount effect with more negative 18δ values
in rain during heavy storms.

−0.27
0.99973
∆1
VPDB-CO 2
VSMOW-CO 2

NBS19-CO 2
Dc ∆2
0.99780 0.99807
−2.20
VPDB
α1
1.01025
NBS19
Dc
0.99780
−2.20
VSMOW
α2 ∆3 ∆4
1.0412 1.0309 1.0415

SLAP-CO 2
Dw
0.94450
−55.50

SLAP
Dw
0.94450
−55.50

Fig. 7.11.  Relations between 18O reference and intercomparison samples with respect to VPDB and VSMOW
[61]. VPDB-CO2 refers to CO2 prepared from hypothetical VPDB by treatment with H3PO4 (95%) at 25°C,
VSMOW–CO2 to CO2 equilibrated with VSMOW at 25°C. The vertical scale is indicative and not entirely propor-
tional to real numbers.
∆1 : Difference between VPDB−CO2 and SMOW−CO2 (−0.22‰) [62, 45] plus the  difference between
SMOW(CO2) and VSMOW(CO2) (−0.05‰) (Eq. 7.20)
Dc : defined value of NBS19 relative to VPDB (Eq. 7.24)
∆2 = Dc − ∆1
α1 : according to [53]
α2 : average of 3 independent methods applied by 4 different laboratories
∆3: from α2 , α1 , and ∆1; 1.03086 is the exact figure quoted by [53], in agreement with α2 = 1.04115 [54]
∆4: f from ∆3 and α1

67

7.2.4.3. Surface water
In Fig. 7.8 some data are shown on δ varia-
tions in riverwater. The seasonal variation with
relatively high values in summer is characteristic
for precipitation in temperate regions. The basis
of both curves represents the average 18δ val-
ues of precipitation and groundwater in the re-
charge areas, i.e. N.W. Europe (Meuse) and
Switzerland/S.Germany (Rhine), the latter with
a large transport of relatively isotopically light
meltwater in spring.
Evaporation, especially in tropical and semi-arid
regions, causes 18O enrichment in surface waters.
This results, for instance, in 18δ of the river Nile
to be +3 to +4‰, and of certain lakes as high as
+20‰ (Sect. 4.4.5 and 7.5).
7.2.5. Climatic variations
The slow precipitation of calcium carbonate is
a process during which carbonate and water are
in isotopic equilibrium, as was pointed out earlier.
The 18O content of the carbonate is, therefore, pri-
marily determined by that of the water. The sec-
ond determining factor is the temperature, as is
indicated in Fig. 7.10. Consequently we can in
principle deduce the water temperature from 18δ
of carbonate samples in marine sediment cores,
provided 18δ of the water is known (≈ 0 ‰). This
was originally believed to be the basis of the 18O
palaeothermometry of fossil marine shells [63].
The present-day opinions assume a varying 18δ of
the surface ocean water during glacial/intergla-
cial transitions [64, 65], due to varying amounts
of accumulated ice with low 18δ as polar ice caps.
As a realistic order of magnitude, an estimated
amount of 5 × 105 km3 of ice (=Vice) laid down
especially on the northern polar ice cap dur-
ing the last ice age with an average 18δ value of
−20‰ changes the 18δ value (at present = 0‰) of
the 107 km3 of ocean water (= Vocean) by +1‰, as
is simply deduced from the mass balance:
Vpresent ocean × 18δ present seawater  = Vce-age ocean × 18δice-age
seawater + Vice caps × δice (7.29)
18
Another spectacular application of isotope varia-
tions in nature is the deduction of climatic chang-
es in the past from 18O/16O or 2H/1H ratios in polar
ice cores. If the process of gradual isotope deple-
tion of precipitation is studied in detail as a func-
tion of latitude and thus of air temperature, a rela-
68
INTRODUCTION
tion can be derived (Volume 2) which comes to
the temperature dependence [16, 66]:
18
d18δ / dt ≈ +0.7‰ / °C (7.30)
By this relation it is possible to translate isotope
variations into climatic variations during geo-
logic times. Records have been obtained on ice
cores from Greenland and the Antarctic, showing
the alternation of low-18δ (or low-2δ) and high-18δ
(or high-2δ) periods, respectively cold and warm
periods (Eq. 7.30).
7.3. Relation between 13C and 18O
variations in H2O, HCO!, and
CO$
Differences and the relations between the vari-
ous natural water-carbonate systems can nicely
be displayed by considering both 18δ of the water
and 13δ of the dissolved bicarbonate. Fig. 7.15 is
a schematic representation of three waters of re-
alistic isotopic composition, each provided with
the temperature dependent range of calcite pre-
cipitated under equilibrium conditions. This fig-
ure essentially is a combined graph of Figs 7.5
and 7.12.
From an isotopic point of view, the 4 common
types of water are:
(1) Seawater, with 18δ values around 0‰ (by
definition) at present; the  carbonate range
is that of recent marine carbonates. Because
of changing glacial and interglacial periods
the  18δ of ocean water varied in the past.
Also the 18δ values of marine limestone have
increased during the course of geological
time, while the 13δ values have essentially re-
mained the same [68].
(2) Ground- and river water, with an arbitrarily
chosen value of 18δ. In freshwater bicarbon-
ate 13δ generally is around –11 to –12‰.
The isotopic compositions of fresh-water
carbonates derived from this water may re-
sult from the known equilibrium fraction-
ations (Tables 6.2 and 6.4), in a similar way
as is indicated for marine carbonate.
(3) Stagnant surface or lake water can be sub-
jected to processes altering the isotopic
composition. Provided the water has a suf-
ficient residence time in the  basin, isotope
exchange will cause the 13C content to reach
isotopic equilibrium with atmospheric CO2.
 natural abundance of the stable isotopes of C, O and H

marine
ocean water
freshwater 5°C 25°C

carbonate tropical preci pitation

river/lake ocean
increasingly equatorial
depleted marine
vapour

δ VSMOW
arbitrary freshwater evaporation
precipitation

18
temperate increasingly
polar high low tropical depleted vapour

precipitation

higher latitudes
water vapour
equilibrium
kinetic lower temperatures

ocean water

polar precipitation
−25 −20 −15 −10 −5 0 +5
18
for water : δ VSMOW (‰)
18 air temperature
for carbonate: δ VPDB (‰)

Fig. 7.12.  Schematic survey of natural 18δ variations
in nature, especially relevant in the hydrological cycle.
The marine vapour gradually becomes depleted in 18O
during the  transport to higher latitudes (Fig. 7.13).
Evaporation of surface water may cause the water to
become enriched in 18O. Finally the formation of solid
carbonate results in a  shift in 18δ depending on tem-
perature (cf. Fig. 7.5).
Fig. 7.13.  Schematic representation of the  gradual
depletion in 18O of atmospheric water vapour and
the  condensing precipitation, the  further the  vapour
and precipitation process are removed from the main
source of the  vapour: the  tropical marine belt. At
lower temperatures the isotope fractionation between
water vapour and liquid water is larger, counteracting
but loosing from the  Rayleigh depletion process (cf.
Fig. 7.7 and 7.12).

Then 13δ equals that in the ocean. Carbonate 7.4. Stable hydrogen isotopes
δ and 18δ are related to, respectively, HCO!
13

and H2O as indicated for the marine values. 7.4.1. The natural abundance

The  18O content of the water, especially in
The chemical element hydrogen consists of two
warmer climates, will change towards less
negative or even positive values due to evap- stable isotopes, 1H and 2H (D or Deuterium), with
oration. an abundance of about 99.985 and 0.015% and
(4) Estuarine water has intermediate values of an isotope ratio 2H/1H ≈ 0.00015 [69]. This iso-
13
δ(HCO!) or 13δ(DIC) and 18δ(H2O), depend- tope ratio has a natural variation of about 250‰,
ing on the degree of mixing of the river- and higher than the 13δ and 18δ variations, because of
seawater. The latter behaves conservatively, the relatively larger mass differences between
i.e. is only determined by the mixing ratio;
the isotopes (Fig. 7.16).
13
δ(DIC) also depends on the DIC values of
the mixing components. Therefore, the mix- As with 18O, high 2H concentrations are observed
ing line is generally not straight. The relation in strongly evaporated surface waters, while low
with 13δ of the bicarbonate fraction is even
more complicated, as the dissociation equi-
2
H contents are found in polar ice. Variations of
libria change with pH (even the pH does not about 250‰ are present in the part of the hydro-
at all behave conservatively) (Sect. 9.5.4). logical cycle to be discussed here.

69
 INTRODUCTION
7.4.2. Hydrogen isotope
fractionations
The most important hydrogen isotope fraction-
ation is that between the liquid and the vapour
phases of water. Under equilibrium conditions
water vapour is isotopically lighter (contains
less 2H) than liquid water by amounts given in
Table 7.6. Fig. 7.3 shows some actual isotope
ratios of equilibrium systems and the matching
2
δ values. The fractionation by diffusion of H2O
through air (2δd) varies between −22.9 ± 1.7‰
[57] and −20.4 ± 1.4‰. (unpubl.), slightly more
than the value calculated from Eq. 3.34 (−16.3‰)
(cf. Sect. 7.3.2).
7.4.3. Reporting 2H variations and
the 2H standard
VSMOW is the standard for 2H/1H as it is for
18
O/16O ratios. Values for the absolute 2H/1H ra-
tio of VSMOW and SLAP are reported to be
(155.76 ± 0.07) × 10 – 6 and (89.02 ± 0.05) × 10 – 6,
respectively, by [70], (155.75 ± 0.08) × 10 – 6
and (89.12 ± 0.07) × 10 – 6 by [71], and (155.60
± 0.12) × 10 – 6 and (88.88 ± 0.18) × 10 – 6 by [72].
The average 2δ value of the secondary standard
SLAP on the VSMOW scale (Sect. 7.2.3) conse-
quently is −428.2 ± 0.1‰. Based on these data
the 2δ value has been defined as:
2
δSLAP / VSMOW = −428.0‰ (7.33)
No significant difference in 2δ has been detect-
ed between the original SMOW standard and
VSMOW [59].
Reference and intercomparison water samples
are available from the IAEA (Table 11.3). The 2H
contents of hydrogen-containing samples are de-
termined by completely converting them to hy-
drogen gas. Therefore, fundamental problems of
isotope fractionation during sample preparation,
as with 18O, do not occur; however, the analyses
are more troublesome (Sect. 10).
Henceforth all 2δ values will be reported rela-
tive to VSMOW.
More details on the measurement and calculation
procedures, and on isotope reference samples are
given in Chapter 10.
70
δ 18
marine Arctic Antarctic
carbonate ice ice
+1.5 0 −40 −36 −49 −45
0
20
40
60
80
3
Fig.Time (10Palaeotemperature
7.14.  years BP) records represented
by δ variations in time in the  CaCO3 fraction from
18
foraminifera shells in deep-sea core sediments (left),
in glacier ice of a  Northern Greenland glacier (at
Summit), and in glacier ice of an Antarctic ice core
(at Vostok), respectively from left to right (figure modi-
fied from [67]). In each record the left side indicates
the lower temperatures, for instance, at 20 000 years
BP each curve shows the  most recent glacial maxi-
mum. The  upper 10 000 years contain the  present
warm interglacial, the Holocene.
7.4.4. Survey of natural 2H
variations
From the foregoing it is evident that some correla-
tion should exist between 2H and 18O fractionation
effects. Therefore, in natural waters a relation be-
tween 2δ and 18δ values is to be expected. Indeed,
the 2δ and 18δ variations in precipitation, ice, most
groundwaters and non-evaporated surface waters
have appeared to be closely related. Therefore,
the qualitative discussion given in Sect. 7.2.4 for
18
δ applies to 2δ equally well. The next section is
devoted to this relation.
7.5. Relation between 2H and 18O
variations in water
If we simply assume that evaporation and con-
densation in nature occur in isotopic equilibri-
um, the relation between the 2δ and 18δ values of
natural waters is determined by both equilibrium
fractionations 2εv/l and 18εv/l. In Table 7.6 the ratio
 natural abundance of the stable isotopes of C, O and H

25 °C
lake
5 °C
0 evaporation

ocean
δ VPDB (‰)

exchange with atm. CO2

13

−5

estuarine mixing H 218O / H 13CO −3

of DIC

Ca 13C 18O 16O −2

−10

rivers

−10 −5 0
18
δ VPDB , 18δ VSMOW (‰)

Fig. 7.15.  Relation between the natural variations of 13δ(HCO! and CaCO3) and 18δ(H2O and CaCO3). The graph
is essentially a combination of Figs.7.5 and 7.12. Estuarine mixing only results in a straight line between the river
and sea values of 13δDIC, if CT of the components is equal. Because this is rarely the case, the relation between
the two members mostly is observed as a slightly curved line. Additionally, 13δ(HCO !) in estuaries is not subject
to conservative mixing, because the mixing process rearranges the carbonate fractions (Sect. 9.5.4). Depending
on the residence times of the water at the surface, evaporation and isotope exchange changes the isotopic compo-
sition to higher δ values.

ocean water
arctic sea ice
marine moisture
(sub)tropical precipitation
temperate zone
polar ice
Alpine glaciers
Lake Chad
wood cellulose temperate
peat zone
clay minerals

−200 −150 −100 − 50 0 + 50

2
δ VSMOW (‰)

Fig. 7.16.  General view of 2H/1H variations in natural compounds. The ranges are indicative for the majority of
materials shown.

71
 INTRODUCTION

TABLE 6.5.  The stable and radioactive isotopes of hydrogen

1
H 2
H 3
H
natural abundance 0.99985 0.00015 < 10−17
stability stable stable radioactive
natural specific activity < 1,2 Bq/L water
decay mode / daughter β− / 3He
half-life (T1/2) 12.320 ± 0.022 a 
decay constant (λ) 5.576 × 10−2/a = 1/18.33 a−1
β 18 keV
abundance range
250‰ 0 to 10−16
in hydrological cycle
reported as 2
δ or δ2H or δD 3
A
in ‰ TU, Bq/L H2O
instrument MS PGC, LSS
analytical medium H2 H2O, C2H6, C6H6
usual standard deviation 0.5‰ ≥ 1% at high level
international standard VSMOW NBS-SRM 4361
3
H/1H = 6600 TU
with absolute value H/ H = 0.00015575
1
or = 0.780 Bq/g H2O
as of Jan.1, 1988

Note: Practical data for the natural abundance, properties, analytical techniques and standards. Further
details are given in Sect. 7.4 and 8.3, and in Chapters 10 and 11.
MS = mass spectrometry, PGC = proportional gas counting, LSS = liquid scintillation
spectrometry, AMS = accelerator mass spectrometry.

TABLE 6.6.  Hydrogen isotope Note: εy / x represents the fractionation of compound y rela-

fractionation in the equilibrium tive to compound x and is approximately equal to
system liquid water (l), water
2
δ(y) – 2δ(x). Values for intermediate temperatures
may be obtained by linear interpolation; T = t (°C) +
vapour (v), and ice (i) 273.15 K.
t (°C) 2
εv/l a (‰) 18
εv/l (‰) 2
εv/l / 18εv/l b
a 
  [51]: ln2α = −24 844/T2 + 76.248/T − 0.052612
0 −101.0 −11.55 8.7 (7.31a)
5 −94.8 −11.07 8.55 1/T adjustment: 2εv/l = −85 626/T + 213.4‰ (7.31b)
10 −89.0 −10.60 8.4
Values at higher temperatures can be obtained from
15 −83.5 −10.15 8.25 [52].
20 −78.4 − 9.71 8.1 b
The ratios between the fractionations for 18O and 2H
25 −73.5 −9.29 7.9 at the liquid-vapour equilibrium are obtained from
[51]: 2εi/l = + 19.3‰ (at 0°C) (7.32)
30 −68.9 −8.89 7.75
35 −64.6 −8.49 7.6
40 −60.6 −8.11 7.4

72
 natural abundance of the stable isotopes of C, O and H

+ 40
meteoric water line: 2δ = 8 18δ + 10 ‰

0
ocean
rain water
δ VSMOW (‰)

condensation
− 40

marine atmospheric water vapour

2

− 80 vapour at equator in equilibrium

at 200C

−120
remaining
vapour
−160

−20 −16 −12 −8 −4 0 +4

18
δ VSMOW (‰)

Fig. 7.17.  Relation between natural variations of 18δ and 2δ ocean water, atmospheric vapour and precipitation.
The black round represents the hypothetical value of water vapour in isotopic equilibrium with ocean water, black
square the observed isotopic composition of equatorial marine vapour, originated from the more realistic non-
equilibrium fractionation. Marine vapour gradually condenses into precipitation (hatched arrow) with a positive
fractionation, leaving the vapour progressively depleted in 18O and 2H (grey arrow) (cf. Fig. 7.13).

of these factors is presented for the temperature 2

range of 0 – 40°C.
[73, 16] found a relation between the 2δ and 18δ
values of precipitation from various parts of
the world:
2
δ = 8 18δ + 10‰ (7.34)
This relation, shown in Fig. 7.17 has become
known as the Global Meteoric Water Line
(GMWL) and is characterised by a slope of 8
and a certain intercept with the 2H axis (= the 2δ
value at 18δ = 0‰). The general relation is of
the MWL is:
δ = s × 18δ + d (7.35)
where the slope s = 8, as is explained by the ratio
between the equilibrium isotope fractionations of
hydrogen and oxygen for the rain condensation
process (Table 7.6); d is referred to as the deute-
rium excess (d-excess), the intercept with the 2δ
axis. In several regions of the world as well as
during certain periods of the year and even cer-
tain storms the 2δ value is different from 10‰,
depending on the humudity and temperature con-
ditions in the evaporation region.
The isotopic composition of water vapour over
seawater with 2δ = 18δ = 0‰ vs VSMOW is

73
 INTRODUCTION

somewhat lighter than would follow from isoto-
pic equilibrium with the water: the evaporation
is a non-equilibrium (partly kinetic) process.
However, from the observed vapour composi-
tion onward the vapour and precipitation remain
in isotopic equilibrium, because the formation
of precipitation is likely to occur from saturated
vapour (i.e. vapour in physical equilibrium with
water). Consequently the 18δ and 2δ values both
move along the meteoric water line (Eq. 7.33).
In Volume 3 (Surface Water) certain circumstanc-
es will be discussed leading to deviations from
the common MWL. For instance, larger values of
d are occasionally observed.
Apart from this, deviations occur in evaporating
surface waters, showing slopes of 4 to 5 rather
than 8. If 2δo and 18δo denote the original isotopic
composition of an arbitrary surface water, the δ
values after evaporation are related by:
2
δ – 2δo ≈ 4.5 (18δ – 18δo)   or   ∆2δ ≈ 4.5 ∆18δ
(7.36)
(Fig. 7.18). The release of relatively low-δ wa-
ter vapour to the air results in a increase in δ of
the remaining water, as illustrated by the model
of Sect. 4.4.5, here for 2δ as well as 18δ.

+ 20
meteoric water line:
2
δ = 8 18δ + 10 ‰ ocean
water
0

estuarine mixing
δ VSMOW (‰)

− 20
arbitrary
freshwaters
evaporated water
2

− 40 ∆ 2δ = 4.5 ∆ 18δ

escaping
vapour
−60

−80

−10 −8 −6 −4 −2 0 +2
18
δ VSMOW (‰)

Fig. 7.18.  Relation between 18δ and 2δ for estuarine mixing and for evaporating surface water. Because the evap-
oration is a non-equilibrium process, isotope fractionations involved are not necessarily related by a factor of
8, as is the equilibrium condensation process, the basis for the meteoric water line (Fig. 7.17). As in the preced-
ing figure, the arrows indicate the direction of change of the isotopic composition of the escaping vapour and of
the remaining evaporated water.

74
8. NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H

In this chapter the two nuclides, 14C and 3H, will 14

be treated that are the most relevant in the hy-
drological cycle. Chapter 12 contains a survey of
the isotopes with less extensive applications.
8.1. The radioactive carbon
isotope
8.1.1. Origin of 14C, decay and
half-life
The natural occurrence of the radioactive carbon
isotope, 14C or radiocarbon, was first recognised
by [74]. It is naturally formed in the transitional
region between the stratosphere and troposphere
about 12 km above the earth’s surface through
the nuclear reaction:
N + n → 14C + p
14
(8.1)
The thermal neutrons required are produced by
reactions between very high-energy primary cos-
mic ray protons and molecules of the atmosphere.
C thus formed very soon oxidises to 14CO, and
ultimately to 14CO2 which mixes with the inactive
atmospheric CO2 (Fig. 8.1). Through exchange
with oceanic dissolved carbon (primarily bicar-
bonate), most 14CO2 molecules enter the oceans
and living marine organisms. Some are also as-
similated by land plants, so that all living organ-
isms, vegetable as well as animal, contain 14C in
concentrations about equal (Sect. 8.1.3) to that of
atmospheric CO2.
14
C decays according to:
14
C → 14N + ß− (8.2)
with a maximum ß- energy of 156 keV and a half-
life of 5730 ± 40 years [75] (Fig. 8.2). Originally
the half-life was thought to be 5568 years, so that
during the first decade or two 14C age determina-
tions were based on the ‘wrong” half-life. Later,
when the ‘better’ half-life became known, so many
14
C ages were already published that, in order to
avoid confusion, it was decided that the original

cosmic radiation

14 14
N+n → C+p 14
C → 14
N + β− 14 14
C C
14
C
14 12
CO 2 + CO 2
12
CO 2
exchange assimilation fossil nuclear bomb
fuel
exchange

H14CO 3
shells humus 14CO 2
−
LAKE
Ca14 CO 3
OCEAN groundwater table
ageing
+ Ca12CO 3 + H 2O → H 14CO −3 + H 12CO −3

Fig. 8.1.  Origin and distribution of 14C in nature. The natural 14C concentration by the production by neutrons
from cosmic radiation has been influenced by — chronologically — the addition to the air of CO2 without 14C by
the combustion of fossil fuels and the production of 14C by neutrons released by the fission and fusion reactions
during nuclear explosions.
 3
H T1/2 = 12.43 a
β− − Emaxβ=− 18 keVEmax = 156 keV
β Emax = 18 keV

β− Emax = 18 keV INTRODUCTION 3 14

He
3 14N
He
3 14
A
3 natural = 0.6 Bq / liter H2O Anatural = 250 Bq / k
half-life should continued to be used3 for reporting AnaturalThe absolute
= 0.6 Bq / liter H2O 14C activity, that is the 1414
(specific) ACnatural = 250 Bq /
14
14
C ages. Moreover, it was meanwhile known that He radioactivity (in Bq or, conventionally, in disinte- N
3
ages would still be in= error,
Anatural 0.6 Bqeven using
/ liter H2Othe right grations per14minute Anatural(dpm) = 250 perBq gram
/ kg Cof carbon) is
Fig.8.2 Decay schemes of tritium and radiocarbon. Both nuclides are pure β− −
half-life, because of the natural variations Fig.8.2 in Decaygiven the symbol
schemes of tritium and radiocarbon. Both nuclides are pure β
the  14C content of atmospheric CO2 during geo-present-day specific activities are given as 3A and 14A.
present-day specific activities are given as 3A and 14A.
logicFig.8.2
times and deviating
Decay schemes from the present.
of tritium and These 14
radiocarbon. a = number of disintegrations
Both nuclides are pure β−per minuteThe
emitters.
errors were even larger. Nowadays the  C cali- 14
(dpm/gC)
3 14 (8.3)
present-day specific activities are given as A and14 A.
bration, based on the known 14C content of tree (specific) 14C activity, that is the 1414C radioactivity (in Bq or, conve
The absolute
The absolute (specific) It is extremely C activity,
difficultthat is the anCabsolute
to make radioactivity
mea- (in Bq or, conv
rings with exactly known age, removes both er- per minute (dpm)
disintegrations 14 per gram of carbon) is given the symbol
surement of a  C activity. Moreover,
disintegrations per minute (dpm) per gram of carbon) is given the symbol the absolute
rors at once (Sect. 8.1.4). 14
The absolute (specific) C activity, that is the A =Cnumber
14 1414C
14
contentofofdisintegrations
radioactivity a sample
(in Bq or, is generally not(dpm/gC)
conventionally,
per minute relevant.
in
The production and distribution of C in nature ATherefore,
14 = number of disintegrations
the sample per minute
activities are (dpm/gC)
compared
disintegrations per minute (dpm) per gram of carbon) is given the symbol
occurs through series of chemical andIt biological is extremely with difficult to makeofan
the activity absolute In
a standard. measurement
reality, the num- of a 1414C activity. M
14 It is extremely difficult to make an absolute measurement of a C activity. M
processes which has A =become
numberstationnary through-
of disintegrations
absolute 14 per minute
ber ofof(dpm/gC)
C content
14 aCsample
14
registrations (β registrations
is generally (8.3)from
not relevant. 14
C
Therefore, the sample
out much of geologic time. As a consequence, absolute C content of a sample is generally not relevant. Therefore, the sample
decay in radiometric detectors such as propor- of 1414C reg
It is extremely
the concentration of 14difficult to makecompared
C in the atmosphere, an absolute
compared
with
oceanswith
the activityofofa a14C
measurement
the
tional activity
counters of
and a
standard.
activity.
standard.
liquid
InMoreover,
In
reality, the
reality,
scintillation the number
the
counters, number of C re
14
absolute 14reached
and biosphere C content of a samplevalue
a steady-state registrations
isregistrations
generally
which not from C
relevant.
14
registrationsdecay in radiometric
Therefore, the detectors
sample such
activities as
are proportional counte
from C decayofin radiometric
14
C concentration
1414
detectorsin AMS
such assys- proportional count
has been almostwith
compared constant the during of scintillation
activitya geologic period counters,
ascintillation
standard. In tems)
reality,are
counters,
registrations
therelated
number
registrations to of CC concentration
the number
of
of 14C
in
of registrations
registrations
concentration (β AMS systems) are r
in AMS systems) are
which is long compared to the life span number of a ofCregistrations
14
from the standard under equal
registrations from 14C decay in radiometric from such
detectors the standard under equal
as proportional counters andconditions.
conditions. liquid
nucleus. This natural concentration, 14number C/C, 14 is of
ofregistrations from the14standard under equal conditions.
scintillation
the order of 10 – 12counters,
, which isregistrations
equivalent This C concentration
toofresults
a spe- in aThis
14 results
C activity in inAMSa  or
ratio Csystems)
activity
14 are
ratiorelated
C concentration or C14
toconcen-
the
ratio:
This results in a 14C activity ratio or 14C concentration ratio:
cific number
activity of registrations
about 0.25 Bq/gC from (disintegrations
the standard under equal tration ratio:
conditions.
14
14Asample
14
per second per gram of 14A
14 carbon) (Sect. 5.3). 14 14
a = A = A=
This results in a C activity ratio or C concentration 14
a =1414A ratio: =1414A =
sample

Areference
reference AR
R
14
14 Asample 14
A
8.1.2. Reporting 14
a = 14 C variations = = and 14
14C decay rate in the sample
14
14C concentration in the samp
the 14C standard Areference 14 AR = 14 C decay rate in the sample = 14 C concentration in the samp
= 14C decay rate in the reference = 14C concentration in the referen
Three modes of reporting 14
C activities are in use, C decay rate in the reference C concentration in the refere
14 14
C decay
in part analogous to =the conventions Because rate in the
internation-sample
in the nominator C concentrat ion in the sample
and denominator of the last two fractions the detection
14
C decay inBecause
rate are thecancelled in the =nominator
reference 14
C and denominator
concentrat ion in theand of the last two fractions the detectio
reference
ally agreed (IAEA) for stable isotopes [76, 77]. being equal for sample reference (8.4) material, the use of the
are cancelled being equal for sample and reference material, the use of th
Because in the nominator and denominator adequate forofany thetype
last of measuring
fractions technique.
adequate for any typetwo of measuring the detection efficiencies
technique.
are cancelled being equal for sample and reference material, the use of the ratio 14a is
adequate for any type of measuring technique. 14C T1/2 = 5730 a

3
H T1/2 = 12.43 a 127

β− E max = 156 keV

β− E max = 18 keV

3 14
He N
3 14
A natural = 0.6 Bq / liter H 2O A natural = 250 Bq / kg C

Fig. 8.2.  Decay schemes of tritium and radiocarbon. Both nuclides are pure β– emitters. The present-day specific
activities are given as 3A and 14A.

76
 between C3 plants such as trees (13δ ≈ −25‰)each
and assimilating the as
a C4 plant such same cane (13δ ≈CO
atmospheric
sugar 2. Therefore, in defining the st
−10‰),
14
Chapitre 8 CO2also
each assimilating the same atmospheric in our treatment
. Therefore, in definingofthe
all standard
C data,activity,
we have butto normalise the 14C resu
also in our treatment of all 14C data, we have
value. In Chapterthe1114C
to normalise weresults
will go more13δdetail. Here we suffice
intosame
to the
14 14 14
value.C tauxdedécr
In Chapteroissancede l ' échantillo
11 NATURAL
we will go into
ABUNDANCE international
n more
OFCRADIOACTIVE
concentratagreement
ionISOTOPES
detail. Here dans of C C
all
we lsuffice byresults
' échantillo
andnstating
H have
thattobybe corrected for a deviati
= 14 = 14
C tauxdedécr
international oissance
agreement allde laCréférence
14
results havefrom C concentrat
to be−25‰, ion for
with
corrected dans ladeviation
référence
theaexception ofofOx1 13
the which has to be corrected to −19‰
δ value
(8.4)
from
Because −25‰, in with the exception
the nominator andofdenominator
Ox1 whichThe has
of14toC be corrected
content
standard of to −19‰.
carbon
activity or in naturally growing
concentration was chosen plants.
to represent as clo
the  last
14 two fractions the  detection efficiencies
14
Cdernières
contentto The  of
14
C standard
carbon in activity does not need to be, in
14
Parce que, dans
The leCnominateur standard activity et le dénominateur
or concentration des deux was chosen fractions,
represent asnaturally
l’efficacité
closely de growing
as possible plants.
the The C standard activi
are cancelled being equal for sample and refer- fact it is not, equal to the 
14
14
C activity of the stan-
la détection14ence
est annulée carcarbon
égale pour l’échantillon a isetadequate
leplants.
matériel
be, in fact deit14référence,
is not, equall’utilisation
to the duactivity
C of14Cthe standard.
14
C content material, of the use inofnaturally
the ratio growing
14 The dard. C The definition
standard activity of does not need
the standard toactivity is The definition
rapport a est foradéquate
be, in
any facttype it pour
isofnot, tout typetode
equal
measuring thetechnique
14
technique. C activityde mesure.
activity
of isbased
the standard. basedon on95%
The 95%ofof
definition theofspecific
the specific the standard activity
activity
14
ofCof the original NBS oxali
the origi-
Ainsi donc,activity
le symbole is based14on A doit95% êtreof theutilisé
specific pour year
activity
la of
teneur thenal
AD1950 NBS
original
en 14
C oxalic
(Karlén NBS acid
et al., 1966),
oxalic
(radioactivité (Ox1)
acid in
willthe year
ouas(Ox1) be the AD1950
indiscussed in more detail later
Under natural
Henceforth, circumstances
the symbol 14
a the values
may be usedof 14fora [78], as will be discussed in more detail later.
yeard’un
concentration) AD1950 (Karlénque et al.,méthode
1966), asanalytique
will beThe discussed
14 insoitmore detail later.
C échantillon,
are14between
the  content 0 and 1. Inlaorder
(radioactivity to avoid
or the use
concentration) appliquée
C standard laactivity
radiométrie is defined ou laby:
The  14
C standard activity is defined by:
spectrométrie ofof
The decimals,
dea sample,
14 masse
C standard itwhether
(SMA). isactivity
generalthe analytical
ispractice
definedtoby: report these
technique
values in
applied is %, which is equivalent
radiometric or mass to the factor
spectrometric 14 0
Astandard = 0.95 14 AOx1 0
= 13.56 ± 0.07 dpm/gC = 0.226 ± 0.001 Bq/g
Sous conditions  – 2naturelles, les valeurs de 14a sont comprises entre 0 et 1. Afin d’éviter
10
(AMS). 14 0 (see also Sect. 11.5.1).
14 0
It is incorrect to
d’utiliser des write
décimales,14 Astandard
est=courant
a/10il2 instead 0.95 A
of merely =1413
a..56ces
deOx1reporter ± 0valeurs
.07 dpm/gC en %,= ce 0.226 qui ±est0.équivalent
001 Bq/gC à un (8.6) (8.6)
−2 14 2 14
facteur 10 (voir aussi Part. 11.5.1). Il est incorrect d’écrire a/10dpm/gC au lieu de means a. Radioactive
disintegrations Isotopesper minute and
of Hydrogen perCarbon
In several cases the differences in 14C content be- Radioactive Isotopes of Hydrogen and Carbon
gram of carbon, while the superscript 0
refers to
tween the project
Dans de nombreux cas, les différences samples are danssmall. Therefore,
les teneurs en 14C entre les échantillons d’une
the  fact that the  definition is valid for the  year
même étudethe use
sont faibles. has been Ainsi, taken
l’usageovera from the stable-iso-
été instauré dpm/gC
pour tousmeans
dpm/gC les
means
disintegrations
champs
1950 only.disciplinaires
disintegrations
per minute
per minutedes per gram of carbon, while the supe
per gram of carbon, while the supe
tope field to define relative abundances, the in casu
fact that the definition 14 is valid for the year 1950 only.
isotopes de définir les abondances relatives, telles que thelafactteneur relative
thatBecause
the definition en Cis(activité forouthe year
valid supply 1950 only.
the  relative 14C content (activity or concentra- the original of oxalic acid has
14 14 14
concentration), δ , et de définir la
tion), δ, defined as the  difference between différence de teneur en
Because thebeen C entre
original un échantillon
exhausted,
supplya new et
of oxalic une
batchacid of oxalic
has been acid exhausted,
(Ox2) a new batc
sampleune andfraction
reference Because the original supply of oxalic acid has been exhausted, a new batc
référence, comme de la14C content
valeur as a fraction
de référence : of is available for distribution by
(Ox2) is available for distribution by the NIST (formerly US-Nat. Bureau of S the NIST (former-
the reference value: (Ox2) is available ly US-Nat. for distribution
Bureau of Standards).by the NIST (formerly US-Nat. Bureau of S
14 14 14 Through careful measurement by a number of laboratories (Mann, 1983), the
14 A − AR A 14 Through
2 careful
Through measurement by a number by
careful measurement of laboratories
a number of (Mann, 1983), the
δ= = − 1 = a − 1 (× 10 %)
become related to that of the original (8.5) Ox1 by:has become re-
14
AR 14
AR become laboratories[79], the  14
C activity
related to that of the original Ox1 by:
lated to that of the original Ox1 by:
(8.5) 14 0
14 AOx20 = (1.2736 ± 0.0004) 14 0
14 AOx1
0
Les valeurs de δ sont des petits nombres et sont donc généralement exprimées A Ox2 = (1 . 2736 ± 0 . 0004 )
en ‰, ce qui Ox1 (8.7) A
The values of δ−3are small numbers and there-
est équivalentfore à ungenerally
facteur 10given (cf.inPart.
‰, 4.1).
which is equivalent Both activities referConsequently
to AD1950. the Consequently
Both activities refer to AD1950. standard activity is:
to the factor 10  (cf. Sect. 4.1).
– 3 Both activities refer to AD1950.
the standard activity is: Consequently the standard activity is:
Dans le Chapitre 7, nous avons vu que lors de n’importe quel processus dans la nature, le
14 0
fractionnement se produit, 14 A = 0.7459 14 0
AOx2 (8.8)
In Chapter 7 wenon haveseulement
seen that pour duringlesany isotopes
processstables Amais
0
standard
standard
également
= 0 . 7459 pour
14
A 0 les
Ox2

14
isotopes radioactifs
in nature tels isotope le C. Négliger
que fractionation occurs, cetnot effetonly introduirait
where the  une 14erreur
a0 values dansforlaOx1 and Ox2 refer to
for the stable isotopes but
détermination de l’âge, parce que la teneur originelle where similarly for the radio-14
en C the
14 0
14A 0 values
du matériau serait offor Ox1 and
différente de Ox2 referirrespective
to the activity of the m
active isotope such as 14C. Neglecting this where
effect the the activity
A values 13
forthe material
Ox1 and Ox2 in 1950, refer to the activity of the m
celle supposée. Le degré de fractionnement est indiqué irrespective
par la valeur of
of the time
the
en time δ du of
of measurement.
measurement.
matériau. Un
would introduce an error in an age determina- irrespective of the time of measurement.
exemple est tion,
fourni par la différence
because the originald’âge 14 apparentofentre
C content the ma-
Details les onplantes Details
the en Con
measurement3 comme les calculation
the measurement
and arbres andprocedures calculationare pro-
given in Chapter 1
13
( δ ≈ −25‰) terial
et les would
plantes be en different
C4 comme fromlawhat cannewe Details
assume.
à sucre 13on the
( δ ≈ cedures measurement
−10‰), are chacune and
givenassimilant calculation
in Chapter 11. procedures are given in Chapter 1
14
A survey of available C reference samples of different compounds and
le même COThe degree of fractionation is nicely indicated
2 atmosphérique. Ainsi, en définissant lesA activités
survey standard,
ofA survey
available mais 14
aussi dans
C reference
of available 14 nossamples of different compounds and
C reference samples of dif-
by the  δ value13
of the material. An example Table 11.5.is
traitements des données 14
the apparent C, nous devons
difference normaliser
in age between les
CTable 11.5. ferent
résultats
plants à la compounds
même valeurand deages13 is given in Table 11.5.
δ.
3
Dans le chapitre
such11 as nous
treesverrons( δ ≈ cela
13
−25‰) plusand en détail.
a C4 plant Ici, noussuchnous baserons simplement sur le 14
fait que, par as un sugar accord ( δ ≈ −10‰),
caneinternational,
13
touseach 8.1.3
les assimilating
résultats 14 SURVEY
8.1.3. OF
Survey NATURALofd’une natural 14C VARIATIONS C
8.1.3 C doivent SURVEY être OF corrigés
NATURAL 14
C VARIATIONS
the same atmospheric
13 CO . Therefore, in
déviation de la valeur de δ à −25‰, avec l’exception du Ox1 qui lui, doit être corrigé à
2 defining variations
the standard activity, but also in our treatment 8.1.3.1of ATMOSPHERIC CO2
−19‰. all 14C data, we have to normalise the 14C8.1.3.1 results ATMOSPHERIC
8.1.3.1. Atmospheric CO2 CO2
to the same δ value. In Chapter 11 we Certain
13
will go fluctuations occur in occur
Certain fluctuations the stationary state mentioned
in the  stationary state in Sect.8.1
Certain fluctuations occur in the stationary state mentioned in Sect.8.
into more detail. Here we suffice by stating that
variations inmentioned cosmic rayinintensity, Sect.  8.1.1. andBecause
in climate of affecting
variations the size of the c
128 by international agreement all 14C results the variations
have 14 to
in cosmic ray intensity, and in climate affecting the size of the c
14C content in cosmic ray intensity,
of atmospheric carbon andhas in not
climatealways affecting
been precisely the sam
be corrected for a deviation of the  δ value 13
thefrom C content the size of atmospheric
of the carbon carbon has notthe 
reservoirs, always
14
C been precisely the sa
content
14
−25‰, with the exception of Ox1 which has This to phenomenon
be has been observed by measuring the 14C content of tree ring
This phenomenon has been carbon
of atmospheric observed hasbynot measuring
always been the C content of tree rin
pre-
corrected to −19‰. These fluctuations cisely the same do not exceed as at present. a few This per phenomenon
cent over relatively short p
These fluctuations do not exceed a few per cent over relatively short p
The  14C standard activity or concentration was of
therefore, hasvery beenlittleobserved relevanceby measuring the 14C content
to the hydrologist who is generally
chosen to represent as closely as possibledissolved therefore,
the 14C carbon of veryrings
of tree little(see relevance
Fig. 8.5). to the hydrologist who is generally
from a variable vegetation covering a long and uncertain pe
dissolved carbon from a variable vegetation covering a long and uncertain pe
The strong increase in the atmospheric 14 C level due to the nuclear test explo
The strong increase in the atmospheric 14C level due to the77 nuclear test explo
relevance to the hydrologist. During the bomb explosions 14 3
14C (and 3H) is be
relevance to the hydrologist. During the bomb explosions C (and H) is be
the same nuclear reactions that are responsible for the natural production.
the same nuclear reactions that are responsible for the natural production.
hemisphere the peak concentration occurred during the spring of 1963, wh
hemisphere the peak concentration occurred during the spring of 1963, wh
 INTRODUCTION
These fluctuations do not exceed a  few per cent
over relatively short periods, and are, therefore,
of very little relevance to the hydrologist who is
generally confronted with dissolved carbon from
a variable vegetation covering a long and uncer-
tain period of time.
The strong increase in the atmospheric 14C lev-
el due to the nuclear test explosions is of more
relevance to the hydrologist. During the bomb
explosions 14C (and 3H) is being produced by
the same nuclear reactions that are responsible
for the natural production. In the northern hemi-
sphere the peak concentration occurred during
the spring of 1963, when it was about double
the natural concentration (Fig. 8.3). In the south-
ern hemisphere a more gradual increase has taken
place. This is due to the fact that the seasonal in-
jections of 14C from the stratosphere into the tro-
posphere primarily occurred over the northern
hemisphere, while air is not easily and simply
transported across the equator. The 14C increase
only gradually leaked through the equatorial re-
gions to the southern troposphere.
8.1.3.2. Vegetation and soils
The higher 14C levels have entered the soil vegeta-
tion, and have become detectable in the CO2 gas,
present in the soil and playing a major role in
the formation of dissolved inorganic carbon in
groundwater. In this way the ‘bomb effect’ pos-
sibly increases the 14C content of young ground-
water.
The CO2 generated in the soil by decaying plant
remains and by root respiration is relatively
young and therefore contains about the atmo-
spheric 14C concentration (14a = 100%) (Fig. 8.3).
8.1.3.3. Seawater and marine carbonate
Because seawater is in constant exchange with
atmospheric CO2, one would expect that, like
the stable carbon isotopes, that an isotopic equi-
librium exists between the two reservoirs. This is
not the case, due to the phenomenon of upwell-
ing of water from greater depth and a consider-
able age. This may extent to ages of 1500 years,
equivalent to an 14a value of the order of 85%. In
general, in surface seawater 14C contents are ob-
served in the range of 95%.
78
1200
C content (‰) of atmospheric CO 2
1000
northern hemis phere
800
600
400
200
southern hemisphere
14
0
1960
60 65 1970
70 75 1980
80 85 90 199095
14
C content of atmospheric CO 2
Fig. 8.3.  Curve representing the natural 14C content
of atmospheric CO2 (data for Nordkapp, Norway,
representative for the  northern hemisphere) (Nydal,
pers.comm.). Test explosions of nuclear weapons
since the fifties and especially the early sixties have
temporarily increased the  concentration by a  factor
of two. Due to isotopic exchange with the  oceans,
14
C is slowly returning to ‘normal’. The  influence
on the  southern hemisphere was obviously small-
er. The  seasonal variation of some per cent during
the late 1960s has been smoothed out, since they are
not relevant in hydrology, contrary to the  3H varia-
tions to be discussed later in this chapte
8.1.3.4. Groundwater
By processes of erosion and re-sedimentation
fossil carbonate is generally part of terrestrial
soils. Here it may be dissolved by the action of
soil-CO2, which is contained by the  infiltrating
rain water. In this way the dissolved inorganic
carbon in groundwater also contains 14C [17].
As the carbonate is very old and thus without
14
C (14a = 0%) — generally, but not always (see
Volume 4 on Groundwater) — the bicarbonate re-
sulting from the reaction:
CO2 + H2O + CaCO3 → Ca2+ + 2HCO ! (8.9)
will have a 14C content one half that of the CO2
(14a = 50%) (cf. 13C, Fig. 7.7). Isotopic exchange
with soil CO2 or atmospheric CO2 lead to higher
14
C concentrations of the inorganic carbon frac-
tion of recent groundwater, in combination with
respectively decreased or increased 13δ (see
Sect. 7.2). The increased level of 14C in atmo-
spheric CO2 since 1963 can lead to 14C contents
in soil organic matter and soil CO2, which even
exceed the natural atmospheric value.
 NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H

8.1.4. C age determination

14
14
Asample
14 0
A
T 5568 sample
T = − 1/ 2 ln =− ln 14 0 = − 8033 ln 14 asample
Knowing the rate of radioactive decay (λ or T1/2), ln 2 14
Astandard 0.693 Astandard
the age (T = time elapsed since death) of a carbo-
14 0
T /2
14
Asample 5568 A
naceous sample,
T = − 1organic
ln 14 or inorganic,
= − canlnbe14cal-
sample
= − 8033 ln 14 asample (8.10)
Astandard 14 0
ln 2
culated from the measured a, if the A
activity, 014.693 C
standard
activity at the time of death, 14ainitial , is known
(Eq. 6.7): In order to avoid confusion, the original (con-
ventional) half-life of T1/2 = 5568 years is still
T = − (T1/2/ln2)(14a/14ainitial) being usedisby
The result international
called agreement
the conventional 14 for geo-
C age BP
logical and archaeological dating. In
of the sample, that is the age Before Present hydrol-
(by
Considering this equation, 3 quantities have to ogy, however, we will apply the true half-life
be well established: T1/2, a and the proper val-
14 i definition: before AD1950).
of 5730 years.
ue 14a of the 14C activity of the sample. As was
explained before, the condition that sample and The practice using these conventional ages is neat
reference activity are determined at the same time but of course a  simplification. Apart from using
and under similar conditions results in the 14a val- the ‘wrong’ half-life, the assumption of a constant
ue valid for the year 1950, i.e. the age obtained 14
C content of living organic matter is proven un-
counts back from 1950. true. However, by applying the 14C calibration
curve, i.e. the empirical relation between the con-
By international convention:
ventional age of tree rings (to 10 000 years BC)
(1) the initial activity equals the standard activ- and their real age, both problems are solved and
ity in AD1950; 14
C ages are translated into real ages (Fig. 8.5).
The ‘wiggles’ of the calibration curve are due
(2) the  14C activities have to be normalised for
to the natural variations in the atmospheric 14C
fractionation (samples to 13δ = −25‰, Ox1
content, mentioned in Sect. 8.1.3. Further details
to −19‰, Ox2 to −25‰) (see Chapter 10);
about radiocarbon dating are, for instance, given
(3) the original (Libby) half-life of 5568 has to by [82, 83]
be used.
This results in the relation:

atmosph. CO2
exchange 105% precipitation

plants / humus
100% soil H 2O
oceanic HCO −3
100%

humus CO 2 dissolved CO 2
100% 100%
groundwater
50% HCO −3
marine CaCO 3 soil CaCO 3
≤ 100% 0%
erosion / sedimentation
groundwater
65–85% DIC

Fig. 8.4.  Schematic representation of the formation of dissolved inorganic carbon in groundwater. The percent-
ages are the 14a values indicative for the carbonate dissolution, which is the most relevant process in most types
of groundwater. The  14a value of groundwater HCO −3 of 50% results in higher values of 14a in the total dissolved
carbon because of the additional CO2 and of isotopic exchange with the soil-CO2.

79
 INTRODUCTION

8.1.5. Dating groundwater 350

300
Dating water as such has no meaning. Dating 250
groundwater is determining the age of groundwa-

δN (‰)
200
ter, i.e. the time elapsed since the water became

14 i
150
groundwater, in other words, since it infiltrated 100
into the soil as precipitation or any other type of 50
surface water (rivers, lakes). 0
real age in years BC/AD

In principle there are some methods of calculat- -50

-14000 -12000 -10000 -8000 -6000 -4000 -2000 0 2000
ing or estimating groundwater ages, for instance, 14000
based on hydrodynamical modelling. Here we 12000

C age in years BP
discuss the application of radioactive decay. 10000

Essential to know is the input function, i.e. 8000

14
the (time dependent) amount of radioactive tracer

Conventional
6000

that infiltrated. The water molecule itself has one 4000

radioactive isotope, tritium or 3H. The disadvan- 2000
tages are that both the activity and the half-life 0
are very small. Possible applications will be dis- -14000 -12000 -10000 -8000 -6000 -4000 -2000 0 2000

cussed in Sect. 8.3. Therefore, we are driven back

BC AD
Real age in years AD/BC

on radioactive compounds dissolved in the water,
rather than the water itself. In Chapter 12 we will
discuss several radioactive isotopes that can be
applied. Here we are concerned with 14C, which
has a very attractive half-life for solving hydro-
logical problems. It is contained by dissolved in-
organic carbon (DIC) as well as dissolved organic
molecules (DOC).
8.1.5.1. Dating groundwater with DIC
If 14ai were known and if no carbon entered or
escaped the groundwater in the course of time,
the water age (since infiltration) would be given by:
T = −8267 ln [(14a / 14a0standard) / (14ai / 14a0standard)]
= −8267 ln(14a / 14ai) (8.1
we have to warn the reader that, for geochemi-
Itcal reasons, to
is tempting to obtain trustworthy
apply this 14 groundwa-
C method to DIC:
ter ages by applying the radiocarbon
the sampling and measuring techniques are dating
rela-
technique
tively simpletoand
DIC is by noHowever,
available. means simple and
straightforward.
Volume 4 of this series will discuss the various
problems. Here we limit ourselves with a brief
review.
The initial 14C activity 14ainitial (= 14ai) in the total
dissolved inorganic carbon content (DIC) of in-
filtrating groundwater can not simply be taken as
being equal to 14astandard, as in the procedure of cal-
culating conventional ages (Eq. 8.9). Estimating
the original, real value 14ai or 14ai of recent
groundwater is more complicated.
Fig. 8.5.  Variations in the 14C content of atmospher-
ic CO2 in the  past (upper curve), resulting from 14C
measurements of treerings of accurately known age by
a number of laboratories, and of annual growthrings
in corals [80]. The parameter showing the deviations
from the  standard is defined by Eq. 11.47. The  data
result in the calibration curve (lower curve), used for
translating conventional 14C ages into real ages [81]
(Sect. 11.5.4.3). The  straight line in the  calibration
curve represents y = x.
8.1.5.1.1. The origin of 14C in DIC
In general, the formation of DIC in groundwater
essentially consists of two processes: (i) the dis-
solution of carbonate by H+ in H2CO3 from at-
mospheric CO2 (in arid regions) or soil CO2, or
in organic acids, and (ii) isotopic exchange with
CO2 as mentioned in Sect. 8.1.3. Various mod-
els are dealing with the development of DIC and
the concurrent 13δ and 14a values.
8.1.5.1.2. The chemical/isotopic mass balance
The CO2-CaCO3 concept first proposed by [17]
is based on the mass balance of inorganic carbon
(Fig. 8.4) in the closed system of soil CO2, soil
CaCO3 and water. CaCO3 is dissolved by an equal
molar amount of biogenic CO2 (0.5b), whereas an
additional amount of CO2 (a ) is required to stabi-
lise the solution chemically. For the 14C analysis
of ground water all CO2 is extracted from the so-
lution after acidification. Rewriting Eq. 8.9 in
a more complete form gives:

80
8.1.5.1.2 Les balances de masse chimique/isotopique δ g − δl a+b
Le concept CO2−CaCO3 proposé initialement par Münnich (1975) est basé sur le bilan de
masse du carbone inorganique (Fig. 8.4) dans un système avec les closexpressions
vis-à-vis du respectives
CO2 du des sol, valeurs
du de 14ai et 13δ en lieu et place de a
CaCO3 du sol et de l’eau. Le CaCO 3 est dissous parNumériquement,
une part molaire avec l’utilisation
équivalente des valeurs de 13δ et 14a des Figs. 7.7.et 8.
NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of Cde and CO H2
biogénique (0,5b), tandis que un taux additionnel dedeCO 20%
2 (a) deest 2 dissous dans
COnécessaire eaux souterraines conduit à des valeurs 13δ et
pourlesstabiliser
chimiquement la solution. Pour l’analyse du 14C deset eaux 60%, souterraines,
respectivement. tous les CO2 sont
(a +0.5b)CO2 + 0.5b CaCO3 + H2O → 0.5b Ca2+ 8.1.5.1.3. Isotopic exchange in an open system
extraits de la
+ bsolution
HCO! +après a COacidification. La ré-écriture de l’Eq. 8.9 sous une forme plus
(8.12)
complexe donne:
2
8.1.5.1.3 Echange In an open system the 
isotopique
13
δ and 14aouvert
en système values may fur-
where a and b are the respective concentrations ther change by isotopic exchange of DIC thus
13 14
of dissolved carbon dioxide and bicarbonate. Dans2+un In système
formed −ouvert,
with les valeurs de CO
surrounding δ 2et a peuvent
, which may évoluer
be dans le tem
(a +0,5 b)CO + 0,5b CaCO
this simple concept the chemical composition
2 3 + H 2 O → 0,5b Ca + b HCO 3 + a CO 2 (8.12)
soil- as well as atmospheric CO
isotopique du DIC ainsi formé et le CO22 environnant qui peut être du C in the unsaturat-
of the water, in casu the carbonic acid fractions, ed dans
zone.laInzone principle both values change
atmosphérique non saturée. En principe, lesinvaleurs
par- changent en pa
ou a et b sont les concentrations
determine the originalrespectives
14
a value of de the mixture
dioxyde de carboneof dissous et de bicarbonate.
allel to an isotopic equilibrium situation between
CO2 and HCO!: situation d’équilibre isotopique entre le DIC et le CO2, de telle façon que les v
Dans ce contexte simple, la composition chimique de l’eau c’est-à-dire DIC andlesthe CO fractions that the 14a and 13δ values
2, sod’acide are
13
δ14soient couplées
coupled par:
by: −
carbonique, permettent de déterminer la valeur originelle a du mélange entre CO2 et HCO3 :
(a + b)14a = 0.5b 14al + (a + 0.5b)14ag (8.13)
14
aex − 14 a0 13 δ ex − 13δ 0
where the subscripts
14 14 l
(a + b) a = 0,5b al + (a + 0,5b) agand g refer14to the solid car- = (8.17)
bonate and the gaseous CO2, respectively. As in
14
aeq − 14 a0 13 δ eq(8.13) − 13δ 0

most groundwaters, pH is low so that the only car-
où les indices l et g se réfèrent au carbonate solide et CO où les gazindices where ex, the subscripts
respectivement. eq etComme ex, eq
0 se réfèrent,
pour la and 0 respectivelyà re-
respectivement, la valeur actuelle
bonic acid fractions are the dissolved CO2 (a)2 and
fer to the actual values after isotopic exchange,
plupart des HCO! 
eaux souterraines
(b). With the  le pH a values given in isotopique,
14 est faible, les fractions
Fig. 8.4 d’acide à l’ultime
carbonique valeur quand l’équilibre isotopique avec le CO2 environna
correspondent
− 14 the ultimate values when isotopic equilibrium
seulement auxthe dissolved
CO2 (a) et bicarbonate
HCO3 (b) dissous.is expected Avecto lesà valeurs
have laa valeur
14
C aoriginale
données après dans ladissolution
Fig. 8.4, leen système fermé. La combinaison de l
content of 50%, while an additional amount 14 of
with the surrounding CO2 has been reached and
bicarbonate dissous est supposé avoir une teneur en dilution C de isotopique
50%, tandis et desqu’unecorrections
partie d’échange ont été utilisées par de nom
CO2 (with 14a = 100%) shifts the  14C content of the original values after closed-system dissolou-
14 14
additionnelle du CO2 (avec a = 100%) déplace la teneur (Gonfiantini,
en C tion, du1971;
DICrespectively. The combination of the isoto-1979). Toutefois,
Mook,
(= a + 1976;
b) vers 1980;
une Fontes et Garnier,
DIC (= a + b) to a somewhat higher value. This
valeur quelque
methodpeu plus élevée. Cette
of estimating méthode 14
the original chimiques
d’estimation
C content de laetpic
of teneur en 14Ccorrection
géochimiques
dilution en milieuand
originelle souterrain
des sont si correc-
the exchange compliquées que les mo
eaux souterraines, et donc and
groundwater, de correction constituent
de l’âgethe apparent
thus correcting apparent de par des tion
le fait have
approchesbeen used
que a ≠raisonnables
14 i by several authors [87–90].
100%, est mais ne peuvent pas être considér
age for the fact that a
14 ii
≠ 100% is referrred to
méthodes as de However,
corrections the chemical
précises. and geochemical con-
appelée la correction de dilution chimique (Ingerson et Pearson, 1964; Geyh et Wendt, 1965).
the lachemical dilutionencorrection ditions underground are so complicated that
Avec 14al = 0% teneur originale 14
C du DIC[84, est: 85].
Sous
With
climat the above
tempéré avec models desmay solsbeà reasonable végétale, les valeurs de 1
couvertureapproaches
14
al = 0% the original C content of the DIC is:
14

observées sont butgénéralement

are not to be considered
dans la gamme cleandecorrection
−11 à −14‰ meth-et 65 à 85%, respe
14 i a + 0.5b 14 a + 0.5b ods.
a = ag = ×100% (8.14)
a+b a+b (8.14) In temperate climates where the land has a veg-
etation cover, the observed values of 13δDIC and
The factor 14 i a14/ ag  =  a / a0 is called the dilution
14 i 14 14 i 14
14 i 14
a / agwith
Le facteur factor = aa value
/ a0 estbetween
nommé0.5 facteur
and 1. de dilution avec une 14 valeur comprise entre 0,5
aDIC are generally in the range of −11 to −14‰
et 1. and 65 to 85%, respectively.
An alternative approach is to consider the stable
carbon isotopic composition of DIC in the ground-
water, instead of the chemical composition. For 8.1.5.2. Dating groundwater with DOC
136 13
C a similar mass balance can be written as for 14C
Attempts were made to determine the age of
in Eq. 8.13:
groundwater, i.e. the  time elapsed since infiltra-
tion, by means of dating the dissolved organic
(a + b)13δDIC = 0.5b 13δl + (a + 0.5b)13δg (8.15)
carbon (DOC) content of the water sample. Based
where the subscripts are the same as in Eq. 8.13. on their solubilities in specific acid solutions,
The isotopic and the chemical dilution correction the soluble and thus mobile organic compounds
are now related by [86]: are subdivided in fulvic acids (soluble at low pH)
and humic acids. These organic molecules, origi-
13
δ DIC − 13δ l a + 0.5b nating from the decomposition of organic matter,
= (8.16) (8.16)
13
δ g − 13δ l a+b are relatively resistent against further degrada-
tion.
with the respective expression for 14ai and 13δ val-
with the respective
ues instead expression
of a and for
14 i
b (Eq. 8.14).
13
δ values instead
a and Numerically, Alsoofhere a weandareb confronted
(Eq.8.14). with the problem to
δ δand assign a
14 i
values to the recently infiltrated water.
Numerically,usingusingthe  and 14aavalues
values of of Figs 7.7 and 8.4 8.4 a 20% fraction of dissolved
13 14
the 13 Figs.7.7.and CO2
a 20% fraction [91] concluded that only the fulvic fraction origi-
13 of dissolved
14 i CO2 in groundwater
in groundwater results13in δ and a values of −14.6‰ and 60%, nates respectively.
with certainty in the soil zone and thus is
results in δ and a values of −14.6‰ and 60%,
14 i

respectively. able to produce reliable 14

C ages, based on an 14ai
8.1.5.1.3 Isotopic exchange in an open system value in the range of 85 ± 10%. This range of val-
ues depends on the average age of the soil organic
In an open system the 13δ and 14a values may further change by isotopic exchange of DIC thus
formed with surrounding CO2, which may be soil- as well as atmospheric CO2 in the
81
unsaturated zone. In principle both values change in parallel to an isotopic equilibrium situation
between DIC and the CO2, so that the 14a and 13δ values are coupled by:
 INTRODUCTION
matter in the recharge zone, which can be hun-
dreds of years.
8.2. Relation between C and C 13 14
variations
A survey of the relevant values of the 14C (14a in
%) and 13C content (13δ in ‰) in the reservoirs
relevant for the hydrological cycle is given in
Fig. 8.6.
The values are merely indicative and do not ex-
clude deviations. The  figure is a  combination of
the above discussions represented schematically
in the Figs.7.5, 7.7 and 8.4.
Special attention in this figure needs the  value
for marine carbonate. Accidentally the observed
14
a values for vegetation and marine carbonate
are almost equal. The fact is that two processes
cancel each other: (i) starting with organic mat-
ter on land with 13δ about −25‰ and 14a = 100%
(by definition, cf. Sect. 7.1.2), the  difference in
13
δ between land vegetation and marine carbon-
ate (via atmospheric CO2) of about 25‰ requires
14
a of the latter to be 5% (= 2 × 25‰) larger; (ii)
the upwelling of deep sea water with ages of up
to 1500 years generally causes the surface ocean
water to be depleted by (accidentally) also 5%.
8.3. The radioactive hydrogen
isotope
8.3.1. Origin of 3H, decay and half-
life
The radioactive isotope of hydrogen, 3H (tritium
or T), originates (as does 14C) from a nuclear re-
action between atmospheric nitrogen and thermal
neutrons [74]:
14
N + n → 12C + 3H (8.18)
The  3H thus formed enters the hydrologic cycle
after oxidation to 1H3HO (Fig. 8.7). It finally de-
cays according to:
3
H → 3He + ß− (8.19)
According to a recent re-evaluation [93],
a more
with preferable
Eβmax = 18 keV value is 4500 ± 
and a half-life of8 12 
days
430
(equivalent to 12.32 year; the former value has
years [92] (Fig. 8.2).
been used in this text).
82
8.3.2. Reporting 3H activities and
the 3H standard
Because the nuclear reaction (Eq.  8.18) has
a lower probability than reaction (Eq. 8.1) and be-
cause the residence time of 3H in the atmosphere
is much smaller than that of 14C, the natural 3H
concentration in the air is much smaller than that
of 14C. Natural 3H abundances are either present-
ed as specific activities in Bq per litre of water)
or in Tritium Units (TU), the latter by definition
equivalent to a concentration of 3H/1H = 10 – 18 (1
TU = 3.19 pCi/L = 0.118 Bq/L) (Sect. 4.3).
For 3H, as for 14C, it is extremely difficult to de-
termine the  absolute specific activities. Tritium
activities, are therefore related to a reference wa-
ter sample which is measured under equal con-
ditions. For this purpose the IAEA and NIST
(the former NBS) has available a tritium standard
NBS-SRM 4361 of 11 100 TU as of September 3,
1978 [92]. After being related to this standard, 3H
concentrations are reported in absolute values (3A
in TU), corrected for decay to the date of sample
collection.
8.3.3. Survey of natural 3H
variations
Under undisturbed natural conditions the 3H con-
centration in precipitation was probably about
5 TU, which is equivalent to a specific activity of
about 0.6 Bq/L [94].
Following the nuclear weapon tests of the early
sixties, the 3H content of precipitation temporar-
ily increased by a 1000-fold in the northern hemi-
sphere (Fig. 8.8). Since 1963 this extreme 3H
content has decreased to essentially natural val-
ues in winter and about twice natural in summer.
A large part of the 3H (as well as 14C) produced
by the nuclear explosions has been injected into
the stratosphere and returns to the troposphere
each year during spring and early summer. This
causes the seasonal variation in both 3H and 14C,
more pronounced in the former, because the resi-
dence time of H2O to which 3H is coupled in
the atmosphere is very small ( in the order of
weeks).
The probability of contamination of young
groundwater by bomb 3H prevents the water to
be simply dated by measuring the degree of 3H
decay. Nevertheless, 3H data can often be used to
determine dates ante quem or post quem. For in-
 NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H

stance, water with 3A < 5 TU must have a mean
residence time of more than 40 years; water
having 3A > 20 TU must date from after 1961.
The tracer use of 3H will further be discussed in
the Volume 4 of this series.
8.4. Comparison of 3H and 14C
variations
8.4.1. Relation between 3H and 14C
in the atmosphere
At first we will compare the  curves showing
the 14C and 3H variations in atmospheric CO2 and
H2O, respectively (Figs 8.3 and 8.8), because they
give important information on the global carbon
and water cycle, respectively. The main differ-
ences are the following.
(1) The effect of the nuclear bomb 14C and 3H
had a much more pronounced effect on
the atmospheric content of the latter, because
the natural 3H concentration is so much
lower.
(2) The restoration to natural conditions goes
faster for 3H than for 14C, because the turn-
over time of water in the atmosphere from
evaporation of ocean water to precipita-
tion very short (in the order of weeks),
while the exchange of CO2 between the at-
mosphere and ocean water is very slow (in
the order of years).
(3) For the same reason does 14C show much
smaller seasonal amplitudes than 3H;
the consequence for the latter is that in tem-
perate climates, where the  main infiltration
of rain occurs during the winter half-year,
groundwater rarely shows the high 3H values
observed in precipitation during the early
1960s.
(4) The  14C increase after 1960 in the air over
the southern hemisphere is less pronounced
than over the northern hemisphere, as
the majority of the nuclear tests took place
in the north and, moreover, since the air is
not easily transported across the equator; for
3
H the consequences are that the equivalent
curve for the Southern hemisphere is much
different: it is less regular, shows a maxi-
mum at 30 TU around 1963 – 1965 with oc-

HCO −3 in isotopic
equilibrium
vegetation/soil
CaCO 3
air CO 2
100
apparent
80 exchange with air CO 2
as surface water
a (%)
14

60
ageing groundwater ageing
40
ageing
20

fossil fuels fossil carbonate

−32 −28 −24 −20 −16 −12 −8 − 4 0 +4

13
δ (‰)

Fig. 8.6.  Schematic representation of the  relation between variations in 13C and 14C in nature. The  groundwa-
ter values have been explained in the  Figs 7.7 and 8.5. The  marine bicarbonate and solid carbonate (verti-
cally dashed) values for the case of an isotopic equilibrium with atmospheric CO2 are not observed in the ocean.
The upwelling of deep, relatively old (1500 a) water causes the surface water to be lightly depleted in 14C. The ap-
parent age of this water — and consequently of the marine carbonate formed in this water (horizontally dashed)
— is about 400 years (equivalent to 5% 14C).

83
 Isotopes radioactifs de l’Hydrogène et du Carbone

INTRODUCTION
Le principal obstacle est la valeur isotopique inconnue au temps zéro,
l’infiltration, pour le 3H aussi bien que pour le 14C. Toutefois, le 14C et le
casional peaks up to 80 TU, and a slow de-de façon
offrent oftensure
equally relevant)de ismettre
la possibilité less des
complicated,
limites auxatâges absolus, en p
crease to the natural level (5 TU) at present.
les combine avec des preuves hydrogéologiques ettohydrochimiques.
least if the chemistry does not point the action
(5) 14C is being used to calibrate global carbon of processes underground — such as carbonate
cycle models, indicating the exchange Déterminer
(and des âges relatifs
dissolution, (i.e. les différences
decomposition of additionald’âges
(old) entre
or- des échantillo
moins
transition) time of (additional) CO2 between ganic
compliqué, matter,
au and
moins si certainly
la chimieif we are
montre dealing
l’absencewith
de processus soute
air and sea; H is being applied in oceanog-
3 a  mixture of different water — that could influ-
la dissolution de carbonates, la décomposition de matière organique (ancienn
water de ence
raphy, indicating the rate of verticalcertaine the carbon isotopic composition. In that case
mélanges d’eaux différentes- qui pourraient influencer la composi
movement and lateral water flow. the age difference between water samples col-
du carbone. Dans ce cas, la différence d’âges entre des échantillons d’eaux p
lected at two geographical locations k and k+1 is
endroits géographiques
expressed as: k et k+1 s’exprime ainsi:
8.4.2. Relation between 3H and 14C
14
in groundwater a
ΔT = 8270 ln 14 k +1 (8.20)
We have already emphasised that our discussion a k
of the occurrence of 14C and 3H in groundwater
où 8270 = where(ln2)/T1/28270 = (ln2)/T
ans. D’un 1/2 years.
point de From a qualita- des conclusions
vue qualitatif,
may not lead to the idea that, using these iso-
approximativestive point of view,
peuvent être a few
renduesapproximate
à partir desconclusions
données isotopiques. P
topes, we are able to simply measure the age of
l’échantillon can be drawn from isotopic data.
3 For
d’eau montre une activité H mesurable (supérieureinstance, if à 1 UT),
groundwater, i.e. the period of time elapsed since
the water sample shows a measurable 3H activity
the infiltration of the water. récente, i.e. inférieure à 50 ans, ou correspond à un mélange d’eaux récente
(larger than 1 TU), the water is subrecent, i.e. less
The main obstacle is the unknown isotopicenfin, valuescontient
than un ajout old,
50 years d’unor certain pourcentage
is a mixture of young d’eau
and oldrécente. Avec de
14 3
at time zero, the moment of infiltration, for 3
H as
mesurables en Coretat least
water, H, l’eau est an
contains certainement
admixture âgée de plusieurs dizain
of a cer-
well as for 14C. However, 14C and 3H together cer-
d’années. Sitain l’eau est très récente,
percentage of recentlawater.
teneurWith 14
en no C doit être proche ou supé
measur-
tainly offer the possibility to set limits to absolute able 14
C and 3
H the water is certainly a few
14 tens of
parce que le CO2 du sol contient probablement du C thermonucléaire.
ages, especially in combination with hydrogeo- thousands of years old. If the water is very recent,
logical and hydrochemical evidence. Le volume 4the  de14cette série est
C content tout particulièrement
is expected to be close todévolu a ces problèmes et (
or above
Determining relative ages (i.e. the ageUne differ-
synthèse100%, because
simplifiée et the soil–CO then is likely
générale est2 donnée sur la to con-
Fig. 8.9. Avec les eaux
ences between neighbouring samples, which is tain bomb C. 14
nous refèrons aux eaux qui se sont infiltrées depuis quelques dizaines d’an
souterraines jeunes peuvent avoir n’importe quel âge compté en centaines d’a
souterraines anciennes en plusieurs milliers d’années. Enfin, le terme très a
également aux eaux souterraines fossiles qui ne contiennent plus de 3H et 14C e
3
H 3H 3H
3
H 3
plusieurs dizaines de milliers d’années. Les eaux qui ont des teneurs relativem
H 3
H et plus faibles en 14C que les eaux récentes sont probablement des mélange
14
N + n → 12C + 3H 3
H → 3He + β−
3
H et anciennes.

3
H 1HO
hy drol og ical c y c l e

precipitation
surface runoff
evaporation

oceans i nfil tra ti on rivers

hy dr ol ogic al c y c l e

Fig. 8.7.  Origin and distribution of 3H in nature. Contrary to 14C, the turnover of 3H is very fast, except where it
is fixed in glacier ice or groundwater.

84
 NATURAL ABUNDANCE OF RADIOACTIVE ISOTOPES of C and H

4000

northern hemisphere

H concentration (TU)
3000

2000
3

1000

0
1955 1960 1965 1970 1975 1980 1985 1990

Fig. 8.8.  Smoothed curve representing the  average 3H content of precipitation over the  continental surface of
the Northern hemisphere.

Volume 4 of this series is especially devoted to 100

these problems and (im)possibilities.
A  general and simplified survey is shown in 75
Fig. 8.9. With recent groundwater we refer to
A (TU)

water that infiltrated not more than some tens of

mixed recent
3

years ago. Young groundwater may have any age 50 waters groundwater
of hundreds of years, old groundwater thousends.
Finally very old, also referred to as fossil ground-
water does not contain 3H and 14C and is several 25

tens of thousands of years old. Waters which are

relatively high in 3H and lower in 14C than re- 0 fossil old groundwater young
cent water are likely to be mixtures of young
and old water. 0 25 50 75 100
14
a (%)

Fig. 8.9.  Schematic representation of relations

between the 14C and 3H content in groundwater.
The  scheme is merely indicative and serves to give
a general impression. The terminology is discussed in
the text.

85
9. CHEMISTRY OF CARBONIC ACID IN WATER

9.1. Introduction balance has to be taken into account. In

this chapter some examples are given.
Studying the carbon isotopic composition of wa-
ter, whether it concerns freshwater or seawater, (b) Measuring the carbon isotopic compo-
a complication arises from the fact that the dis- sition of a solution comes to extracting
solved inorganic carbon always consists of more the total CO2 from the sample after acid-
than one compound, while also the presence of ification, instead of single compounds.
gaseous CO2 and solid calcium carbonate may be
relevant. In fact we are dealing with the follow-
ing compounds and concentrations: For the essential translation of 13δ of total dis-
solved carbon to 13δ of single compounds, and
●● gaseous CO2 (occasionally denoted by CO2g) conversely, the inorganic carbon chemistry, i.e.
with a partial pressure PCO2 of the dissolved inorganic carbon is required.
●● dissolved CO2 (denoted by CO2aq)
●● dissolved carbonic acid, H2CO3 with a  = Once the various concentrations of the dissolved
Chapitre
species, to be deduced in the next 9
sections are
[H2CO3] + [CO2aq]
known,
Chapitre 9 the 13C mass balance:
●● dissolved bicarbonate, HCO ! with
b = [HCO!] ([CO 2 aq] + [H 2CO 3 ] + [HCO3− ]Chapitre + [CO 2−9]) 13 RDIC =
Chapitre3 9
([CO 2 aq]CO$
●● dissolved carbonate, + [H 2 CO + [HCO 3− ] + [CO 32−=][CO
with3 ]c = [CO$] ) 13 RDIC
2 aq= ] 13 RCO22aq + [H 2 CO 3 ] 13 RH 22CO33 + [HCO 3− ] 13 RHCO33 + [CO 32− ] 13
(
([CO 2 aq ] +3[H
− 13 CO ] + [HCO 2− − 13
3 + [CO 3 3−] ] +R[CO 32− ]) 13 RDIC =
(9.1)
2− 13

3 ]) R
= [CO 2 aq] 13 RCO2aq + [H 2 CO 3 ] 13 RH 2CO + [HCO
aq + ] 2R + + (9.1)
●● total dissolved inorganic carbon, DIC, ou, with [CO ] [H CO ] [HCO ] [CO DIC− =13
3 HCO 3 CO 3
en =insérant
[CO 2 aq] 13 RCO2aq + [H 2 CO 3 ] 13 RH 2CO3 + [HCO 3− ] 13 RHCOprécédemment
2
les 13symboles
2 3
des divers 3 13
composés mentionnés + [CO 322−− ] 13 e
CT = a + b + c 13 RCO
= [COor, aq ]
inserting R + [H
the previously CO ] Rmentioned + [HCO ]
symbols R 3
+ [CO ] R
ou, en insérant les symboles des diversconcentrations 2 en CO2CO
composés mentionnés aqprécédemment
et en acide
2 aq 2 3 carbonique,
H 2CO 3
et en H2CO33,les
combinant ce dernier
HCO3 étant3 une fra CO
●● solid carbonate, CaCO3 (occasionally denot- donc for the various
négligeable, la composition concentrations
isotopique du and
carbone combining
total dissous (C = a + b +
ed concentrations en CO2aq et en acide ou, carbonique, H2CO les3, symboles
ce dernierdes étant une fraction très petite et précédemment et en
T
en insérant
by s) ou, en insérant the concentration
les symboles des of divers
CO2aqcomposés
divers and the carbonic
composés
mentionnés
mentionnés acid,
précédemment et en
donc négligeable, la composition isotopique du carbone
concentrations en total
CO dissous
aq et en(Cacide T=a+ ba negligibly
+ c) est : H2CO
carbonique, 3, ce dernier étant une fracti
H CO ,
13 CO2aqaR
2the latter
+ bR being cRc small frac-
The ambiguity in using carbon isotopes now con-
concentrations en et aen acideb + carbonique, H2CO3, ce dernier étant une fracti
2 3
donc négligeable, R
la
tion, the isotopic=
composition composition of the total dis- T = a + b + c) e
isotopique du carbone total dissous (C
sists of two observations: aR + bR + cRdonc négligeable, CTT
la composition C isotopique du carbone total dissous (CT = a + b + c) e
13
RCT = a b c solved carbon (CT = a + b + c) is: (9.2)
T

(1) On the one hand, only the isotopic CT composi- 13 aR + bRb + cRc

tion of a single compound in relation toetthat 13 RCT en
inversement, = insérant
aRaa + bR les + cRc de fractionnement propres tels que mentionn
facteurs
RCT = CTb (9.2)
ofetanother compound
inversement, is les
en insérant geochemically or
facteurs de fractionnement
C
propres telsTque mentionnés avant:
hydrologically meaningful. We have seen an 13
CT inserting
RCTT
et inversement, anden13 conversely,
Rinsérant
= les facteurs de the proper
fractionnement
b fractionation
propres tels que mentionnés
example of this statement while discussing
et inversement, en insérant
b les +facteurs de fractionnement propres tels que mentionnés
C 13
R factors as a α
mentioned b + c α
before:
the carbon isotopic
13
Rb = compositionT of ground-
T C
b
a / b c / b
(9.3)
water, for 13C as well aαas 14 b + cα
a / b +C (Figsc / b 7.7 and
CT 13 RCT
Les
13
R
paragraphes = CT 13 Rseront b (9.3)
Rb = aα a / b + b + cTα c / b bconsacrés à l’analyse de la composition
suivants C
8.4). In other words: an isotopic fraction- 13 b

carbonatées. aα a / b +lab +composition

cα c / b
ation
Les factor is a fundamental,
paragraphes suivants seront physico/chem-
consacrés à l’analyse de chimiques d’eaux
ical quantity
carbonatées. only if it is the ratio between The next sections will be devoted
Les paragraphes suivants seront consacrés à l’analyse de la composition ch
to analysing
two isotopic ratios of single compounds. Les For the chemical
paragraphes suivants composition
seront consacrés of carbonate
à l’analyse waters.
de la composition ch
instance:
9.2
carbonatées. LES EQUILIBRES DE L’ACIDE CARBONIQUE
carbonatées.
3 9.2 LES EQUILIBRES DE L’ACIDE CARBONIQUE
αa/b = 13Ra/13Rb   and   13αc/b = 13Rc/13Rbb En présence de CO2 gaz, le CO2 dissous échange avec le CO2 gaz:
9.2. Carbonic acid equilibria
9.2 LESle EQUILIBRES DE L’ACIDE CARBONIQUE
(2) 9.2
En présence de CO2 gaz, le CO2 dissous échange avec
LES
In CO
CO2 gaz:
EQUILIBRES
the presence
2(g) + H2O ⇔
DE
ofCO L’ACIDE
gaseous CO
2(aq) + H
CARBONIQUE
2O2, dissolved CO2
En présence de CO
exchangesgaz, le CO
with dissous échange avec le CO2 gaz:
COCO 2 gas:échange avec le CO2 gaz:
2 2
(a) On the other hand,
CO2(g) + Hin mass balance con- de
En présence
2O ⇔ CO2(aq) + H2O
CO2 gaz, le 2 dissous (9.4)
siderations the carbon isotopic composi- COCO
tion of a mixture of compounds is rel- CO CO22(g) 2(aq)
(g) ++HH+ H⇔
2OO ⇔⇔CO
2OCO H2CO
2(aq) +3H2O
2(aq) + H2O (9.4)
2(g) + H2O ⇔ CO2(aq) + H2O
2

evant. For 2(aq) + H2O

COinstance, if ⇔
COH2CO
2 or CaCO
3
CO se2(aq) + H2aux
O ⇔phases
H2COgaz
(9.5)
ou g 3 et aq réfèrent 3 (9.5)
et dissoutes respectivement. Bien que l
are being removed from a dissolved car- soit CO2(aq) + H2O ⇔ H2CO3
largement 3
oubon
g etsolution,
aq se réfèrent aux phases gaz CO
et dissoutes (aq) + H Osupérieure
2(aq) CO2respectivement. 2CO3àque
⇔ HBien celle
la de H2CO3 dissous
concentration en (d’un facteur de 10
of for estuarine mixing of where g and2 aq refer to the gaseous and dissolved
COfresh- concentration de tous(d’un
les CO 2 dissous par
3 [H2CO 3]. La condition d’ équilibre e
2(aq) soit
andlargement
seawater,supérieure
the totalà 13cellegdeet Haq
C mass
ou 2CO dissous
phase,
se3 réfèrent facteur
respectively.
aux phases de 10
Although
gaz ), nous noterons la
the concentration
et dissoutes respectivement. Bien que la c
ou quantifiée
g et aq separréfèrent aux phases
la solubilité molaire gaz et dissoutes
Ko (Loi de Henry) respectivement.
: Bien que la c
concentration de tous les CO2 dissous COpar [Hsoit
2(aq) 2CO3largement
]. La condition d’ équilibre
supérieure à celle entre
de les 3 phases
H2CO dissousest
(d’un facteur de 1033), n
CO2(aq) soit largement supérieure à celle de H2CO3 dissous (d’un facteur de 10 ), n
quantifiée par la solubilité molaire Ko (Loi de Henry)de
concentration : tous les CO2 dissous par [H2CO3]. La condition d’ équilibre entr
concentration de tous[H les2 CO
CO32] dissous par [H2CO3]. La condition d’ équilibre entr
quantifiée par la K o =
solubilité molaire Ko (Loi de Henry) :
[H 2 CO 3 ] quantifiée par la solubilitéPCO
molaire Ko (Loi de Henry) :
Ko =
2
2
(9.6)
PCO2 [H 2 CO 3 ]
K o =partielle
ou la pression [H CO 3 ] CO2 atmosphérique PCO2, est exprimée en atm, Ko est l
K = P2 du
En présence de CO2 gaz, le CO2 dissous échange avec le CO2 gaz:

CO2(g) + H2O ⇔ CO2(aq) + H2O (9.4)

INTRODUCTION
CO2(aq) + H2O ⇔ H2CO3 (9.5)

ou g et aq se CO2(aq)aux
of réfèrent farphases
exceeds gazthat of dissolved
et dissoutes H2CO3 Bien
respectivement. AT = [HCO!] + 2[CO$] +en[OH−] − [H+] + [other
que la concentration
CO2(aq) soit (in the order of 10 ) àwe denote
de H2the concentration weakdeacid
10 ),anions] (9.14)
3 3
largement supérieure celle CO3 dissous (d’un facteur nous noterons la
of all dissolved CO
concentration de tous les CO2 dissous by [H
parCO ]. The equilibrium
2 [H32CO3]. La condition d’ équilibre entre les phases est
2
in which concentrations of other weak acids may
quantifiée parcondition
la solubilitébetween
molaire Kthe 
o
phases
(Loi is quantified
de Henry) : by
be included in the interest of high precision, such
the molar solubility Ko (Henry’s law):
as humic acids in freshwater or borate, [B(OH) −4  ],
[H 2 CO 3 ] in seawater.
Ko = (9.6) (9.6)
PCO2 Under natural conditions [H+] and [OH-] are neg-

ligibly small compared to the carbonate species
ou la pressionwhere the atmospheric
partielle CO2 partial
du CO2 atmosphérique PCO2pressure, PCO2en
, est exprimée , atm,
concentrations. The sum
Ko est la solubilité molaireof the weak acid and
is −1in atm, Ko is the solubility in mol·L · atm
−1 −1
−1
en mol L atm , et [H2CO3] est la concentration en CO2 dissous en mol/kg alkali-ion
d’eau. concentrations, determined by an acid
and [H2CO3] is the dissolved CO2 concentration titration, referred to as the total alkalinity, thus
H2CO3 se dissocie en eauofselon
in mol/kg water. about equals the carbonate alkalinity defined as:
H CO dissociates in water according to
H22CO3 3+ ⇔ H+ + HCO3− AC = [HCO!] + 2[CO$] (9.7) = b + 2c (9.15)
H2CO3 + ⇔ H + HCO! (9.7)
+

et If the water contains Ca2+ (or Mg2+) and carbon-

and ate or is in contact with calcite also the disso-
− + 2−
HCO 3 ⇔ H + + CO3
HCO! ⇔ H + CO$ (9.8) Chimie de l’acide carbonique ciation equilibrium(9.8) of calcite affects the carbon
ou les conditions d’équilibre sont quantifiées les constantes
parl’acide chemistry:
carboniquede dissociation ou d’acidité:
where the  equilibriumChimie de
conditions are quantified
144 [H ][HCO 3 ] or acidity constants:
by the dissociation
+ – CaCO3 ⇔ Ca2+ + CO$ (9.16)
K1 = + – (9.9)
[H[H][HCO
CO ]3]
K1 = 2 3 (9.9) where the concentrations
(9.9) are limited by the solu-
[H 2 CO 3 ] bility product:
et
and
et KCaCO3 = [Ca2+][CO$] (9.17)
+ 2–
[H ][CO ]
K2 = + 3
– 2– (9.10) (9.10)
[H ][CO ]
K 2 = [HCO ] 33
–
(9.10)
9.3. The equilibrium constants
[HCO ] 3

Enfin, la dissociation de l’eau obéit à la condition d’équilibre suivante Basically all values of the solubilities and dis-
Here de
wel’eau
have to à emphasise that, although sociation constants are temperature Chapitre 9dependent.
Enfin, la dissociation obéit la condition d’équilibre suivante
the hydrogen
Finally
Kw = [H ][OH ] − ion, H
+ the dissociation +
, is
of commonly
water obeyshydrated
the equi- However, the K values (9.11)also depend on the solute
to form
Klibrium H− O+ or even to multiple hydrated
+ condition
w = [H ][OH 3] concentrations, because (9.11) the formation of ion com-
ions, we will write the hydrated hydrogen 9.3 ion LES CONSTANTES D’EQUILIBRE
plexes between the carbonic
Ici nous devons préciser +
que,− bien que l’ion hydrogène, H , soit communément hydraté pour former ions and molecules
K as =H[H as][OH
+ +
the hydrated
] (9.11) structure does notFondamentalement,
+ enter and ions in
toutes the solution
les valeurs dehinder the dissolved
solubilité et constantescar-
de dissociation sont d
Ici
H3Onous
+ devons
, nous w préciser
écrirons l’ionque, bien que l’ion hydrogène, H , soit
hydrogène + communément hydraté pourprise
former
the chemical models.en tant que H+ puisque la structure
température.
hydratée
bonic
Toutefois,
n’est pas
molecules and ions
en
to take part in the ther-
H +
3O , nous
compte dansécrirons l’ionchimiques.
les modèles hydrogène en tant que H puisque la structure hydratée les valeurs
n’est de Kendépendent aussi des concentrations en solu
pas prise
formation modynamic
d’ions complexes equilibrium
entre reactions.
les ions Therefore,
carboniques et les in
ions et molécules
compte dans les modèles + + chimiques.
The [H ] concentration is generally
La concentration en [H ] est généralement donnée au traversgiven as a pH
de la the thermodynamic
valeur du pH, définie commeequation,
son the concentrations
empêche les molécules et les ions de prendre part aux réactions d’équilibre thermody
value,
La concentration en defined
logarithme ] est as
[H+inverse :the negative
généralement logarithm:
donnée au travers have
del’équation
la valeur du to be
pH, replaced
définie comme their activities, that are
byson
dans thermodynamique, les concentrations doivent être remplacées par le
logarithme inverse : smaller than the concentrations. The thermody-
pH==−−1010log[H
pH log[H ] ] (9.12)
+ + sont plus faibles. La constante de (9.12)
solubilité thermodynamique est :
namic solubility constant is:
pH = −10log[H+] (9.12)
The total
La concentration totale enconcentration of dissolved
carbone inorganique dissous (=inorganic
carbone total, également
a H 2COnotée
γ par
[H ΣCO 2 ou
2 CO 3 ]
La concentration totale
carbon en carbone
(= total
ΣC ou DIC) est définie comme: inorganique
carbon, also dissous
denoted (=
by carbone
SCO total,
or K =
également
0
3
=
notée
a
par ΣCO 2 ou (9.18a)
2 PCO 2 PCO 2
ΣC ou DIC) est or DIC)
SCdéfinie is defined by:
comme:
CT = [CO2aq] + [H2CO3] + [HCO3−] + [CO32−] = a + b + c (9.13)
CCT ==[CO aq] + [H CO ] + [HCO −
] + [CO 2−
] = a + b + c where in general (9.13) the activity coefficients γ < 1
où en général, les coefficients d’activité γ < 1 (γ = 1 pour une solution idéal
L’alcalinité estTune[CO 2aq] pratique,
+ [H2COdéduite3] + [HCO!] + [CO $] de l’électroneutralité
2 2 3 3 3
quantité de la conservation (γ = 1 for andes ideal solution,
solutions ou i.e. with zero solute
L’alcalinité est concentration en solutés nulles ou une force ionique nulle).
les = aune
concentrations +enbquantité pratique,
+ c (9.13)
ion-métal (Na, Ca, déduite
Mg) etdelelapHconservation
sont constants de l’électroneutralité
: concentrations desorsolutions ou strength).
zero ionic
les concentrations en ion-métal (Na,2−Ca, Mg) −et le pH sont constants
Dans les : solution non-idéales d’eaux marines ou de saumures, il est plus pratiqu
AThe  alkalinity
− is a practical quantity,
+ following
T = [HCO3 ] + 2[CO3 ] + [OH ] − [H ] + [autres anions ouIn the non-ideal
acides faibles] solutions
(9.14) of seawater and brack-
from the conservation
− 2− of electroneutrality
− + relations
in solu- entreish
leswater
concentrations
it is more réelles et lesto
practical concentrations mesurables par la consta
describe the rela-
AT = [HCO3 ] + 2[CO3 ] + [OH ] − [H ] + [autres anions ou acides faibles] (9.14)
Dans laquelletions
les concentrations en d’autres acides
where the metal-ion concentrations (Na, faibles peuvent
apparente être incluses pour obtenir une plus
Ca, : tion between the real, measurable concentrations
Dans laquelle
grande les
précision, concentrations
tels que les en
acides
Mg) and pH are constant: d’autres acides
humiques dansfaibles
les peuvent
eaux êtreouincluses
douces pour obtenir
bylesthe apparent
borates, [B(OH) une
− plus
4 ] dans
solubility constant:
grandedeprécision,
l’eau mer. tels que les acides humiques dans les eaux douces ou les borates, ] K 4−] dans
[H CO [B(OH)
K 0' = 2 3 = 0
l’eau de mer. P 2 γa
En conditions88naturelles, [H+] et [OH−] sont négligeables par comparaison aux COconcentrations des
−
En conditions
espèces naturelles,
carbonatées. [H+] et
La somme des[OH ] sont négligeables
concentrations en acides par comparaison
faibles aux concentrations
et en ions alcalins, déterminée des
par
espèces carbonatées. La somme en
destant
concentrations Les constantes thermodynamique et d’acidité apparente (dissociation) des prem
une titration acide, référencée qu’alcalinitéentotale,
acides équivaut
faibles etdonc
en ions alcalins,
presque déterminée des
à l’alcalinité par
une titrationdéfinie dissociations de l’acide carbonique
référencée en tant qu’alcalinité totale, équivaut donc presque à l’alcalinité des
acide,par: (Eqs. 9.6, 9.9 et 9.10) sont maintenant reliées par:
carbonates
Dans
où enles solution
général, lesnon-idéales
coefficientsd’eaux marines
d’activité γ < ou
1 (deγ =saumures,
1 pour une il estsolution
plus pratique
idéale, de
i.e.décrire les
avec des
apparente
où en
relations : lesles
général,
entre coefficients
concentrations d’activité
réelles et γ
les < 1 ( γ = 1
concentrations pour une
mesurables solution
par la idéale,
constante i.e.
de avec des
solubilité
concentration en solutés nulles ou une force ionique nulle).
concentration
apparente : en solutés nulles ou une force ionique nulle).
Dans les solution [H 2 CO 3 ]
non-idéales K0
d’eaux marines ou de saumures, il est plus pratique de décrire les
Dans les K 0' = non-idéales
solution = d’eaux marines ou de saumures, il est plus (9.18b)les
relations entre les concentrations
[HP2 CO
CO 2 3 ] γréelles
K a0
et les concentrations mesurables par lapratique
CHEMISTRY OF CARBONIC ACID IN WATER
constantedededécrire
solubilité
'
relations : Kles
apparenteentre 0 =concentrations
PCO2
= réelles et les concentrations mesurables par la constante de (9.18b)
γa
solubilité
apparente :
Les constantes thermodynamique et d’acidité apparente (dissociation) des première et seconde
[H CO 33 ] K 00 practically equal to those reported by [95] for
dissociations
Les constantes de0'' l’acide
K carbonique
= [H 22 CO
thermodynamique = K (Eqs. 9.6, 9.9 et
et d’acidité 9.10) sont
apparente maintenant reliées
(dissociation)
(9.18b) par:
des première et(9.18b)
seconde
0'
P 3] γ freshwater (at S = 0‰):
K =
dissociations de0 l’acideCO
2
CO =
carbonique a
0

a (Eqs. 9.6, 9.9 et 9.10) sont maintenant reliées par: (9.18b)
P 2 γa +
22

a H aCO γ H [H ]γ b [HCO 3− ]
K
The  =
HCO3
thermodynamic = and the apparent acidity pK0 = −2622.38/T −(9.19a)
0.0178471T + 15.5873
Les constantes thermodynamique
1 + d’acidité− apparente (dissociation) des première et seconde
et
a a
(dissociation) a γ [Hγ [H ]γ CO
[HCO ] ] [96] (9.22)
=constants b of the  3 first and second
H H HCO
CO a 2 3
Les constantes
dissociations K thermodynamique
=
de1 l’acide
2 3 3
carbonique
H et d’acidité
(Eqs. 9.6, 9.9 et apparente
9.10) sont(dissociation) des première
maintenant reliées par: et(9.19a)
seconde
dissociations de l’acide a
dissociation of
carbonique
H 2CO γ
carbonic [H
(Eqs.
a COacid ] (Eqs.9.6, 9.9 and
2 9.6,3 9.9 et 9.10) sont maintenant reliées par:
pK1 = 3404.71/T + 0.032786T − 14.8435
3
et 9.10) are now related ++by:
a HH a HCO γ HH [H ]γ bb [HCO 33−− ] [96] (9.23)
et K11 = a H a HCO = γ [H + ]γ [HCO − ]
HCO33
(9.19a)
a HH+2][HCO − H γ [H bCO ] 3
K1' = [H CO
CO
3
= ] a
a γ 2
2 3
3 (9.19a) (9.19a)
K1 = a H+22CO33 =γ a [Ha2 CO K13 ]
3 3
pK2 = 2902.39/T + (9.19b)
0.02379T − 6.4980
[H[H][HCO 2 CO 3 ]3 ]
−
γ γHγa b
et K1 ='
= K [97] (9.24) (9.19b)
et and [H 2 CO 3 ] γ Hγ b 1
lnKw = 148.9802 − 13847.26/T − 23.6521 lnT
[H ++ ][HCO −− ]
K11'' = [H + ][HCO33− ] = γγ aa K11 (9.19b) [98] (9.25) (9.19b)
K1' = [H 22 CO 33 ]3 = γ HHγa bb K1 (9.19b)
[H 2 CO 3constante
et, par rapport à la deuxième ] γ Hγdeb dissociation: where the absolute temperature T = t(oC) +
and with respect to the second dissociation con- 273.15 K.
et, par rapport à la deuxième constante de dissociation:
stant: a a
H CO3 γ [H + ]γ [CO 2− ]
K2 = = H + c − 32− (9.20a)
aaHHCO
aCO3 3 γ H [H γ b [HCO
]γ c [CO 3 ]3 ]
9.3.2. Seawater
et, par rapportKà2 la= deuxième=constante de dissociation: (9.20a) (9.20a)
a HCO3 constante
et, par rapport à la deuxième γ b [HCO −
3]
de dissociation: The  salt concentration of seawater is defined by
et the  salinity, given in g/kg of seawater, or in ‰.
and a HH aCO γ HH [H ++ ]γ cc [CO 3322−− ]
et K 22 = a H aCO = γ [H + ]γ [CO
CO33
2−
− 3 ]
Probably the best (9.20a)
data have been reported by
a HCO 2 − H γ [HCO −
]
K 2' = [H +
HCO ][CO
3
= ] b
b γ c
3
3 [95]; these values (9.20a)
for the temperature range of 0
K 2 = a HCO =γ b [HCO K3−2]
3 3 b
(9.20b) (9.20b)
3

[H[HCO+ 3
][CO3 3] ] γ γH γb c
− 2− to 40°C and the salinity range of 0 to 40‰ are
et K 2' = = K 2 (9.20b)
shown in Figs 9.1 to 9.4 and in Table 9.1 (right-
et [HCO 3− ]also γtakes
The definition H γ c into account that in re-
146 hand shaded column). The seawater values (at
146
ality instead
[H +
+
][CO of − [H ] the pH is being measured
22 −
]
+
γ S = 35‰) are practically equal to the values pub-
K 22'' = [H
based on + a series
][CO
33
2− =
] of γ
bb
buffer K 22 solutions. Therefore, lished by [99, 100],(9.20b)
as reported by [101]:
K '
= [HCO −
− 3]
= γ γb
K (9.20b)
in 2these[HCO equations 3
3
−
] [Hγ ]γis to2 be replaced by 10 .
+H
H c
c - pH
3 H c
146 Comparing fresh and seawater, the differences lnKo’ = −60.2409 + 9345.17/T
146 in the  first and second dissociation constants of + 23.3585 ln(0.01T) + S [0.023517
carbonic acid — K1 and K2 for freshwater, and
K1’ and K2’ for seawater — and the consequences − 0.023656 (0.01T) + 0.0047036 (0.01T)2 (9.26)
thereof will appear spectacular.
pK1’ = 3670.7/T − 62,008 + 9.7944 lnT
For practical reasons the values of the dissocia-
tion constants are generally given as: − 0.0118 S + 0.000116 S2 (9.27)

pK = − 10log K     or     K = 10− pK (9.21) pK2’ = 1394.7/T + 4.777 − 0.0184 S + 0.000118 S2

The  K0, K1 and K2 values for freshwater (ideal
solution) and seawater as a function of the water
temperature and the water salinity are discussed
in the next section and shown in Figs 9.1 – 9.4.
9.3.1. Ideal solutions
(9.28)
(K0’: [99]), (K1’, K2’: [100], reported by [101].
The salinity values S are related to the originally
used chlorinity, i.e. the concentration of chloride
(+bromide and iodide, also given in g/kg or ‰),
by:

Most freshwaters can be considered as ideal solu- S = 1.80655 Cl (9.29)

tions (extrapolated to zero ionic strength). Values
for the temperature range of 0 to 40°C and the sa-
linity range of 0 to 40‰ are shown in Figs.9.1 to
9.4 and in Table 9.1 (left-hand shaded column).
The classic data of Harned and co-authors are
The solubility product of calcium carbonate dif-
fers for the two different crystalline types, calcite
and aragonite. Figs 9.5 and 9.6 show values at
specific temperatures and salinities.

89
 Fig. 9.5. Produit de solubilité (Eq. 9.17) de la calcite (CaCO3) dépendant de la tem
salinité
Fig. 9.5. Produit de l’eau pendant
de solubilité la précipitation
(Eq. 9.17) de la calcite(valeurs
(CaCOselon l’Eq. 9.43
3) dépendant de (Mucci
la tem
salinité de l’eau pendant la précipitation (valeurs selon l’Eq. 9.43 (Mucci
INTRODUCTION
9.4 CONCENTRATIONS
Fig. 9.5. Produit EN ACIDE
de solubilité (Eq. 9.17) CARBONIQUE
de la calcite (CaCO3) dépendant de la tem
9.4 CONCENTRATIONS
salinité de
Comme mentionné, les l’eau
différences EN
pendantentre ACIDE CARBONIQUE
la précipitation (valeurs
les constantes selonpour
d’acidité l’Eq.les
9.43 (Mucci
eaux douc
9.3.3. Brackish water 9.4. Carbonic acid
considérables.
Comme ProduitCeci
Fig. 9.5. mentionné, affecte
les grandement
différences
deconcentrations
solubilité entre la
(Eq. 9.17) lesdistribution
de laconstantes des fractions
d’acidité
calcite (CaCO pourdelesl’acide
3) dépendant eaux carb
de la douc
tem
The large differences between K and eaux
K’, i.e.
9.4 naturelles.
considérables. Des
Ceci de
salinité exemples
affecte
CONCENTRATIONS
the large effect of salt concentrations on the acid-
seront
l’eaugrandementmontrés
pendant EN dans
la précipitation
ACIDE les
la distribution parties suivantes.
des fractions
(valeurs
CARBONIQUE
As we have mentioned the difference between
de 9.43
selon l’Eq. l’acide carb
(Mucci
eaux
La naturelles.des
distribution Desespèces
exemples seront montrés
de l’acide carbonique dansdissous
les parties
dans suivantes.
unepour
eau pure peut douc
être
ity constants (Fig. 9.4), result in an entirely
Comme the acidity
dif- mentionné, constants
les différences for
entre the fresh and d’acidité
les constantes seawater les eaux
ferent chemical character of freshwater and 9.4distribution
une
La fonction are
sea-
considérables. considerable.
duCeci
carbone
des espèces
CONCENTRATIONS
affecte de This EN
inorganique
l’acide
grandement greatly
total
carbonique
ACIDE effects
ladissous. the distribu-
A partir
dissous des
dans
CARBONIQUE
distribution des équations
une eau de
fractions 9.6,
pure 9.9être
peut
l’acide et 9
carb
water, as will be illustrated in the next sections.
9.20
une
eauxfonction tion
respectivement,
du Des
naturelles. of
carbonethe carbonic
nous obtenons
inorganique
exemples acid
: fractions
total dissous.
serontentre
montrés dans Ain natural
lespartir wa-
dessuivantes.
parties équations 9.6, 9.9 et 9
Comme mentionné, les différences
ters. Examples of this les constantes d’acidité pour les eaux douc
The acidity constants for freshwater with 9.20zero
respectivement, nous obtenons : will be shown in the fol-
salinity and for seawater have extensively considérables.
La [HCeci
distribution
been des
lowing affecte
espèces grandement
de
sections. la distribution
l’acide carbonique dissousdes
dansfractions
une eau de
purel’acide carb
peut être
2 CO 3 ] = K 0 PCO 2
studied experimentally. The problem remains eaux
une naturelles.
fonction du Des exemples
carbone seront
inorganique montrés
total dans
dissous. les
A parties
partir dessuivantes.
équations 9.6, 9.9 et 9
[H 2 CO 3 ] = K 0 PCO2of the dissolved carbonic acid
The distribution
the proper treatment of waters with varying 9.20low
respectivement,
species
La distribution nous
des espèces obtenons
in pure water: can
de l’acide be specified
carbonique dissousas a frac-
dans une eau pure peut être
salt concentrations. In order to obtain the proper tion of the total dissolved inorganic carbon. From
une fonction du carbone inorganique total dissous. A partir des équations 9.6, 9.9 et 9
K’ values, the K values must be corrected with [H 2 CO
Eqs = Kand
]9.9
9.6,3nous PCO9.10,
9.20 respectivement, [H0+
] 2 : respectively,
obtenons −
Eqs 9.18, 9.19
the help of the Debye-Hückel theory applicable [H 2 CO
and = obtain:
9.203 ]we [HCO 3 ]
at low concentrations. The treatment of non- K+1 ]
[H −
[H CO ] =
[H 2 CO 3 ] = KK0 PCO2
2 3 [HCO 3] (9.33)
ideal solutions is illustrated here by considering 1
freshwaters with less dissolved salts than about [H + ]
400 mg/L [102]. [H 2 CO 3 ] = [HCO 3− ] (9.34)
2− K 2K1 −
A measure for the salt concentration is the ionic [CO 3 ] = + +[HCO 3 ]
K[H] ]
[H − −
strength (I) of the water. This can be approximat- [H
[CO 2 CO
2−
3 ] 3=
] = +2 [HCO [HCO 3 ]3
] (9.35)
ed by: [H K]1
ce qui donne
so that K2
I ≅ 2.5 × 10 S (9.30)
−5 ce qui donne [CO 32− ] = +
[HCO 3− ]
+[H ]
⎛ [H ] K ⎞
where S is the salt concentration in mg/L. The ap- CT = ⎜⎜ + + 1 + +2 ⎟⎟[HCO 3− ] (9.36)
2 −⎛
⎝ [H K
K1 ] 2 [HCO K 2 ]− ⎞⎠]
[H −
[CO
ce qui donne CT =3 ⎜⎜
proximate values for the two acidity constants ] = +1+ 3 ⎟[HCO 3 ]
[H + ] [H + ] ⎟⎠
then are: ⎝ K1 Chimie de l’acide carbonique
Les concentrations fractionnées
The fractional peuvent
concentrations être de
Chimie maintenant
can bedonnées
nowcarbonique
l’acide given en fonction de la te
ce qui donne ⎛ [H ] +
K2 ⎞
0.5 I 2 I in
total:concentrations = ⎜⎜fractionnées
CTterms + 1 + peuvent
of the total ⎟[HCO
+carbon
−
]
content:
pK 1' = pK 1 − and pK 2' = pKLes2 − ⎝ K1 [H[H ]+⎟⎠]K1
être3 maintenant données en fonction de la te
1 + 1.4 I 152 1 + 1.4 [HCO
total: I −
] =+ + 2 [H ++ ]K CT
[HCO ⎛3−[H
] = ] ] +K[H
[H ⎞
2 ]K11 + K −1K 2 C (9.37)
CT = ⎜⎜fractionnées ⎟[HCO 3 maintenant
[H++1]+2 [H + K1]K 2
3 T
0.5 I 2 I 152
Les concentrations [H+ +⎟]K être
+peuvent données en fonction de la te
'
and pK 2 = pK 2 − ⎝ 1 K ] ⎠ 1
(9.31)
total:
+ 1.4 I 1 + 1.4 I
[H + ]2
Les [H
concentrations
152 [95] CO ] = [CO
fractionnées aq] =
peuvent être maintenant
[H++]]K2 + Kdonnées CT en fonction de la te
The acidity constant values published by [H
2
CO
3
] = [CO
2
aq] = [H + ]2 + [H 1 1 K 2 C
total: 2 3 2 T
are derived from the above considerations on [H + ]2 + [H + ]K1 + K1 K 2
(9.38)
non-ideal solutions taking into account a series
152
of different compounds. Sets of data for various 2− KK
[CO 3 ] = + 2 K1+K 2 CT (9.39)
temperatures and salinities are further presented [CO 3 ] = [H + ]2 + [H 1+ ]K2 1 + K1 K 2 CT
2 −

in Table 9.1. [H ] + [H ]K1 + K1 K 2
and likewise for the apparent acidity constants K’
à peu près de façon identique pour les constantes d’acidité apparentes K' dans de
Values of the solubility product of etcalcite in non-ideal solutions such as seawater.
et à peutelles
idéales
(CaCO3) (Eq. 9.17) used in this volume are taken
près que
de façon
l’eau de mer. pour les constantes d’acidité apparentes K' dans de
identique
idéales tellesThe relative
que l’eau de contributions of [H2CO3], [HCO!]
mer.
from [103]: Les contributions relativesto de [H2CO3carbon −
], [HCOcontent 2−
and [CO$] the total 3 ] et [CO is 32− ] dans la teneur en ca
shown
−
Les contributions
indiquées surinla Fig.  relatives
Fig. 9.6 de
9.6 enasfonction[H CO
a function ],
2 du3 pH of [HCO
pourpH ]
3 deuxet [CO 3 ] dif-
fortempératures
two dans différentes,
la teneur en ca
pour
pKcal = −10logKcal = 171.9065 + 0.077993 T(de
indiquées surferent
force ionique la Fig.
nulle) 9.6 etenenfonction
temperaturesmoyennedu forpHfreshwater
pour pour
les deux
eaux températures
(at (S
marines ionic différentes,
= 35,0‰ ou Cl =pour
19,3
− 2839.319 / T − 71.595 logT + (0.77712 (de force ionique strength = 0)
nulle) et enand average
moyenne pourseawater (S = 35.0‰
les eaux marines (S = 35,0‰ ou Cl = 19,3
Comme nousorl’avons Cl = 19.37‰).anticipé, les constantes d’acidité de l’acide carbonique change
− 0.0028426 T − 178.34 / T)S1/2 + 0.07711 S
Comme nous l’avonset anticipé,
avec la température les constantes
la force ionique d’acidité
de la solution decela
que l’acide carbonique
produit une très change
forte d
− 0.0041249 S (9.32)
3/2 As
avec la températurewas anticipated, the acidity constants of car-
distribution à la fois et
surlalaforce ionique et
température delalasalinité.
solution que cela produit une très forte d
bonic acid change so rapidly with temperature
distribution à la fois sur la température et la salinité.
Values are shown in Fig. 9.5 as functions of and with the ionic strength of the solution that it
9.5 and
the water temperature for fresh- and seawater results
EXEMPLESin a strong dependenceOUVERTS
SUR SYSTEMES of the distribution
ET FERMES
as a function of salinity at 20°C. 9.5 on both temperature
EXEMPLES and salinity.
SUR SYSTEMES OUVERTS ET FERMES
Dans ce paragraphe, quelques exemples seront donnés sur la manière de résoud
Dans ce paragraphe,
mentionnées ci-dessus.quelques
Nous nous exemples seront
référerons auxdonnés surclos
systèmes la manière de résoud
dans lesquels les
90 mentionnées ci-dessus. Nous nous référerons aux systèmes clos
carbonique n’échangent pas, que ce soit avec le système gaz (CO2 atmosphériqueles
dans lesquels ou
carbonique n’échangent
la phase solide (CaCO3pas, que ce
). Dans unsoit avec leouvert,
système systèmelagaz (CO2 atmosphérique
solution échange soit ave ou
la phase solide (CaCO ). Dans un système ouvert, la solution échange
(= système ouvert sur la 3phase gaz), ou avec le solide (ouvert sur CaCO3). Nous allon soit ave
(= système
avec (i) laouvert sur la phase
comparaison entregaz),
eauoudouce
avec leetsolide (ouvert
eau de deux3). en
mer,surlesCaCO Nous allon
équilib
 CHEMISTRY OF CARBONIC ACID IN WATER

TABLE 8.1.  Apparent solubility and acidity (dissociation) constants

of carbonic acid for various temperatures and salinities.
The values are according to [95].
K0 × 102 S (‰)
t (°C) 0 5 10 15 20 25 30 35 40
0 7.691 7.499 7.295 7.112 6.934 6.761 6.592 6.412 6.252
5 6.383 6.223 6.067 5.916 5.754 5.610 5.470 5.321 5.188
10 5.370 5.236 5.105 4.977 4.842 4.721 4.603 4.477 4.365
15 4.571 4.457 4.345 4.236 4.121 4.018 3.917 3.811 3.715
20 3.936 3.837 3.741 3.648 3.556 3.459 3.373 3.289 3.199
25 3.428 3.342 3.258 3.177 3.090 3.013 2.938 2.858 2.786
30 3.013 2.938 2.864 2.793 2.723 2.655 2.582 2.518 2.449
35 2.679 2.612 2.547 2.483 2.415 2.355 2.296 2.234 2.178
40 2.404 2.344 2.286 2.223 2.168 2.113 2.061 2.004 1.954

K1 × 107
t (°C) 0 5 10 15 20 25 30 35 40
0 2.667 4.667 5.433 5.984 6.412 6.761 7.047 7.278 7.464
5 3.069 5.420 6.353 7.015 7.534 7.962 8.299 8.610 8.851
10 3.467 6.194 7.295 8.072 8.690 9.204 9.638 10.00 10.30
15 3.846 6.966 8.241 9.162 9.908 10.52 11.04 11.48 11.86
20 4.188 7.727 9.183 10.26 11.12 11.83 12.45 13.00 13.46
25 4.498 8.433 10.09 11.32 12.33 13.18 13.90 14.52 15.07
30 4.753 9.099 10.96 12.36 13.52 14.49 15.35 16.11 16.75
35 4.966 9.705 11.80 13.37 14.69 15.81 16.79 17.66 18.41
40 5.105 10.26 12.56 14.32 15.81 17.06 18.20 19.19 20.09

K2 × 1010
t (°C) 0 5 10 15 20 25 30 35 40
0 0.240 1.291 1.879 2.355 2.773 3.155 3.508 3.837 4.150
5 0.284 1.600 2.339 2.951 3.491 3.981 4.436 4.864 5.272
10 0.331 1.950 2.877 3.639 4.325 4.943 5.534 6.095 6.607
15 0.380 2.350 3.491 4.436 5.284 6.081 6.823 7.516 8.185
20 0.430 2.793 4.188 5.346 6.397 7.379 8.299 9.183 10.05
25 0.479 3.289 4.966 6.383 7.656 8.872 10.02 11.12 12.19
30 0.527 3.828 5.834 7.534 9.099 10.57 11.99 13.34 14.66
35 0.573 4.426 6.792 8.831 10.72 12.50 14.22 15.89 17.50
40 0.617 5.070 7.870 10.28 12.53 14.69 16.79 18.79 20.75

91
 Freshwater S = 0 ‰
6

K 0' × 10 2
5
5

4
INTRODUCTION 15

3
Seawater S = 35 ‰
25

2
8 0 5 10 15 20 25 30 35 40
t ( oC)
7
Freshwater S = 0 ‰ 4
[96] Harned & Davis, 1943
6
3.8
K 0' × 10 2

5
3.6

K 0' × 10 2
5
[95] Millero & Roy, 1997
25
4 3.4
15

3 20
3.2
Seawater S = 35 ‰
25 t = 20 oC Seawater S = 35 ‰
2 3
15 25

K 1' × 10 7
0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
o 15
t ( C) S (‰ or g/kg)
10
5
Fig.4 9.1.  The solubility constants (= solubilities in M/L.atm) for CO in freshwater, seawater and brackish water
[96] Harned & Davis, 1943 2
as3.8a function of temperature at salinities of 0, 5, 15, 25, and 35‰ 5
(= g of salt per kg of water) (upper graph) and
S=0‰
as a function of salinity at 20°C (lower graph). All values are according to [95], at higher salinities similar to
3.6 0
K 0' × 10 2

[99] (Eq. 9.26); the values for freshwater are &similar

[95] Millero Roy, 1997 to those of
0 [96]5 (Eq. 9.22).
10 15 20 25 30 35 40
3.4 t ( oC)
25
3.2
t = 20 oC 6
320
0 5 10 15 Seawater
20 S = 35
25‰ 30 35 40 Freshwater S = 0‰
5
15
S (‰ or g/kg) 25
K 1' × 10 7

K 1 × 107

15
4
10
5

5 3

S=0‰ 25

0 2
0 5 10 15 20 25 30 35 40 20 0 5 10 15 20 25 30 35 40
o
t ( oC) t ( C) S = 35 ‰
Seawater
K 2' × 10 10

15 25

6
Fig. 9.2.  The acidity constants for the first dissociation of carbonic acid in freshwater and seawater as a function
15
10
of the water temperature at salinities
Freshwater of 0, 5, 15, 25, and 35‰. The values are according to [95]. The freshwater
S = 0‰
5
values are equal to those of [96] (Eq. 9.23), the marine values are in good agreement with those reported5 by
5
[100] as discussed by [101] (Eq. 9.27).
K 1 × 107

4 S=0‰
0
0 5 10 15 20 25 30 35 40
3
25 t ( oC)

0.8
2
20
0 5 10 15 20
Seawater S 25
= 35 ‰ 30 35 40
Freshwater S = 0‰
t ( oC)
10

15 25
0.6
K 2' × 10

K 2 × 1010

15
10
0.4
5
5

S=0‰
0.2
0
0 5 10 15 20 25 30 35 40
0 5 10 15 20 25 30 35 40
t ( oC) t ( oC)

0.8
Fig. 9.3.  The acidity constants for the second dissociation of carbonic acid in freshwater and seawater as a func-
tion of the water temperature at salinities
Freshwater S = 0‰ of 0, 5, 15, 25, and 35‰. The values are according to [95]. The fresh-
water
0.6 values are equal to those of [97] (Eq. 9.24), the marine values are in good agreement with those reported
10

by [100] as reported by [101] (Eq. 9.28).

K 2 × 10

0.4

92
0.2
0 5 10 15 20 25 30 35 40
t ( oC)
 12
[95] Millero & Roy, 1997

K 1' × 10 7
10

8
CHEMISTRY OF CARBONIC ACID IN WATER
6

[96] Harned & Davies, 1943

4
0 5 10 15 20 25 30 35 40
S (‰)
14
12
K 1' at t = 20 oC K 2' at t = 20 oC
12 10
[95] Millero & Roy, 1997
8
K 1' × 10 7

10

K 2' × 10 10
6
8 [95] Millero & Roy, 1997
4

6
2

[96] Harned & Davies, 1943 [97] Harned & Scholes, 1941
4 0
0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
S (‰) S (‰)

12
K 2' at t = 20 oC
Fig.
10
9.4.  Values for the first and second dissociation constants of dissolved carbonic acid as a function of the sa-
linity [95]. The values are valid for a water temperature of 20°C.
8
K 2' × 10 10

6
[95] Millero & Roy, 1997
4

4.4 [97] Harned & Scholes, 1941

9.5. Examples for open and
0
0 5 10 15 20
Seawater S = 35‰
25 30 35 40
closed systems
S (‰)
4.2 In this section a few examples will be given of
K cal ' × 10 7 t ( oC) how to deal with the above equations. We will
4
0 5 10 15 20 25 30 35 40
refer to closed systems in which the dissolved
4.5 carbonic acid fractions do not exchange, nor with
Freshwater S = 0‰
the gaseous system (atmospheric or soil CO2),
4 neither the solid phase (CaCO3). In an open sys-
tem the solution exchanges with either the gas-
3.5
eous phase (= open to the gas phase), or the sol-
3
id (open to CaCO3). We will be dealing with (i)
a comparison with fresh and seawater, both in
2.5 equilibrium with atmospheric CO2, (ii) a ground-
K cal × 109 t ( oC) water sample of which [H2CO3] corresponds to
2 a  PCO2 value far exceeding the atmospheric con-
0 5 10 15 20 25 30 35 40
centration and which is brought into contact with
6 the atmosphere at a constant temperature, (iii)
K cal ' × 10 7 t = 20 oC
water exposed to the atmosphere in the presence
5
of calcium carbonate rock, and (iv) mixing fresh-
4 water and seawater (in an estuary) under closed
conditions.
3

2
9.5.1. Comparison of freshwater
1
and seawater exposed to
S (‰) the atmosphere
0
0 5 10 15 20 25 30 35 40 Here we are dealing with an open system to
the atmosphere (exchange with atmospheric CO2)
Fig. 9.5.  The  solubility product (Eq. 9.17) of calcite at a constant temperature. The latter is consid-
(CaCO3) depending on the  water temperature and ered to be of infinite dimensions, so that PCO2 is
salinity during precipitation (values according to constant. The system is closed to CaCO3, so that
Eq. 9.43 [103]). the carbonate alkalinity (= the concentration of

93
 INTRODUCTION

positive metal ions) is constant. The given condi-

tions are shown in Fig. 9.7.
Here we will use the symbols: AC = b + 2c = 6.154 × 10−12/[H+] + 4.677 
× 10−22/[H+]2 = 2.2 × 10−3 M/L
a = [H2CO3] + [CO2aq]   b = [HCO!]  c = [CO$]
From this quadratic equation [H+] and the pH can
The values of the first and second (apparent) acid-
be obtained, resulting in:
ity constants are calculated from Eqs 9.22 to 9.28.
Furthermore, we apply the Eqs 9.37 to 9.39 for [H+] = 2.871 × 10−9 M/L and pH = 8.542
calculating the various dissolved fractions.
Starting with the known value of the atmospheric The total carbon content of the water then is ob-
partial pressure of CO2, the dissolved CO2 con- tained by inserting [H+] in the above equations:
centration is obtained, and from that the pH de-
pendent other concentrations. CT = a + b + c = 0.016 + 2.14 + 0.028 = 2,19 mM/L

9.5.1.2. For seawater

9.5.1.1. For freshwater
a = 0.03811(M/kg.atm)  × 350 × 10−6(atm)
a = [H2CO3] = K0PCO2 = 0.04571(M/L.atm)
= 1.334 × 10−5 M/kg
× 350 × 10−6(atm) = 1.600 × 10−5 M/L

b = [HCO!] = (K1/[H+])a = (3.846 × 10−7/[H+])a = b = (11.480 × 10−7/[H+]) × 1.334 × 10−5

6.154 × 10−12/[H+] = 15.314 × 10−12/[H+]

c = [CO32−] = (K1K2/[H+]2)a = (3.846×10−7 × 3.800 c = (11.480 × 10−7 × 7.516 × 10−10/[H+]2)  × 1.334

× 10−11/[H+]2)a = 2.338 × 10−22/[H+]2 × 10−5 = 1.151 × 10−20/[H+]2
The carbonate alkalinity is known: Again the carbonate alkalinity is known:

[H 2CO 3], [HCO3− ], [CO 32−] / C T (%)

100
100

H 2CO 3 HCO −
3
CO 32−
HCO −3
80
80

60
60
S= 35 0 35 0‰

40
40
5 0C
25 0C
20
20
HCO −3 CO 2−
3 HCO−3
H 2CO
00
44 55 6 6 7 7 8 8 9 9 10 10
11 11 12
12
pH

Fig. 9.6.  Distribution of the carbonic acid fractions as percentages of the total carbon content, CT. The values are
calculated using Eqs 9.37, 9.38, 9.39 for temperatures of 5 and 10°C and for salinities of 0 and 35‰ as a function
of the pH. Seawater has pH values around 8.2. However, the carbon distributions are shown for an (unrealistic)
wider range of pH values, to illustrate the dependence of the carbon distribution on salinity.

94
 CHEMISTRY OF CARBONIC ACID IN WATER

Fig. 9.7.  Schematic representation of the conditions of fresh (0‰) and seawater (35‰), both in equilibrium at
a constant temperature with the atmosphere with constant CO2 concentration (partial pressure). The upper part
shows the given conditions, the lower part the resulting data.

b + 2c = 15.31 × 10−12/[H+] + 2.302 × 10−20/[H+]2 ions and a possible precipitation of calcite (open

= 2.2 × 10−3 M/kg to the solid phase).
Solving this quadratic equation results in:
9.5.2.1. Starting conditions
[H+] = 8.232 × 10−9 M/kg et pH = 8,084
We assume that the temperature, pH (resulting in
The total carbon content is: [H+] = 10-pH) and the titration alkalinity (A ) are
Chimie de l’acide carbonique
known by measurement. The H+ concentration
CT = 0.013 + 1.86 + 0.170 = 2.04 mM/kg
will be denoted by the symbol h instead of [H+].
Nous pouvons utiliser les équations:
Comparison of these results, as shown in Fig. 9.7, We can use the equations:
reveals that in the freshwater the carbonic species A = b + 2c + 10−14.34 −−
/h/h h, h,
oùwhere
les deux derniers2termes
consists for 98% of dissolved bicarbonate, while A = b + 2c + 10−14,34 the latter termspeuvent être néglig
the seawater with a lower pH still contains about b/a can=be K1neglected
/h
10% of dissolved carbonate ions. b/a =
c/b = KK 1/h
2/h

c/b = K
La multiplication 2/hdeux dernières relations donne:
de ces
9.5.2. System open for CO2 escape
Multiplication
c/a = K1K2/h2 orofcthe latter
= (K1K2/htwo
2
) a relations gives:
and CaCO3 formation
avec c/a = K1K2/h2 or c = (K1K2/h2) a 
The second example describes the chemical
changes in a certain given fresh (ground)water AWith = b + 2c
from which excess CO2 escapes to the atmo- A = b + 2c
sphere and in which CaCO3 precipitates atcesatura-
qui donne:
tion. In part (1) we shall indicate how the various Athis results in:
= (K1 / h) a + (2K1K2 / h2) a
carbon concentrations are calculated. In part (2) A = (K1 / h) a + (2K1K2 / h2) a 
ainsi:
the solution looses CO2 to the air (open to the at-
so that:
mosphere) at constant temperature until chemical
equilibrium between PCO2 and the dissolved CO2 h2
a= A (9.40)
fraction. Part (3) considers the presence of Ca2+ hK1 + 2 K1 K 2

hK1 h
b= A= A 95
hK1 + 2 K1 K 2 h + 2K 2

K1 K 2 K2
ainsi:
ainsi:
h 22
a= h A (9.40)
a = hK1 + 2 K1 K 2 A INTRODUCTION
(9.40)
hK1 + 2 K1 K 2

hK1 h
b= hK1 A= h A 9.5.2.3. Precipitation
(9.41)of CaCO3
b = hK1 + 2 K1 K 2 A = h + 2 K 2 A (9.41) (9.41)
hK1 + 2 K1 K 2 h + 2K 2 Here we have, apart from the known atmospher-
ic PCO2, the additional complication that calcite
K1 K 2 K precipitates if the product
(9.42) of [Ca ] and [CO3 ]
2+ 2-
c= K1 K 2 A = K2 A (9.42)
c = hK1 + 2 K1 K 2 A = h + 22K 2 A (9.42)
exceeds the solubility product given by Eq. 9.32
hK1 + 2 K1 K 2 h + 2K 2
(Fig. 9.5), so that CA decreases.
i.e. 3 equations with 3 unknowns. At a tempera-
i.e. 3 équations avec 3 inconnues. A une température de 15°C, une valeur de pH de démarrage de 6.0
i.e. 3 tureavec
équations of 315°C, a starting
inconnues. A unepH value ofde6.0
température andune
15°C, The amount
an valeur of calcite 6.0 Ca ) removed from
de (or
2+
et une alcalinité de 2 mM/L, les concentrations finales sont données en Fig. de
9.8pH de démarrage
phase 1. 2+
alkalinity
et une alcalinité of 2 mM/L
de 2 mM/L, the resulting
les concentrations concentrations
finales the water,
sont données en Fig. 9.8 phaseD[Ca
1. ], equals the amount of carbon
are given in Fig. 9.8 phase 1. removed from the water, DCT. We then have
9.5.2.2 LIBERATION DE CO2 the following equations:
9.5.2.2 LIBERATION DE CO2
Si l’eau perd du CO2 lors du contact avec l’atmosphère, et, en premier abord, si l’on néglige la
Si l’eau perd9.5.2.2.
présence de du Escape of CO
2+ CO lors du contact 2avec l’atmosphère, et, en premier
Ca , jusqu’à
2
a2 = K 0p = a
abord,  = a néglige la
si 1l’on
ce que l’équilibre avec la PCO2 atmosphérique (notée par p) soit atteinte,
2+
présence de
nous avons: If the water ce
Ca , jusqu’à que l’équilibre
looses PCO2 atmosphérique
avec la with
CO2 in contact the at- (notée par p) soit atteinte,
nous avons: mosphere, and in the  first instance neglecting b2/c2 = b1/c1 = (K1/K2)a or c2 = (c1/b1)b2
athe presence
= K0p of Ca2+, until equilibrium with the at-
a = K0p
bmospheric
2
PCO2
/(ac) = K1/K2 (denoted by p) has been reached, A2 − A1 = [Ca2+]2 − [Ca2+]1 = CT2 − CT1
2
bwe /(ac) = K1/K2
have: or ∆[Ca2+] = ∆CT
A ≈ b + 2c
Aa = ≈ bK+p2c
0 [Ca2+]2 c2 = 10
De nouveau 3 équations avec 3 inconnues (en gras). Avec les valeurs additionnelles
− pKcal
([Cala2+]1 + ∆CT)c2 = Kcal
de départorpour
De nouveau
teneur en CO3b2 atmosphérique
2équations avec 3 inconnues (en gras). Avec les valeurs additionnelles de départ pour la
/(ac) = K1/K2 (p), la concentration peut être calculée (Fig. 9.8, phase 2).
teneur en CO2 atmosphérique (p), la concentration peut être calculée (Fig. ∆C 9.8, phase 2).
 = (a + b + c ) − (a + b + c )
A ≈ b + 2c T 2 2 1 1

or ∆CT = b2 + c2 − (b1 + c1)

again 3 equations with 3 unknowns (bald type).
With the additional starting values for the atmo- For reasons of simplicity we assume that the al-
spheric CO2 concentration (p), the concentration kalinity is balanced by the Ca2+ ions alone,
can be calculated (Fig. 9.8, phase 2). so that [Ca2+]1 = 0.5A
157
157

Fig. 9.8.  Schematic representation of the numerical results from exposing a water sample with given conditions
(upper part of 1) to the  atmosphere (upper part of 2) and allowing precipitation of calcite (upper part of 3).
The lower part of the boxes show the calculated data. All concentrations are in M/kg.

96
 Chapitre 9

9.5.4 SYSTEME FERME, MELANGE ENTRE EAU DOUCE ET EAU DE

CHEMISTRY OF CARBONIC ACID IN WATER
Pour illustrer un système clos, nous allons discuter du mélange entre une eau douce
13
eau de mer, tel que cela se produit dans les estuaires. Le calcul de δ de, par exem
where the subscript (1) refers to the values ob-
bicarbonatée The solution of this
du mélange à partir equation
des valeurs de and the resulting
δ des 13
bicarbonates des deux pôles d
tained by step 2, and (2) to the  final values A values
af- parce
pas direct que leforprocessus
4 different temperatures
de mélange are shown
des fractions molaires de bicarbo
ter precipitation of CaCO3. These 4 independent in Fig. 9.10. Also the corresponding pH values
conservatif, c’est-à-dire que les équilibres de dissociation de l’acide carbonique évol
equations with 4 unknowns (bald type) can now
des changementsare indicated.
de pH, et les valeurs des constantes d’acidité changent en fonction d
be solved. The numerical result is shown in
la salinité de l’eau.
Fig. 9.8.
9.5.4. Closed system, mixing of
Comparison of boxes 1 and 2 shows that: freshwater and seawater
(1) the amount of CO2 escaped to the atmo- As an example of a closed system we will discuss
sphere (= 143 mL STP) is of the order of the mixing of fresh river water and seawater, such
the amount of dissolved CO2 present at as occurs in an estuary. Calculating 13δ of, for
the start of the experiment; instance, the bicarbonate fraction of the brack-
ish mixture from the 13δ values of bicarbonate
(2) the amount of calcite formed is 25.4 mg/L
in the end members (fresh and seawater) is not
straightforward, because the mixing process of
9.5.3. System exposed to CO2 in the mole fractions of bicarbonate is not conser-
the presence of Caco3 vative, i.e. the dissociation equilibria of carbonic
Fig. 9.10. Représentation schématique d’un système ouvert, consistantacid en une
shiftmasse d’eau en échange
by the changes pH, and the values of
In avecthe presence of carbonate rock water may be
un réservoir de CO2 infini et une roche carbonatée. the acidity constants
Les alcalinités change by the changes in
sont calculées
exposed to a certain CO2 pressure. The question the salinity d’eau
of indiquées
the water. The system of the two
un système ouvert, pour 4 températures différentes. Les valeurs de pH correspondantes
en une massesont dans le
Fig. 9.10. isconsistant
Représentation
how much enschématique
une masse
CaCO3 can d’eau
d’un en échange
besystème
dissolved ouvert, consistant
in Fig.
equilib-
9.11. Représentation
components
en échange
schématique
together is de la formation
closed, however, d’une
so saumure
that, par mélange d
nfini et une roche avec graphique,
carbonatée.
un ainsialcalinités
Les
réservoir queCO
de la pression partielle de CO2 (PCO2). Les alcalinités sont calculées
sont calculées
rium with the CO 2 infini et une roche carbonatée.(rivière)
2 atmosphere.
tes. Les valeurs depour pH correspondantes sont indiquées
if the end members are denoted by f(resh) andchoisi, les paramètr
et d’une eau de mer. Dans le système fermé
4 températures différentes. Lesdans le de pH correspondantes sont indiquées dans le
valeurs m(arine),
la figure sontthe  final values
supposés for the  conservative
conservatifs.
’un système de
on partielle ouvert, Instead
consistant
COgraphique,
of choosing
en une masse the CO pressure,
d’eau2 en échangethe calcu-
2 (PCO2). ainsi queislathe easiest
pression partielle de CO2 (P CO2).
infini et Au
unelieu lation
de définir
roche procedure
carbonatée. la pression de CO2, lasont
Les alcalinités if
procédurewe
calculées de calcul est simplifiée si l’on commence depuis le the alkalinity and
depart from parameters, i.e. the salinity,
ntes. LespH final de
valeurs the final
que pH l’eau pHatteindre.
doit the water
correspondantes will obtain.
L’alcalinité
sont indiquées étant The alkalinity
dans définie
le par le principe the total carbon content, are:
d’électroneutralité:
isest defined Le système formé de ces deux composants est toutefois clos, ce qui implique que, s
sion partielle
procédure
Au lieu de
de CO
de calcul
définir ). by the electroneutrality
2 (Psimplifiée
la pression side
l’on
COcommence
requirement:
depuis le
2, la procédure de calcul est simplifiée si l’on commence
CO2
sont notés nS = n S
2 K calpar f(eau douce)
f f + n S ou depuis
met S = (nlef /n)Sles
K wmm(eau de mer), f +valeurs
(nm /n)Sfinales
m pour les paramètres c
nité étant définie par
pH final que l’eau le
A = 2doitprincipe2+ d’électroneutralité:
Ca atteindre. +
+ [H ] =L’alcalinité −
[HCO 3 + 2[CO 2−
] + [OH
étant 3définie −
par ] =
le principe + h = b
(9.45) + 2 c +
d’électroneutralité: (9.44)
salinité, l’alcalinité
c et la teneur
h total en carbone, sont:
procédure de calcul 2estK simplifiée si l’on commence
K depuis le where
2[CO 32− ]L’insertion
+ [OHA −
]==2des 2 + + h =+ b + 2c + −w
cal 2 K cal nS = nfSf + nKmSwm ou S = (nf/n)Sf + (nm/n)Sm
inité étant définie par Ca lecEqs. + 9.33, = [HCO + 2[CO
[H d’électroneutralité:
principe ] 9.34 et 9.35 (9.44)
2−
] + [OH − ] =(9.44)
donnel’équation: + h n= +b m = n,
+ 2c + S ≈ 0‰(9.44) et Sm ≈ 35‰ (Fig. 9.11).
h
3 3
c hf
avec n + m = n, 2 Sf ≈ 0‰ et Smof ≈ 35‰ (Fig. 9.11).
nnel’équation:
L’insertion
Inserting
des ⎛2K K1 the Eqs.9.33,
K0cal
Eqs. 9.33,
K0 K
9.34 et 19.35
9.34 ⎛and
w2
K w 9.35⎞ results inK cal hMeasurement
K 2 ⎞Kdonnel’équation: the salinity of the brackish wa-
2− −
+ 2[CO 3 ] + [OH ]the equation:
=⎜ ++h2= b + 22c + ⎟ PCO 2 + ⎜ (9.44)
− h ⎟ PCO2 + 2 ter =results
0 brackishness
⎝ ch h ⎠h ⎝ h ⎠ La mesureK 0 Kde la salinité de la saumure correspond à la (degré(X)
1K 2
in the (degree of) of
de) “saumurisation” (X)
the water, here defined as the fraction of seawater
⎛ Kw ⎞ KKcal h 2 K K K ⎞ 2 ici comme 2la fraction d’eau de mer (pour l’eau de mer, X =1, pour l’eau douce, X ≈ 0):
+⎜ ⎛ K ⎛ K
− h ⎟ PCO2 +⎜ 2 0 1 + 2 =0 0 1 2 ⎟ P + ⎜ w − h ⎟ P + 2 cal⎞ K h (for seawater X = 1, for freshwater X ≈ 0):
onnel’équation: =0
⎝ h La⎠solution⎝ deKhcette
0 K1 K 2
équation
h 2 et⎠les valeurs
CO 2
⎝ h
de A résultantes
⎠
CO 2
Kpour
K 4 températures
K
0 1 2 nf
sont illustrées sur la
n ⎛ n ⎞ n
Fig. 9.10. Les valeurs de pH correspondantes sont également indiquées. S= S f + m S m = ⎜1 − m ⎟ S f + m S m
⎛ KAw résultantes
⎞
2
K températures
h n n ⎝ n ⎠ n
rs+ de h ⎟ PCO2de+pour
⎜ La −solution 2 4cal
cette équation= 0et lessont illustrées
valeurs sur la
de A résultantes pour 4 températures sont illustrées sur la
h
ntes⎝ sont K 0 K1 K 2
⎠ Les valeurs
Fig.également
9.10. indiquées.
de pH correspondantes sont également ouindiquées. or 159

urs de A résultantes pour 4 températures sont illustrées sur la nm S − Sf S

antes sont également indiquées. 159 X = = ≈ 159
n S m − S f 35

159
160

Fig. 9.9.  Schematic representation of an open system, consisting of a water mass in open contact with a CO2 at-
mosphere and with solid CaCO3.

97
 INTRODUCTION

20 The consequence of this non-linear behaviour of

the pH, and thus also of the carbonic acid frac-
0
atmospheric CO
2 tions, is that also 13δ of these fractions does not
Fig. 9.11. Représentation
16 schématique de la formation d’une saumure
10 par
obeymélange d’une eau
conservative douce(Sect. 7.3).
mixing
(rivière) et d’une eau de mer. Dans le système fermé choisi, les paramètres présentés sur
20
The only possible procedure for determining δ 13
A (mM/L)

la figure
12 sont supposés conservatifs.
30 values of the dissolved carbonic components in

t ( C)
water is by quantitatively converting the DIC

o
7
8
6 into dissolved CO2 by the addition of acid (such
Le système formé de ces deux composants est toutefois clos, ce qui implique que, si les deux pôles
as H3PO4) to the water sample and extracting
sont notés par f(eau douce) et m(eau8 de mer), les valeurs finales pour lesthe CO
paramètres conservés, i.e. la
2 from the water. Consequently only δDIC
4 13
pH = 9
salinité, l’alcalinité et la teneur total en carbone, sont: can be obtained. If δ of the constituting frac-
13

0
tions (a , b and c) are to be known, these should
nS = nfS−5f + nmSm−4 ou −3S = (nf/n)S −2 f + (nm/n)S
−1 m 0 be calculated from (9.45)
the 13C mass balance (cf.
10 10 10 10 10 10
P CO2 Sect. 4.3.1):
avec n + m = n, Sf ≈ 0‰ et Sm ≈ 35‰ (Fig. 9.11).
Fig. 9.10.  Schematic representation of an open sys-
La mesure detem,
la salinité de la saumure correspond CT 13RDIC = a 
(X) de Rl’eau,
13
a + bdéfinie
13
Rb + c 13Rc
consisting of a  water mass inà la (degré de)
exchange “saumurisation”
with
ici comme laan infinite
fraction COde
d’eau 2 reservoir
mer (pourand
l’eauwith carbonate
de mer, rock.
X =1, pour l’eau douce, Rb + b 13Rb + c 13αc/b13Rb
= a 13αXa/b≈130): (9.49)
The alkalinities are calculated for 4 different tempera- or with R/Rstd = 1 + δ:
tures.n The 
f n
corresponding⎛ pHn values
⎞ n indicated in
are
S= S f + m S m = ⎜1 − m ⎟ S f + m S m
the graph
n as well n as the atmospheric
⎝ n ⎠ COn2 partial pres-
CT 13δDIC = a 13δa + b 13δb + c 13δc = a (13δb − 13εa/b)
sure (PCO2).
ou + b 13δb + c(13δc − 13εc/b) = CT 13δb −a 13εa/b − c 13εc/b
9.50)
n S − Sf S
X = m = ≈ (9.46) so that (9.46)
n S m − S f 35
13
δDIC = 13δb − (a /CT)13εa/b − (c/CT)13εc/b (9.51)
Furthermore:
and similarly:
160 nA = nfAf + nmAm or A = (1 − X)Af + µAm
(9.47) 13
δDIC = 13δa − (b/CT)13εb/a − (c/CT)13εc/a  (9.52)
and
13
δDIC = 13δc − (a /CT)13εa/c − (b/CT)13εb/c (9.53)
CT = nfCTf + nmCTm or CT = (1 − X)Cf + µCm where the 13ε values are given in Table 7.2.
(9.48)
In order to calculate 13δa and 13δb and 13δc the car-
FRESH
bonic acid fractions have to be obtained by solv-
ing the following 4 equations with 4 unknowns nf A f
(in bald type): S fC Tf BRACKISH
n
A = b + 2c CT = a + b + c
S
K1 = hb/a  K2 = hc/b A
where again h = [H+], a = [CO2], b = [HCO!] and SEA CT
c = [CO$]. K1 and K2 refer to the brackish water
nm A m
values at the proper salinity.
S mCTm
A striking feature of estuaries is the non-linear be-
haviour of pH as a function of salinity. Examples
were shown by [104]. The position of the pH Fig. 9.11.  Schematic representation of the  formation
minimum strongly depends on the carbonate al- of brackish water as a mixture of fresh (river) and sea-
kalinity ratio of the fresh and marine components water. In the supposedly closed system the parameters
(CAf/CAm). shown in the figure are conservative.

98
10. Water sampling and laboratory treatment
This chapter on field and specifically on laborato-
ry practice serves to give the hydrologist as well
as the beginning laboratory worker an impression
of the experimental efforts involved in applying
isotope hydrology. A few parts have been taken
-and slightly adjusted- from the IAEA Guidelines
/ Manual for Operation of an Isotope Hydrology
Laboratory. Detailed descriptions of the  field
practice have been given by Clark and Fritz (see
Recommended Literature). We have intended to
limit the amount of detail on the analytical meth-
ods, so that the contents of (parts of) this chapter
are valid for any isotope laboratory.
10.1. Water sampling and storage
In a successful field sampling programme a vol-
ume of water is to be collected and brought or
sent to the isotope laboratory that is represen-
tative for the water mass under investigation.
The main concern during sampling, transport and
storage is to avoid isotope fractionation through
evaporation or diffusive loss of water vapour,
and/or isotope exchange with the surroundings
as well as with the bottle material. These effects
can be minimised by using appropriate collection
methods and bottles. A careful selection and test-
ing of the methods and bottles needs to be made
at an early stage. This section provides the back-
ground information to help in this selection.
The hydrologist, however, should follow
the specific instructions to be given by the lab-
oratory that is intended to analyse the samples.
10.1.1. Sampling bottles
The bottle and seal must be made of such a design
and appropriate material that any loss by evapo-
ration and diffusion to or exchange of water with
the surroundings is prevented. The isotope effect
of evaporation can be significant: a  10% loss of
sample results in an isotope enrichment of about
10‰ in 2H and 2‰ in 18O. The following conclu-
sions are gained by experience:
●● the most secure vessels for storage are glass
bottles, allowing storage of at least a decade
as long as the seal is not broken;
●● high-density polyethylene is satisfactory for
collection and storage during a few months
(water and carbon dioxide easily diffuse
through low-density plastics);
●● bottles with small necks are the most satisfac-
tory;
●● caps with positive seals (plastic inserts, neo-
prene, etc.) are required;
●● the volume of bottles should normally be
50 mL for the combination of 2H and 18O
analyses, 50 L for conventional 14C dating and
250 mL for AMS 14C dating (Chapter 11), and
500 mL for low-level 3H analysis. If the stor-
age may be longer than several months, it
is preferable to collect a larger volume and
store the samples in glass bottles (the relative
influence of evaporation is than minimised).
Generally, the dissolved carbon content
of large-volume 14C samples are treated in
the field (see below).
Further details on sample quantities are also giv-
en in Volume IV.
10.1.2. General field practice
The  following points emphasise good field prac-
tice that is applicable to all types of water to be
sampled (precipitation, surface water, groundwa-
ter):
always use a  field note book to record observa-
tions and record numbers data on sample collec-
tion sheets to be handed over to the laboratory
●● determine geographical co-ordinates of sam-
pling points using GPS or national co-ordi-
nate systems, maps, aerial photographs, etc.;
●● measure altitude, depth to the water table
(groundwater), sample depth (depth into
groundwater or surface water), well condi-
tion, condition of rain gauge, discharge (riv-
ers, artesian wells), lake level, weather condi-
tions, etc.;
●● it is very important to record other chemical
and physical data to aid interpretation such as
water temperature, pH, alkalinity, conductiv-
ity, and other possible chemical constituents
 INTRODUCTION
●● fill sample bottles completely, provided
the water has no chance of freezing during
air transport (in that case fill the bottles two-
thirds full)
●● mark all bottles individually with waterproof
marker (project code, location, date, sample
number, collector’s name, type of analysis
needed); the information has to be cross-ref-
erenced with the field notebook and the sam-
ple collection sheets.
Specific points of interest will be discussed be-
low.
In the next sections we will discuss sampling of
the various types of water.
10.1.3. Precipitation
The sampling strategy for rain and snow is in
general dictated by the scientific aim of the pro-
gramme. For example, the sampling interval may
be monthly, weekly, daily, or even each hour. In
all cases it is necessary to record the amount of
precipitation so that weighted means of isotopic
compositions can be calculated afterwards.
Of course, the maximum information and least
risk of evaporation results from short-term col-
lection of precipitation. Samples should be stored
individually in bottles. If only monthly mean
compositions are required, daily samples can be
combined in a larger storage bottle.
For samples that are collected on weekly or
monthly basis, the isotopic composition of
the sample is likely to be modified by evaporation.
This can be minimised by a special construction
of the rain gauge, or by placing a small amount
of mineral oil (2 mm minimum) in the collection
bottle which is floating on the water.
Special care is to be taken when collecting snow.
They should be allowed to melt slowly at ambient
air temperature, avoiding evaporation.
10.1.4. Surface water
Generally, the collection method for surface
waters pose few problems, when collected in
relatively small quantity. Special care has to be
taken when collecting water for carbon isotopic
analysis. Field measurement of temperature, pH
and salinity (especially with marine and brackish
water) are needed. The samples are to be stored
in glass bottles, in the dark, preferably at low
100
temperature, and should be poisoned by I2+KI or
HgCl2. The poisoning recipes are:
●● I2+KI solution: to be prepared by dissolving
15 mg of I2 and 30 mg of KI per mL of (ul-
tra)pure water; water is poisoned by adding
0.5 mL of this solution per L of sample
●● HgCl2 solution: to be prepared by dissolving
70 mg HgCl2 per mL of (ultra)pure water;
3 mL of this solution is to be added per L of
water sample.
River and stream samples should be taken from
mid-stream or a  flowing part of the  stream.
Standing water near stream banks should be
avoided as the water may not be well mixed and
show effects due to evaporation or pollution.
Samples from lakes and estuaries should be col-
lected from both the surface and from depth.
Together with other physical and chemical infor-
mation, it may be possible to interpret the results
in terms of the water-column structure.
Care should be taken when sampling near a con-
fluence. For a considerable distance downstream
of a confluence, the river samples may still show
variable isotopic compositions due to incomplete
mixing between the two different river waters. In
large river systems this may amount to a distance
of many tens of kilometres.
10.1.5. Unsaturated zone water
The isotopic profile of soil moisture can provide
information on groundwater recharge. Samples
are often taken from the soil as such. The most
common methods to extract water from the soil
profile in the  laboratory are (i) vacuum distilla-
tion, (ii) freeze drying, (iii) squeezing, and (iv)
centrifugation.
10.1.6. Groundwater
For all groundwater sampling, it is necessary to
characterise as far as possible the hydrogeologi-
cal situation (geophysical, geochemical, etc.) of
the borehole.
Pumped boreholes and production wells present
little problem with the sample readily collected
from the surface supply. This is specifically true
for the large quantity samples for conventional
14
C analysis (see Chapter 11). Sampling observa-
tion wells and especially very deep aquifers may
pose more problems. First one should be aware
 Water sampling and laboratory treatment

that standing water in such passive boreholes in the isotopic composition, or only changes that
may not be representative for the water mass in are accurately known.
Water Sample Treatment
the aquifer, because of evaporation or carbon di- Water Sample Treatment
oxide exchange with the ambient air. It is usual to
pump the borehole until it is purged by approxi- 10.2.1. The 18O/16O analysis of water
(such as dissolved carbonic acid) are to be converted into a chemical compo
mately twice the well volume, or until(such steady as dissolved carbonic acid) are to be converted into a chemical comp
used in the equipment. The specific requirement is that during this conversion
used in the 10.2.1.1.
state chemical conditions (pH, Eh) are obtained. equipment. The specific with
Equilibration requirement
CO forismass that during this conversio
While this is common practice, it should be introduced
borne in the isotopic composition, or only2 changes that are accurately kn
introduced in the isotopic composition,
spectrometric or only changes that are accurately kn
measurement
in mind that in certain situations, the cone of de-
pression resulting from pumping may 10.2.1 draw in THE Since18 water 16 poses many problems in mass
18O/ 16O ANALYSIS OF WATER
water from other sources. 10.2.1 THE
spectrometers O/ O ANALYSIS
–primarily because OF WATER of the adhe-
sion to metal, causing serious memory effects-
It may be practically impossible to collect suf- E
10.2.1.1 the  18
O/16O ratio WITH
QUILIBRATION CO2 FORsample
of the water has to be
MASS SPECTROMETRIC MEASURE
ficient water from a  deep well for routine 10.2.1.1
14
C EQUILIBRATION WITH CO2 FOR
Treatment MASS SPECTROMETRIC
des Echantillons d’Eau MEASUR
transferred to a more suitable gas, such as carbon
Since water poses many problems in mass spectrometers –primarily because
analysis. In that case one has to turn to the AMS
Since waterdioxide. poses many The most problems common in mass sample
spectrometers preparation –primarily because
technique for which 250 mL of sample isto gener-
metal, causing serious memory effects- the 18
O/ 16
O ratio of the water carbss
de l’échantillon
to metal, causing methodserious
d’eau for δ memory
doit être
18
in water is
transféré à the COthe
un
effects- gaz 2 – H
plus 2O equili-
adapté,
18
O/ 16 comme
O ratio of le dioxyde
the water
ally sufficient. transferred tolaaplus more suitable gas, such asestcarbon dioxide.
de préparation
transferred bration
to a more in which
classiquesuitable about
pour 18
δ dans
gas, a millimole
suchl’eau as carbon amount
l’équilibration of COThe
dioxide. 2 – H2most
The O dansc
most
preparation
une milli mole CO
method (10
de2 CO2for to 20 mL)
18
(10 àδ20 in mL) is
water brought
estisamenée into
the COà2l’équilibre isotopic equi-
– H2O equilibration
avec quelques inmLwhich a
de l’é
10.1.7. Geothermal water preparation libriummethodwith for 18a fewδ in watermL of issample
the COwater 2 – H2(generally
O equilibration in which a
(généralement à 25,0 ± 0,2°C):
amount of CO2 (10 to 20 mL) is brought into isotopic equilibrium with a fe
amount of CO at 25.02 (10±to 20 mL) is brought into isotopic equilibrium with a fe
0.2°C):
Both steam and liquid phases should be collected
water (generally at 25.0 ± 0.2 ooC):
from geothermal fields so that the  ratiowater steam/ (generally 18 at 25.0 ± 0.2 C):16
H 2 O + C16 O 2 ⇔ H 2 O + C18 O16 O
water can be determined. This is relatively easy 18 16
H 2 18
An O + C1616
aliquot ofO 2 ⇔ H 2 16O + C18
the equilibrated 18O 16is
CO
16
O
in production plants, but difficult in non-devel- H O + C O ⇔ H O + C O 2 O then trans-
Une fraction aliquote de CO2 équilibré est ensuite transférée
2 2 2 au spectromètre de mass
oped geothermal regions. The steam is to be 18con- ferred to the mass spectrometer for 18O/16O mea-
de O/16O. Comme le rapport 18O/16O 18de CO est différent de celui de H2O (voir P
densed, taking care that this procedure operates
An aliquot18 of surement.
the equilibratedBecause the 2 isO/then
CO O ratio
16 2
transferred in CO2toand the mass spectrom
quantitatively. An aliquot
valeur de αH ofg/l)O the equilibrated
laisvaleur
different
18
de 18(seeδ CO
obtenue
16 2 is then
Sect. 7.2.2 devrait transferred
for être corrigée
the value to ofthe
pourmass spectrom
ce fractionne
measurement. 2 Because the 18O/ 16O ratio in CO and H O is different (see S
2 2
measurement.
l’échantillon etαleBecause
18
the  δthe
)standard 18 de O/obtained
référence
value O international
ratio has in CO beand
to 2(voir H2O is different
Part.7.2.3)
corrected sont traités(see
de lS
Particularly critical for thermal waters is the need
value of 1818αg/léquivalentes
)g/lthe 1818δ value obtained has tode be corrected for this fraction
(i.e. quantités
of αfor g/l)thisthefractionation. d’eau
δ value obtainedet de
However.dioxyde
hassample carbone et même température),
and inter- for this fraction
to identify the source of the spring and tovalue
sample to be corrected
sample
correction andn’estinternational
national
pas reference
nécessaire referencematerial
(Part.4.3.2): material(see (see Sect.7.2.3)
Sect. 7.2.3) are are treated eq
as close to the spring as possible. sample and international reference material (see Sect.7.2.3) are treated eq
amounts of treated water and equally carbon (i.e.dioxide
equal amounts and equal of temperature),
water and so that the c
amounts of water and carbon dioxide and18 equal temperature), so that the
carbon dioxide and
relevant (Sect.4.3.2): 18
RH O equal temperature), α g / l RH 2Oso that
18

10.2. Laboratory treatment of relevant (Sect.4.3.2):

18
δ (water) = 18is not2 relevant
the correction − 1 = (Sect. 4.3.2): −1
18
water samples R VSMOW
18
α g / l R VSMOW
18
18R18 18
18α g / l 18RH 2 O
18
The aim of this section is to offer the hydrologist RH R 2 CO in equil . with H α
O
RH O18 − 1
18δ ( water ) = 18
18 2− 1 = 2O g / l
δ ( water ) = =18R18VSMOW − 1 = 1818α 1818−R1 = 2 δ −(equilibra ted CO 2 )
H2O
some insight in the procedures used by the iso- R 1
RVSMOW α g / l RVSMOW
CO 2 in equil . with VSMOWg / l VSMOW
tope laboratory to determine the isotopic com- 18
18RCO in equil.with H 2 O
positions of the water samples he sent/brought = 18 RCO22 in equil.with 18 H 2 O − 1 = 1818δ (equilibrated CO 2 )
En
to the laboratory. The purpose is not to provide d’autres =
termes, la valeur δ
18RCO 2 in equil. with VSMOW 2
du CO = δ (equilibrat
− 1équilibré CO 2 )
avec edl’échantillon d’eau est équiva
18 RCO 2 in equil. with VSMOW 18
the laboratory detailed recipes for carrying δ deout
l’eau elle-même,
lorsque les valeurs de δ se réfèrent à la référence internationa
the analyses. For that the reader is referred to
doit cependant (10.1)
souligner que les valeurs δ doivent être corrigées pour l’équilibration e
in other words the 1818δ value for CO2 equilibrated with the water sample is
IAEA Guidelines or specific laboratory’sl’Eq.inopera-
other
10.3,words
à causethe du termeδ value additif fordeCO l’Eq. 2 equilibrated
10.2. with the water sample is
tion manuals and literature. The procedures valuewill of theinwater otheritself,wordswhere the 18δthe value18 for CO equilibrated
18δ values 2refer to the international refe
value
Les of the
détails water
et les itself, expérimentaux
indications where theis equal δsuivant
values refer18δtovalue
tos’appliquent the international
à cette méthode. refe
We have to with
be discussed on the basis of the various isotopes. emphasise, the water however,sample that the δ18values the  do have to be corrected fo
We have toof
• Au cours according
emphasise,
the waterhowever,
de l’échange
itself, where that the the δ δvalues values dorefer
havetoto be corrected fo
Nearly all isotopic measurement techniques equilibration the international to isotopique
Eq.10.3,
reference
des atomes
becauseVSMOW. of the d’oxygène
additive
We have
entre
termCO
to
et H2O la
in 2Eq.10.2.
equilibration according to Eq.10.3, because of
l’eau change; il faut donc faire une correction; en considérant le bilan de masse en
the additive term in Eq.10.2.
can not be applied to water as such. Therefore, emphasise, however, that
the underlying principle of all methodsThe The following
is that experimental details andthe δ valuesapply
concerns do have to method.
to this
following experimental for details and concerns apply to ac- this method.
be corrected the water-CO 2 equilibration
the water or the constituents to be analysed• (suchDuring cording
the18isotopic exchange ofR the+ofcoxygen
18
atoms Rterm
c between
•
as dissolved carbonic acid) are to be converted During w the
0 R to+ Eq. 10.3,
isotopic
w0 c 0
18
R
exchange
c0 = because
w 18
of w the the additive
18
oxygenR c = w atoms + c 18 RcCO
between
and
CO22 and
isotopicincomposition
Eq. 10.2. of the water changes; for this ca/ wcorrection has to b
18
α
into a chemical compound that can be used18isotopic in composition of the water changes; for this a correction has to b
the  equipment. The  specific requirement is that 18O mass balance consideration
The following experimental we derive:
details and concerns
où
Owmass
et c ,
balance
et w et c
consideration
sont les quantités
weenderive:
mole des atomes d’oxygène dans l’eau e
during this conversion no changes are introduced 0 apply to this method.
0

carbone respectivement avant et après l’équilibration, et le facteur de fractionn

égal à 1 + 18εg/l tel que défini dans le Tableau 7.4 (généralement à 25°C); en supp
101
et c = c0, et en écrivant ρ = c/w, la valeur corrigée du CO2 équilibré est:

18
αc/w18Rw0 = 18Rc(1 + 18αc/wρ) − 18αc/wρ18Rc0
 W α g /l VSMOW RCO 2 in equil . with VSMOW
(10.1)
in equil . with H 2 O
2
− 1 = δ (equilibrated CO )
18
En d’autres termes, la valeur 18δ du CO2 2 équilibré avec l’échantillon d’eau est équivalente à la valeur
n equil . with VSMOW
18
δ de l’eau elle-même, lorsque les valeurs de 18δ se réfèrent à la référence internationale VSMOW. On
INTRODUCTION
doit cependant souligner que les valeurs δ doivent être corrigées pour l’équilibration eau- CO2 suivant
CO2 équilibré avec l’échantillon d’eau est équivalente à la valeur
l’Eq. 10.3, à cause du terme additif de l’Eq. 10.2.
aleurs de 18δ se réfèrent à la référence internationale VSMOW. On
●● During the isotopic exchange of the oxygen abundant. Otherwise a drop of concentrated
eurs δLes détailsêtre
doivent et les indications
corrigées pour expérimentaux
l’équilibration suivant
eau- COs’appliquent
2 suivant à cette méthode.
atoms between CO2 and H2O the oxygen iso- 3 4 H PO  may be added.
de l’Eq.
• 10.2.
Au cours detopic composition
l’échange isotopiqueofdes
the water changes; entre
atomes d’oxygène for CO2 et H2O la composition de
l’eau change;
mentaux suivant this a correction
il faut
s’appliquent hascorrection;
donc méthode.
à cette faire une to be made;en considérant ●● deThe equilibration
from an 18Ole bilan masse en 18O on obtient:technique determines
mass balance consideration we derive: the oxygen isotopic activity rather than con-
que des atomes d’oxygène entre CO2 et H2O la composition de 18 centration of the sample. Therefore, in saline
18 Rc
w0 18 Rw0 + le
une correction; en considérant 18
c 0bilan w 18 Rwen+ cO18on
Rc 0de=masse Rcobtient:
=w + c 18 Rc waters and brines it is required to determine
18
αc/w
18
the chemistry of the sample.
Rc
w 18 Rw +où
c 18wR c = w
0 et c0, et
+ c 18 R
18 w et c sont lesc quantités en mole des atomes d’oxygène dans l’eau et de di oxyde de
αc/w
carbone respectivement avant et après l’équilibration, et le facteur10.2.1.2. Other methods
de fractionnement 18
αc/w est
égal à 1 + 18εwhere w and c0, and
g/l tel que 0défini dans
w and 7.4
le Tableau c are the mole à 25°C); en supposant que w = w0
(généralement
antités en mole des atomes d’oxygène dans l’eau et de
amounts of oxygen atoms in the water di oxyde de and Equilibrating CO2 with the water sample is
et c = c0, et en écrivant ρ = c/w, la valeur corrigée 18 du CO2 équilibré est:
the most common method for measuring 18O/16O
et après l’équilibration,carbon
et le facteur
dioxidede before and afterαc/w
fractionnement est
the equili-
bration, àrespectively,
ns le Tableau 7.4 (généralement
18 and the fractionation
25°C); en supposant que w = w0 in water. There are other methods which are in an
αc/w18Rw0 =1818Rc(1 + 18αc/wρ) − 18αc/wρ1818Rc0 (10.2)
factor
la valeur corrigée du CO2 équilibréα is
c/w est: equal to 1 + εg/l as defined experimental stage or specifically applicable to
in Table 7.4 (commonly at 25°C); assuming certain problems. These will only briefly be men-
18 En termes
18 de valeurs
that de δ0 ceci
w = w and conduit
c = c ,à and
une valeur
writingcorrigée de 18δ de:
ρ = c/w,
αc/wρ) − αc/wρ Rc0 0 (10.2) tioned.
the corrected value of the equilibrated CO2 is:
18
δc' = (1 + 18α18c/w ρ)18δc − 18αc/w ρ 18δc0 (1) Water can be (10.3)
converted quantitatively to O2
conduit à une valeur 18 corrigée
= 18Rδcde:
αc/w18Rw0 de (1 + 18αc/wρ) − 18αc/wρ18Rc0 (10.2) by fluorination with bromiumpentafluoride:
− 18αc/w ρ 18δc0 In terms of δ values this comes(10.3) to a corrected (2) 6H2O + 2BrF5 → 9HF 171 + 2HBr + 3O2
18
δ value of:
(3) The oxygen released can be isotopically ana-
18
δc’ = (1 + 18αc/w ρ)18δc − 18αc/w ρ 18δc0 (10.3) 171 lysed directly or is reacted with hot graph-
●● Automated units can be procured with either ite to produce CO2 for mass spectrometric
an air bath or water bath. The former are easi- analysis [105]. The advantage of this method
er to operate, but the latter show a better tem- is that only 9 mg of water is needed. The dis-
perature stability and homogeneity through- advantage is that BrF5 is an extremely dan-
out the bath.
gerous liquid and needs extended laboratory
●● A variation in equilibration temperature of installations and precautions.
1°C causes an uncertainty in the 18δc value of
0.2‰. Therefore, the  temporal variation of (4) Water can be reacted in nickel tubes with
the bath should generally be much less than graphite at high temperature to produce
0.5°C, preferably no more than 0.2°C. CO2 [106].
●● The equilibration time depends on the ampli- (5) The  18O/16O and 17O/16O ratios of water can
tude and frequency of shaking and the amount
be determined by analysing O2 mass spectro-
of sample. Typical equilibration times are in
the order of 4 to 8 hours. metrically that is produced by electrolysis of
water. The precision obtained is about 0.1‰;
●● In order to remove oxygen and other gases
from the water sample prior to equilibra- the advantage especially concerns the direct
tion two ways are being used: (i) freez- measurement of 17O which is problematic
ing the sample and removing the gases by in CO2, as the 13C containing molecule has
pumping (repeated procedure), (ii) pump- the same mass and is much more abundant
ing the water sample at ambient temperature [27].
through a capillary, so minimising the evapo-
ration (and consequently isotope fraction- (6) A promising new method is measuring iso-
ation) of the sample. tope ratios (2H/1H, 17O/16O, 18O/16O) in water
●● The pH of the water needs to be in the range directly by laser absorption spectroscopy
of 6 to 7 so that dissolved CO2 and HCO! are [25].

102
 Water sampling and laboratory treatment

10.2.2. The 2H/1H analysis of water (2) measuring the 3H activity by proportional

gas counting (PGC)
10.2.2.1. Reduction of water to H2 for mass
spectrometric analysis (3) measuring the amount of daughter 3He mass
spectrometrically after storing the sam-
Again the introduction of water
Treatment desin the massd’Eau
Echantillons spec- pling for a  specific time in the  laboratory
trometer has to be avoided. Therefore, the  H/1H2
(Sect. 12.1.5.2).
ratio is commonly transferred to a more suitable
10.2.2 L’ANALYSE DE 2H/1H DE L’EAU Moreover, the possibility exists to increase
gas, in casu hydrogen. The production of H2 gas
the original 3H content artificially (i.e. to enrich)
is generally performed by reducing the water at by a known amount, usually through electrolysis,
10.2.2.1 several
R hundred
EDUCTION DE L’degrees
EAU EN H C2 with
POURzinc or (depleted)
L’ANALYSE AU SPECTROMETRE DE MASSE
prior to the 3
H measurement. Therefore, the ad-
uranium: ditional options are:
Encore une fois, l’introduction d’eau dans le spectromètre de masse doit être évitée. C’est pourquoi, le
rapport 2H/1H H 2O + Zn →
est généralement ZnO + àH2un atgaz
transféré 500°C (a) treating
mieux adapté, dans the sample asLait is collected
ce cas l’hydrogène.
H2 est généralement
production deor 2H réalisée en réduisant
2O + U → UO2 + 2H2
l’eau sous plusieurs centaines de degrés avec
at 800°C (b) treating the  sample after artificial enrich-
du zinc ou de l’uranium (appauvri): ment.
The  first method is generally carried out as
a batch
H 2O + Zn → process
ZnO + in H2 steelà 500°C
tubes. In the second The range of choices is extra broad by the com-
method the evaporated sample is running through bination of (1), (2), or (3) with either (a) or (b).
ou 2H2O + U → UO2 + 2H2 à 800°C
a furnace containing uranium turnings. Both op- The choices to be made will be discussed in
La première tions
méthode s’effectue de manière groupée
require about 10 mL of water. Although ap- avec des tubes en acier.
Chapter 11.Dans
Herela weseconde
will restrict ourselves to
l’échantillon plying
évaporéuranium
est traitéhas dans un four contenant
less experimental complica-des copeaux d’uranium. Les deux options
the different chemical/physical procedures.
nécessitent environ 10 μL d’eau. Bien que
tions, the disadvantages arelathatméthode
it is uranium
poisonous soit plus simple expérimentalement,
The LSS technique is being applied to water it-
elle présente and more difficult
les désavantages de latotoxicité
obtain de andl’uranium
dispose et of.d’une plus grande difficulté à l’obtenir
self. The sample then hasettoà be mixed with a prop-
s’en débarrasser. er scintillation liquid (Chapter 11). PGC requires
10.2.2.2. Other methods a suitable gas, as the stable isotopic analyses.
10.2.2.2 AUTRES METHODES
Similar to the equilibration method for 18O/16O
can bede 10.2.3.1. Water 2purification
18
Comme pouranalysis,
la méthode the par
2
H/équilibration
1 utilisée sample
H ratio of a water pour l’analyse O/16O, le rapport H/1H d’un
transferred
échantillon d’eau H2 by isotopic
peut êtretotransféré exchange
à H2 par échange [107]: (Coplen
isotopique et al.,the water
Often 1991): collected contains too many con-
2 1
taminants to allow direct LSS measurement as
H HO + 1H 2 ⇔ 1H 2 O + 2 H1H well as electrolytic enrichment. Especially co-
loured contaminants hamper a proper liquid scin-
Comme pourAs les in
réactions
chemical chimiques,
reactions, la technique d’équilibration
the equilibration tech- est tillation
plus liée aux activités qu’aux
performance. Purification of water is car-
nique
concentrations. is concerned lawith
En conséquence, the activities
chimie de l’eau doitrather
être than
connue. ried
Il y out
a d’autres inconvénients
by distillation. As a matter of fact, most
comme le faitconcentrations.
que cette méthode Consequently, the chemistry
nécessite un investissement of
relativement important et un
laboratories routinely contrôle de
subject all water samples
la températurethe water
très précissample
dans laismesure
to be known. Other disadvan-
où le fractionnement varie fortement avec les The requirement
to distillation. modifications is that no isotopic
tages are that the method needs a relatively large
de la température (6‰ par °C). L’avantage est que cette procédure est plus rapide. change occurs during this treatment. Therefore,
investment and that a very good temperature con- the distillation procedure has to be as quantita-
trol is needed, as3 the isotope fractionation varies tive as possible, i.e. a yield close to 90%. Also
10.2.3 L’ANALYSE DU H DE L’EAU
considerably with the exchange temperature (6‰ the water sample should hardly be in contact with
Pour mesurerper C). The advantage
la oconcentration en tritiumis that the procedure
de l’eau is
il existe plusieurs the ambient
options. Le air,
choixof which the vapour content may
doit être
faster than the other techniques. affect the 
déterminé par la concentration (attendue) de l’échantillon et la précision souhaitée. Les différentes
3
H content of the sample through ex-
procédures de traitement sont : change, which is an extremely fast process.

(1) mesurer 10.2.3. The  H analysis

spectrométrieof water liquide (SSL)
3 3
l’activité en H par à scintillation
10.2.3.2. 3H enrichment
(2) mesurer For measuring
l’activité the tritium
en 3H par content of water
comptage proportionnel du gazsev-
(CPG)
eral options exist. The choice is to be determined Two methods exist for the artificial enrichment of
(3) mesurer by
parthe (expected)
spectrométrie de3Hmasse la quantité
content d’3He fils
of the sample H in water:
andaprès avoir
3
stocké l’échantillon au
laboratoire pendant une durée
the precision donnée
required. (Sect. 12.1.5.2).
The different treatment (1) Electrolysis of the water sample
Par ailleurs ilprocedures
est possibleare:
d’augmenter artificiellement la concentration 3
(2) enThermal
H (i.e. enrichir)
diffusiond’une
of H2 prepared by re-
3
(1) measuring
quantité connue, the 3H
habituellement paractivity by liquid
électrolyse, scintilla-
avant H. Ainsi
de mesurer le duction les options
of water using, for instance, zinc
supplémentaires sont tion: spectrometry (LSS) or magnesium. By this method very high
(a) Traiter l’échantillon au moment du prélèvement,
(b) traiter l’échantillon après enrichissement artificiel. 103

173
 INTRODUCTION
enrichment factors can be obtained, but
the equipment and sample handling is com-
plicated. It is not in use in common labora-
tories. The principle of thermal diffusion is
that, when a gas mixture is in contact with
a cold wall as well as a hot wall, the high-
mass (isotopically heavy) component tends
to concentrate in the cold and the low-mass
(isotopically light) component in the hot
region. If this principle is applied to a ver-
tical, double-wall tube structure in which
the inner tube is heated and the outer wall
is cooled, the heavy component concentrates
at the cold wall and then, having a higher
density (at low temperature) moves down-
ward and concentrates at the lower end of
the tubes. The hot and light component con-
centrates at the top volume. Consequently,
a separation of the (isotopically) heavy and
light molecules, in this case 3H1H and 1H2 re-
spectively, is obtained.
The  first method is relatively simple, requires
little sample handling and supervision during en-
richment, and can be applied simultaneously to
a series of samples including reference samples.
During electrolysis the  purified sample
(sect. 10.2.3.1) is provided with Na2O or 3H-free
NaOH to increase the electrical conductivity and
subsequently decomposed by an electric current:
2H2O → 2H2 + O2
The hydrogen isotope fractionation is remarkably
large (contrary to the oxygen isotope fraction-
ation): about 90% of the 3H content of the orig-
inal water sample remains in the water (the es-
caping H2 gas is very much depleted in 3H). This
means that, if a quantity of water is condensated
by a factor of 10, the enrichment is about 9.
After electrolysis the enriched sample, now con-
taining a large concentration of NaOH, is again to
be distilled to remove the concentrated electrolyte
prior to activity measurement.
Depending on the measurement technique to be
applied, an amount of water is needed of 5 to
20 mL. If the sample is to be enriched, the desired
quantity is 250 mL (see Table 10.2).
10.2.3.3. Preparation of gas for PGC of H 3
For proportional gas counting (Sect. 11.3.1) of 3H
a few gases are suitable:
104
(1) hydrogen, prepared by
H2O + Zn or Mg → ZnO + H2
the hydrogen gas prepared has to be mixed
with a proper counting gas such as argon
(2) ethane or propane, prepared by the addition
of hydrogen made as under 1) to unsaturated
hydrocarbon:
C2H4 + H2 → C2H6 (with Pd catalyst)
C3H6 + H2 → C3H8 (with Pd catalyst)
which are suitable counting gases as such.
The additive reactions given under (2) expire at
elevated temperatures in the presence of a suit-
able catalyst.
10.2.4. The 14C analysis of dissolved
inorganic carbon
10.2.4.1. In the field
In natural waters the inorganic carbon content
plays an important role. As we have seen in pre-
ceding chapters, the total dissolved inorganic car-
bon (DIC) consists of varying concentrations of
carbonic acid (H2CO3 or rather dissolved CO2),
dissolved bicarbonate (HCO!), and dissolved car-
bonate (CO$). There are two methods in use for
obtaining the DIC fraction in water for measuring
the  14C content or the 13C/12C ratio. Both, howev-
er, collect the total amount of DIC (for unravel-
ling the separate 13δ values of the components we
have to use the procedures discussed in Chapter
9):
(1) Addition of acid and extracting the gaseous
CO2 formed:
aCO2(aq) + bHCO!+ cCO $ + (b + 2c)H+
→ (a + b + c)CO2 + ...H2O
Special, simple to operate, equipment takes
care that the escaping CO2 is dissolved
in a small amount of alkaline solution in
a plastic bottle and shipped to the laboratory.
(2) Precipitating DIC as BaCO3 after adding
NaOH solution:
aCO2(aq) + bHCCO$ + cCO$ + (2a
+ b)OH− → (a + b + c)CCO$ + ...H2O
(a + b + c)CO$ + BaCl2 → (a + b + c)
BaCO3 + ...Cl−
 Water sampling and laboratory treatment
Also here the equipment (provided by
the laboratory) is simple: the precipitate
is collected in a small plastic bottle and
shipped to the laboratory.
Both procedures are to be carried out in the field,
to avoid having to transport a large quantity of
water to the laboratory. Depending on the DIC
content of the water, for the conventional 14C
analysis between 25 and 50 L is required. With
the introduction of the AMS technique this prob-
lem no longer exists, as for this method only
a few mg of carbon is needed. The same is valid
for 13C/12C analysis. This means that a quantity of
250  mL of water is generally sufficient for both
carbon analyses. Additionally, no treatment is
required in the  field. The  13C sample, however,
needs careful storage (sect.10.1.4).
10.2.4.2. In the labo0ratory
In principle the procedures for treating the vari-
ous samples received from collection in the field
are analogous: treatment with acid (generally HCl
solution) and purification of the  escaping CO2.
Subsequently different methods are to be applied,
depending on the 14C measurement technique, in
chronological order of first application:
(1) activity measurement in a proportional gas
counter (PGC) as CO2, C2H2, C2H6, or CH4
(a) if CO2 is used in the gas counter directly,
it has to be extremely pure; this purifi-
cation is the main effort of the sample
treatment by the laboratory
(b) preparing acetylene from CO2 is per-
formed in 2 steps:
2CO2 + 9Li   → 4Li2O + Li2C2 (700°C)
Li2C2 + 4LiO2 + 6H2O → 4Li(OH) + C2H2
(c) preparing ethane from the acetylene pre-
pared as under b)
C2H2 + 2H2 → C2H6   (with Pd catalyst)
(d) preparing methane from CO2:
CO2 + 4H2 → 2H2O + CH4    (300°C +
Ru catalyst)
(2) activity measurement in a liquid scintilla-
tion spectrometer (LSS) as C6H6
the acetylene gas prepared under 1b) can be
condensed to benzene:
C2H2 → C6H6 (with catalyst)
the thus formed benzene is to be mixed with
a proper scintillation fluid (Chapt.10).
(3) concentration measurement in an accel-
erator mass spectrometer (AMS) as graphite
or CO2; in the presence of iron catalyst, CO2
is reduced to graphite:
CO2 + 2H2 → 2H2O + C (at 600°C with Fe)
the graphite is directly transferred to the ac-
celerator target (see Chapter 10).
10.2.5. The 13C/12C analysis of
dissolved inorganic carbon
This procedure has been discussed in
sect. 10.2.4.2, as it is similar — and in fact it runs
paralle — to the 14C procedure. The CO2 extrac-
tion can be carried out by acidifying the water
sample and collecting the evading CO2 during
vacuum pumping. The sample can also be flushed
with a clean gas, such as nitrogen or argon, and
the evading CO2 likewise condensed in a cold
trap.
One concern with these samples is that the water
is likely to exchange with the atmosphere, if it is
not completely sealed of. 13C/12C then changes to
ultimately isotopic equilibrium with atmospheric
CO2. Parallel the pH of the water changes to high-
er values. The sample should therefore be stored
in a glass bottle and sealed properly.
The second concern is the ingrowth of organic
matter in the water sample. As this has a 13δ val-
ue much smaller that the DIC, the latter will in-
crease. In order to avoid this process, the sample
is to be stored at low temperature in the dark,
preferably after poisoning (sect. 10.1.4).
105
 11. measuring techniques

11
The aim of this chapter is to give some insight
TECHNIQUES
in DE MESURES
the various existing techniques for measuring A
M a g n e t i c field
isotope ratios and radioactivities. The potential
readers are the hydrologists which apply the iso-
tope techniques and their students assisting in 15 to 50 cm

the laboratory on the one hand, and starting labo- Ion

collectors
ratory technicians receiving a first glance of their Positive ions
Le but de cefuture
chapitre est de
work, ondonner quelques
the other. informations
The review sur les diverses techniques
is general High voltage E utilisées
low hih
mass mass
pour mesurerin des
thisrapports
respect,isotopiques et dethe methodologi-
that it covers la radioactivité. Les lecteurs Ionisation
concernés sont les
chamber

cal field, although laboratories often do not have

hydrologues qui appliquent les techniques isotopiques et leurs étudiants qui les assistent dans
Gas flow
Ion source
all techniques at their disposal. Technical details
leur laboratoire; il s’agit aussi des techniciens débutant qui peuvent recevoir ainsi un premier m q +

vary among laboratories and manufacturers. B v

aperçu de leurs travaux futurs. De ce point de vue, la présentation sera donc générale, de F
Therefore, we restrict ourselves to the underlying r
manière à couvrir
principles.le volet méthodologique, et ceci, bien que les laboratoires n’aient pas B
toujours toutes les techniques à leur disposition. Les détails techniques varient suivant les
laboratoires et les constructeurs. C’est pourquoi nous allons nous restreindre aux principes
11.1. Mass spectrometry for
généraux énoncés ci-dessous. Fig. 11.1.  Schematic view of mass separation in
stable isotopes
a mass spectrometer.
11.1.1. Physical principle
11.1 SPECTROMETRIE DE MASSE POUR LESA.ISOTOPES The  gas containing isotopic molecules enters
A mass spectrometer is able to separate atoms the  ion source and is ionised by electron bombard-
STABLESor rather ions with different mass and measure ment. The  positive ions are extracted from the  ioni-
their relative abundances. This principle is shown sation chamber and accelerated in the  ion source by
11.1.1 PRINCIPE PHYSIQUE
in Fig. 11.1A where the gas containing different a  high voltage E. In a  magnetic field perpendicular
isotopes of an element ( C and C in CO2, for
12 13 to the surface of this paper the isotopically light and
Un spectromètre de masse est capable de séparer des atomes ou desheavyions ions
de masses différentes
are separated and collected by collectors.
instance) is ionised in the ion source. The posi-
et de mesurer leurs abondances relatives. This
sur laresults in electrical
où uncurrents
gaz that can be measured
tive ions are accelerated byCehigh principe
voltage est indiqué
and Fig. 11.1A
contenant différents isotopes d’un 12
élément (field 13
C etperpendicu- very precisely.
C du CO2, par exemple) est ionisé dans
subsequently enter a  magnetic
une source d’ions. Les ions positifs sont accélérés par uneinhauteB.tension
lar to the  electric field (in fig. 11.1A drawn Representation
et entrent of ensuite
the  Lorentz force: a  charged
dans un champthe surface
magnétique of this paper). The path
perpendiculaire au champ électrique (sur la Fig. 11.1A représenté charge q+ and mass m
of the ions particle with positive electric
now becomes circular because of the Lorentz moves in a  flat surface with a  speed v in a  magnetic
par la surface du papier). La trajectoire des ions devient alors circulaire de par la force
field B perpendicular de surface; the  resulting
to that
force (Fig. 11.1B). The circle radius depends on
Lorentz (Fig.the ion
11.1B). Le rayon du cercle dépend de
mass: the ions with heavier masses follow la masse de l’ion: les ions les plus lourds
Lorentz force F is perpendicular to B and v and causes
suivront un the larger
cercle plus grand. De cette façon, les
circle. In this way the different isoto- ions se the particle
séparent to follow
et peuvent donca circular
être path with radius r.
collectés. Dans les collecteurs,
pic ions les ionsand
become separated perdent
can be leur charge électrique, produisant ainsi de
collected.
In these
faibles courants collectors
électriques the ions
qui peuvent êtreloose their(Fig.
mesurés 11.2). The velocity of the particle
electric is due to
Techniques
Techniques de acceleration
de Mesure
Mesure
charge, causing small electric currents that can be by the high voltage in the ion source (Fig. 11.1B):
La magnitude de la force
measured de Lorentz est:
(Fig. 11.2). 1
E
E kin = 1 mv 22 = qV
kin = 2 mv = qV
(11.3)
The magnitude
→ → → of the Lorentz force F is: 2
F→ = B→× q v → (11.1)
F = B × q v Des (11.1) From Eq. 11.2 and 11.3 follows the radius of
Des Eq.Eq. 11.2
11.2 et et 11.3
11.3 on on déduit
déduit le le rayon
rayon de de la
la trajectoire
trajectoire circulaire
circulaire des
des différents
différents
the circular path of the different isotopic ions:
Cette force est égale à la force centripète nécessaire
This force is equal to the centripetal force re- pour garder la particule sur une trajectoire
circulaire : quired for keeping the particle in the circular 1 2 mV ⎛⎛⎜ 22V V // qq ⎞⎞
path: = 1 2 mV =
rr = =⎜ ⎟⎟ m m (11.4)
B
B q
q ⎜⎜ B B ⎟⎟
2 ⎝⎝ ⎠
⎠
mv
F= = Bqv (11.2) (11.2)
r −19
où qq est
où est égal
égal àà la la charge
charge de de l’électron
l’électron = = 1,6
1,6 × × 10
10−19C et B
C et et V
B et V dépendent
dépendent desdes
l’instrument. Pendant la mesure, le 179
voltage électrique
l’instrument. Pendant la mesure, le voltage électrique et le champ magnétiq et le champ magnétiq
constants,
constants, de de telle
telle façon
façon queque lele rayon
rayon estest proportionnel
proportionnel àà la la racine
racine carrée
carrée de
de la
la
rr (:)
(:) m m .. La
La différenciation
différenciation (d (drr/d/dmm conduisant
conduisant àà l’approximation
l’approximation Δr Δr//Δm
Δm)) donn
donn

Δr / r ⎛⎛ 2V / q ⎞⎞ ⎛⎛ 2V / q ⎞⎞
 1 2
E kin = mv = qV (11.3)
2
Des Eq. 11.2 et 11.3 on déduit le rayon de la trajectoire circulaire des différents i

Des Eq. 11.2 et 11.3 on déduit le rayon de la trajectoire circulaire des différents ions:
INTRODUCTION 1 2 mV ⎛⎜ 2V / q ⎞⎟
r= = m
B q ⎜ B ⎟
1 2 mV ⎛⎜ 2V / q ⎞⎟ ⎝ ⎠
r= = m (11.4)
where B q is⎜ Bequal⎟ to the electron carbon dioxide, being representative for 2- and
⎝  – 19 ⎠
charge = 1.6 × 10 C and B and V depend où q estonégal 3-atomic à la charge gases. de l’électron = 1,6 × 10−19C et B et V dépendent des p
the instrument settings. During a measurement l’instrument. Pendant la mesure, le voltage électrique et le champ magnétiqu
où q est égalthe à laelectric
charge voltage
de l’électronand =the  × 10−19C et
1,6magnetic B etare
field V dépendent des paramètres de
constants, de 11.2.1. telle façon que le rayon est proportionnel
Measurement of 2H/1H inàHla2 racine carrée de la m
kept constant, so that the radius is proportion-
l’instrument. Pendant la mesure, le voltage électrique et le champ magnétique sont gardés
constants, dealtelle
to the square
façon que leroot rayon of est
the ion mass: rr à(:)la racine
proportionnel m . La différenciation
The case
carrée de la masse of hydrogen (dder/dl’ion:
m conduisant
is complicated by the fact Δr/Δm) donne:
à l’approximation
Differentiation (dr/dm leading to the approxima- that in the ion source H2 gas combines with a hy-
r (:) m . Lationdifférenciation
∆r/∆m) results (dr/din:m conduisant à l’approximation ΔrΔ/Δm r / r) donne: ⎛ 2toV form / q ⎞ 1H +  which also⎛ has 2Vmass / q ⎞ <3>.
drogen =ion ⎜ ⎟ and3 m / Δm = ⎜ ⎟ r / Δr
Δ m / m
The necessary ⎜ B ⎟
correction is obtained ⎜ B
from ⎟an ex-
Δr / r ⎛⎜ 2V / q ⎞⎟ ⎛ 2V / q ⎞ ⎝ ⎠ ⎝ ⎠
= and m / Δm = ⎜ ⎟ r / Δr trapolation procedure (11.5) to ion source gas pressure
Δm / m ⎜⎝ B ⎟⎠ ⎜ B ⎟
⎝ Cette⎠ dernièreequal équationzero where est une 1 mesure
H +3  disappears. de la résolution du spectromètre de
(11.5) Δm = 1, m estThe constants la résolution dec l’instrument si Δr est suffisamment grand pour p
Cette dernière équation est une mesure de la résolution du spectromètre de masse: 2 and pour c3 contains the propor-
distinction claire tionalityentre les pics pour les masses m etprobabilities, m+1 dans le spectre général.
Δm = 1, m est la résolution
The latter de l’instrument
is a measure si Δr est suffisamment
of the resolution of grand pourfactors permettre for une the ionisation
the mass the  transmission and collection efficiencies of ont typiqueme
distinction claire entrespectrometer:
les pics pour les formasses
Dm = 1, m et mmis+1 the reso-
Les dansSpectromètres
le spectre général. de Masse de Rapports Isotopiques (SMRI)
lution of the instrument if Dr is large enough résolution to (dethe molecules with masses <2> and <3>. Because
l’ordre de 100), contrairement aux spectromètres de masse « org
Les Spectromètres de Masse de Rapports Isotopiques
allow a clear distinction between the peaks for (SMRI) ont these factors
typiquement are
de unequal
faibles unity, the isotope ratios
ont des résolutions de plus 104. Toutefois
dethe current ces derniers ont de plus faibles sen
résolution (demasses
l’ordrem de m+1contrairement
and100), aux spectromètres de masse « organiques » qui ratios have to be com-
in the mass spectrum. obtained from
sont donc pas adaptés aux
pared to those of a common mesures des rapports
Techniques isotopiques.
(internationally
de Mesure ad-
ont des résolutions
IsotopedeRatioplus deMass104.Spectrometers
Toutefois ces derniers
(IRMS)ont have de plus faibles sensibilités et ne
opted (see Chapter 7)) standard:
sont donc pas typically
adaptés auxlowmesures
resolution (in the order
des rapports isotopiques. of 100), Techniques de Mesure
contrary to the ‘organic’ mass spectrometers 11.2 DETERMINATION ( I 3 / I 2 ) sample gas
Techniques de Mesure
(
(c3 / c 2 ) [RAPPORTS
DES 2
H1 H + 1 H 3+ ] /[1 HD’ABONDANC ) 2 ] sample gas
=
with resolutions of more than 104. The latter, on
11.2 DETERMINATION
the other hand, have much DES lowerRAPPORTS ISOTOPES((II3STABLES
sensitivity D’ABONDANCE
and
/I )
3 / I22 )reference
sample gas gas ( 22 11 11 ++
DES((cc33 // cc22 )) [[ HH HH ++ HH33 ]]/[/[ HH22]] reference
11
) gas
sample gas
=
ISOTOPES are therefore
STABLES not suitable for isotope( Iratio mea-
Les faisceaux
3 / I 2 ) sample gas
I 3(/cIcorrespondent
(qui 2 ) reference gas
2
(1 (caux
3 / c 2 ) [ H H + H 3 ] /[ H 2 ] sample
3 cions
1 /+ ( )
2) [ H
2 1
1 positifs H+ H 1 +
des
gas
1
)
3 ] diverses
/[ H 2 ] reference
molécules
gas isotop
surements. Après =
correction pour la participation de H +
et en insérant
(11.7) les rapport(11.7) isotop
Les faisceaux qui correspondent aux ions positifs des ( I 3 sont
I 2 ) dirigés
/diverses
de 2reference
δ
vers(cles/ ccollecteurs.
molécules
valuegas
devient:
2
2) [ H H +
3 isotopiques (1 Là,
du H
1 la
gaz
+ charge 1
) 3électrique est
3 ] /[ H 2 ] reference gas
+
transférée au métal d
ceAprès
qui produitcorrection des courants
pour la participation électriques (de I) dansH3 et lesenconnections
insérant lesdes collecteurs
rapport isotopi
sont dirigés vers les collecteurs. Là, la charge électrique est2transférée au métal des collecteurs
11.2. Reporting stable isotope partir
de δduvaluerapport
Afterentre
devient: correction ces courants for the H les3 rapports
+
contribution isotopiques
and in- des gaz originels
ce qui produit desAbundance
courants électriques Après
(I) dans
ratios correction
les connections pour la des
participation
collecteurs ( 2 de
H/ 1(Fig.
H) H3+11.2).et en Ainsérant les rapport isotopiques, la valeur
2I ) 0 sample
serting ( I /
3 δ2 value
partir du rapport entre ces courants les 2
δ value isotopiques
de rapports
déterminés. Chaque
devient: = 2the isotopic
des gazδ originels
2 courantsample
1 peuvent être
est ratios,− 1 = the 
proportionnel
0
becomes:
(coefficient − 1 c) à la pression pa
The ion beams consisting of positivecomposé ions ofdans2 le gaz.. (( 2 H/ 1H)
H/ H)reference ( I / I ) 0
( I3 / I2 ) sample reference
déterminés. the various
Chaque courant est proportionnel the gas are cfo-
molecules in (coefficient ) à la pression
δ = 2 partielle de−son
sample
isotopic 1
1= 3 2 0 −1
( 2
H/ 1
H) ( H/+ H) reference ( I 3 / I 2 ) reference
composé dans le gaz..
cussed in the collectors. Here the electric charge sample I2 = c0−2[1seH 1 0
(]I 3 / I 2 ) àsample I44 = cde 12 16
O2+]
44[ laC contribution
+
2
δ = où2 l’exposant (11.8) = 2rapporte la correction
− 1 de H 3 à la m
(11.8)
is transferred to the metal collectors, resulting 1
( H/ H) reference ( I / I ) 0
reference
c2[1H2+] currents (I) in the collector
I44 = c44[12C16Ooù valeurs
+ absolues
I3 = c03[se 2pour
H les
1 +
Hrapporte
3
+ 1H
2 standards
+
3à ]la correction
(échantillons
I45 = cde 13 16 deO2référence)
45[ laCcontribution
+
+ 12C17O deseO
16 trouvent
+
H3+] à la m
Iin
2 =electric 2 ] l’exposant
connec-
tions (Fig. 11.2). 11.2. absolues pour les standards (échantillons
1 From the ratios of these 13 160 currents
valeurs I46 44 = cmass 12 de
18 +référence)
16
46 + C seO<3>.
13 17 trouvent
16
+ 12Cd
O+ Les
46[deCH3O àOla +masse
2 1 + + + 12 17 16 mass + 2 mass 3 mass 45 mass
Ithe isotopic
3 = c3[ H H + H3 ] où I = c 45[ C Ose
l’exposant
ratios of the original gases11.2.
45 2 +
can rapporte
be C O àO1 la ] correction (11.6)
de la contribution
H 1H 2 1
H H 12 16
C O2 12 18 16
C O O
determined. Each currentvaleurs = cabsolues
isI46proportional pour
12 18 (coeffi-
46[ C O11.2.2
16
O+ +les 13 standards
C17O16O+ +DE
MESURE
(échantillons
12
C1517N/ O214+]N DANS de référence)
N 2
13 16 se 13trouvent
C O 2 C 17O 16O
dans le tableau
cients c) to the partial pressure 11.2. of the respective mass 28 mass 29
14 14
12 17 16
C O O 12C 17O 2
N N 15N 14
component in the gas. 11.2.2
L’analyse MESUREau spectromètre DE 15NN/14de N DANS masse N du2 rapport 15N/14N des corps contenan
11.2.2 MESURE également
DE 15N/14au
L’analyse simple,
N spectromètre
DANS peut N2êtrede encore masse plus,du dans rapport la mesure
15 14 où dans ce cas l’effet
N/ N des corps contenant
1 +
I2 = c2[ H 2 ]
1 +    provoque, pour
également simple, peut être encorel’hydrogène, la formation de H , n’intervient pas. Les ra
15 plus, 14 dans la mesure où dans ce cas l’effet
c o l l e c t o r s 3
L’analyse au spectromètre mesurés surpour de masse
le faisceau du rapport
se traduisent 181 N/ N
de manière des corpssimple contenant de l’azote est
I3 = c3[2H1H+ + 1H +3  ] provoque, l’hydrogène, la formation de H 1 +
Ien
3 , n’intervient
46
rapports isotopiques
pas. Les rap
également simple, peut être encore plus, Idans I 29
la mesure où dans ce cas l’effet de pression qui
mesurés sur le faisceau se3 ortraduisent de manière simple Ien
45 rapports isotopiques
1
I44 = c44[ C O 2 ]
12 16 +  
provoque, pour l’hydrogène,( Ila formation / I ) I or
de
I cH3+/,c n’intervient
([ 15 14
N N] / pas.
[ 14 Les rapports ioniques
N I ]) échantillon
2 44
mesurés sur le faisceau se traduisent
29 28 échantillo
de
2
manière
n 28
= simple 29 28
en rapports
15 14 isotopiques:
14
=
I45 = c45[ C O 2 + C O O ] ( (I I292911.2. 
Fig. / /I I2828) )échantillo
The  various c29isotopic
/cc28([([15ions N14 N] N]/hydrogen
of /[ [14 NN 2])])and
13 16 +   12 17 16 +
référence c / N référence
carbon dioxide, respectively,
n
= 29 28 are 15 focussed
14 in the  col- =
14
2 échantillon

I46 = c46[12C18O16O+ + 13C17O16O+ + 12C(17I O /+2  ] I ) ( I

lectors
/ I ) c / c ([ N N] / [ N 2 ]) référence
c2929 / c28(Faraday 15 14
cups).
28 ([ N N] / [ N 2 ]) échantillon
référence 29 14
These
28 collect the  electric

29 28 échantillon
= =
( I 29 / I(11.6)
28 ) référence
charges c29 / c(electrons 15 14 are picked
( 1514
28 ([ N N] / [ N 2 ]) référence
N / 14up N) by the positive ions)
resulting in electric=currents 15 for
14
échantillon
the  various = 15δisotopic
+1
( (15 N /14 N) référence
N / N)
The isotopic compositions can now be calculated. molecules. From the ratios = 15 of14these the isotopic
échantillo n
= 15δ +ratios 1
We restrict ourselves to discussing hydrogen and of H215or N214(left) and CO ( 2N(right)/ N)can be deduced.
( N / N) échantillon 15 référence
Le N2 de l’air= qui15varie peu est choisi = δcomme + 1 référence ou standard,:(11.9)
( N / 14 N) référence
108 Le N2 de l’air 15 qui varie peu est choisi comme référence ou standard,:
R(N2 standard de l’air) = 0,0036765
Le N2 de l’air qui varie peu est
15 choisi comme référence ou standard,:
R(N2 standard de l’air) = 0,0036765
La précision de la spectrométrie de masse est d’environ 0,02 ‰. Toutefois, les
15
R(N2 standard de l’air) = 0,0036765 (11.10)
 measuring techniques

where the superscript 0 refers to the correction 11.2.3. Measurement of 13C/12C and

procedure for the H3+ contribution to mass <3> 18
O/16O in CO2
ions. Absolute values for the standards (reference The measurement of the isotopic composition of
samples) are given in Table 11.2. CO2 is complicated by the abundance of mole-
cules with equal mass <45> and <46>, containing
11.2.2. Measurement of 15N/14N in N2 different isotopes (Fig. 11.2).

The mass spectrometric analysis of N2 for obtain- From

I 45 Eq. 11.6 we COcan deduce the following45rela-
= (c / c )
tions for45the isotopic
44
2 with mass 45
ratios: = (c45 / c44 ) R m
ing 15N/14N in nitrogen containing materials is I 44 CO 2 with mass 44
I 45 CO 2 with mass 45
equally simple, even more so, since in that case = (c45 / c44 ) = (c45 / c44 ) 45 R m
we have not the pressure effect in the ion source I 44 CO 2 with mass 44
that resulted in the formation of 1H3+ with hydro-
and
gen. The measured ion beam ratios are simply
translated 15into14isotope14 ratios: I 46 CO 2 with mass 46
( I 29 / I 28 ) sample c / c ([ N N] / [ N 2 ])sample = (c46 / c44 ) = (c46 / c44 ) 46 R m
= 29 28 15 14 = I 44 CO 2 with mass 44
I 29 / I 28 ) reference c(29I / c/28I ([) N N] /c[ 14/Nc2 ])([reference
15 14
N N] / [ 14 N 2 ])sample I 46 CO 2 with mass 46
29 28 sample
= 29 28
= = (c46 / c44 )
(11.11) = (c46 / c44 ) 46 R m
( I 29 / I 28 ) reference c29 / c28 ([ 15 N14 N] / [ 14 N 2 ]) reference I 44 CO 2 with mass 44
The isotopic analysis of CO2 now proceeds in 3
15 14
( N / N) sample or 4 steps, described in the next sections.
= = 15δ + 1 (11.9)
( 15 N / 14 N) reference ( 15 N / 14 N)
sample
= 15 14 = 15δ + 1 11.2.3.1. Comparison with machine reference
(
As reference or standard servesN / N ) referenceair N2 which
shows very little variation: As with hydrogen, the ionisation and transmission
efficiencies of the isotopic molecules and ions are
15
R(standard air N2) = 0.0036765 (11.10) not 100%, so that the values of the proportional-
ity factors c in Eq. 11.6 can not be replaced by
The mass spectrometric precision obtained is 1. This necessitates comparison of the ion beam
about 0.02‰. However, the laboratory samples ratios with those of a reference.
handling to prepare the N2 gas as required for
Routinely laboratories use their own working
the IRMS measurement results in much larger un-
reference gas (often referred to as the working
certainties, because the chemistry involved is less standard or machine standard, which finally has
straightforward. to be calibrated against the international stan-
Techniques de Mesure
For a check of the overall chemical and measure- dard material). Eq. 11.11 applies to the sample (s)
ment procedures a set of reference materials is and the working reference gas (w), we eliminate
available. The values are shown in Table 11.1. the efficiency
(I 45 /I 44 )s 45 Rfactors
m c the mass <45> and mass
<46> = 45 Sm
measurements Techniques
for and de Mesure pro-
other (generally
(I /I
portional ) R
45 44 r or multiplicative)
w instrumental errors:
45
(I 45 /I 44 )s RSm
et
TABLE 10.1.  Reference materials = 45
(I 45 /I 44 )r Rwm
for N/ N analyses [108, 109].
15 14

Reference
and
(I 46 /I 44 )s 46
RSm
Material 15
δ (‰) rel. toetair N2 = 46 (11.12)
sample name (I 46 /I 44 )r Rwm
IAEA-N1 (NH4)2SO4 +0.43 ± 0.07
(I 46 /I 44 )s 46 RSm
IAEA-N2 (NH4)2SO4 +20.41 ± 0.12 = 46 m
11.2.3.2 (IALIBRATION
46 /I 44 )r Calibration
11.2.4.
C Rw
IAEA-N3 KNO3 +4.72 ± 0.13
La The true
vrai valeur isotopicisotopiques
des rapports ratios of the working reference,
des références de travail, 45Rwc et 46R
USGS–25 (NH4)2SO4 −30.41 ± 0.27 45
Rwc and 46Rwc, are known from a repeated com-
USGS–26 (NH4)2SO4 suite
+53.75 ± 0.24 à une comparaison
11.2.3.2 with répétée
CALIBRATION
parison avec les standards
the international standards,internationaux,
R1, (such R1, (tels que
USGS–32 KNO3 +180.00 VSMOW).
La
LesVPDB
as valeursordeVSMOW).
ces derniers peuvent être
The values calculées à partir
of the latter des vale
de travail, 45Rwc et 46R
18 vrai valeur des rapports isotopiques13 des17 références
from the  R, R and R values
NSVEC N2 gaz −2.78 ± 0.04
R donnéescan
dansbelecalculated
Tableau 11.2. 18

suite à une comparaison répétée avec les standards internationaux, R1, (tels que
given in Table 11.2.
VSMOW). Les valeurs de ces derniers peuvent être calculées à partir des vale
18
R données dans le Tableau 11.2.
109
 nouveau proportionnelles.
45RB.etPour
45 46 normaliser, l’échelle 13R ou 18R est étendue de manière à atteindre la valeur
46 R calibrées àà la
R et R calibrées la valeur
valeur correcte
correcte des
des standards
standards sont
sont obtenus
obtenus par
par une
une correction
correction
connue d’un deuxième standard (R2n). Les corrections pour les valeurs de R2 et RS sont de
multiplicatrice:
multiplicatrice: Chapitre 11
nouveau proportionnelles.
ecte 45des
R etstandards
46
R calibrées sont obtenus à la valeur par une correcte correction des standards sont obtenus par une correction Chapitre 11
INTRODUCTION
c c 45 cc
multiplicatrice: RS R
R c Rw c
45
45 Rc =c
45
R R 45 m
S = ou w 45 Rm
w
m =
w
m ou RSS = 4545VSMOW-CO m RSS 3,867 2,0878142
45 R m R
R46SSà la Rvaleurm R m 2
Rww sont obtenus par une correction
R45 etc 46R 45calibrées
R and R calibrated to the proper
w
w correcte des standards
values of (2) With these we calculate R from R 18 46
5 c Rw 45 mR c R c 45
Rwc 45 SMOW-COVSMOW-CO 2 2 3,867 2,0878142
2,0879186
RS =multiplicatrice:
45 m
R Sthe standards
S
= w are ou obtained 45 by
R c
= a multiplicativeR m
(Eq. 11.15)
Rw et RSm Rwm
et correction:
S 45
Rwm SLAP-eau
S
(11.13)
(11.13)
SMOW-CO2 3,683 2,0879186
1,8939104
45 (3) Now the  R values can be calculated
17
RSc Rwc 46
46 Rc c 45 c R c
w 45 m
= 46 46 cc
RS == 46or Rww 4646 Rmm R(11.13) S = 45 RSLAP-CO
SLAP-eau 2 (Eq. 11.16) 3,683
3,758 1,8939104
1,9719405 8
et RSm Rwm R S 46 Rm m R SS R w
m S
(11.13)
Rww (4) Inserting these in Eq. 11.14
1SLAP-CO2 3,758 results in new 1,9719405
and
46 c
Rw 46 m ) Craig, 1957
et
46 c
RS = 46 m RS (11.13) and better values for R 13
Les rapports
Les rapports Risotopiques,
isotopiques, malgré tout
malgré toujours21appliqués
tout toujours )appliqués
Baertschi, àà lala1976molécule entière
molécule entière(11.13) dedeCO CO2,2,sont sont
w ) Craig, 1957
maintenant calibrés. 3 (5) This procedure is repeated
2) Hageman et al., 1970; De Wit et al., 1980, assez bien confirmé par Tse et al.(
until the 13R, 17R
maintenant calibrés.
46
R c
) Baertschi, 1976and 18R do no longer change.
oujours The isotopic
46
R c
à Sla= molécule
w 46 m
ratios,
Rentière however CO2,still applying to
Les appliqués
rapportsthe entire
isotopiques, 46
R
CO
m
malgréS
tout detoujours
w  molecule, are now calibrated.
sontappliqués 3
Les à la
valeurs
) Hageman et al., molécule
de 45 entière
et 46RDe
R11970; deWit CO
1 s’obtiennent et2,al.,
sont à partir
1980, assez de:bien confirmé par Tse et al.(19 al.(1
2
maintenant 11.2.3.3 C
calibrés. CORRECTIONS ISOTOPIQUES
11.2.3.3 ORRECTIONS ISOTOPIQUES The values thus obtained for the isotope ratios of
45 45 13 46 17
Les valeurs de R =R1 R
the sample et + R R c and 18R cà are
2131 Rs’obtiennent partir de:
automatically ad-
Les rapports Comme
Comme isotopiques,
indiqué
indiqué sur
sur malgré
la Fig.
la Fig. tout
11.2,
11.2, toujours
les faisceaux
les appliqués
faisceaux ioniques
ioniques à lades molécule
des massesentière
masses <45>etetde
<45>
S CO , sont
<46>contiennent
<46> 2contiennent
S
11.2.4.1. Isotopic corrections 45justed
46 on
1318 the VPDB
17 13 17 or
17 VSMOW
2 scales for 13
C
ES 11.2.3.3
maintenant Ccalibrés.
ORRECTIONS ISOTOPIQUES R == 2 R R+ +2 2R R R + R
différents
différents
As is shown ions isotopiques:
ions isotopiques:
in Fig. 11.2, the mass <45> and <46> 46and O. 18
The δ values17 of2 the sample relative to
sceaux
Comme ioniques indiquédes masses
ion beams sur la contain <45>
Fig. 11.2, et <46> contiennent
les faisceaux
different isotopic ioniques
ions: des massesthe international = 218et
R<45> R+ <46> 213Rcontiennent
17
R+ R
standard can now easily be writ-
11.2.3.3 CORRECTIONS 12ISOTOPIQUES
16 16
O16O] 13 16 16 16
O]++[[1212CC17 17 1616
différents ions isotopiques: II44
44 = = [[12 C16
C O O] II4545==[[13CC16ten OO as:
13
O] 13 O
ORSc O] O]
18
18
RSc
Comme indiqué I 44 = [ C
12 16 16
O O]
sur la Fig. 11.2, les faisceaux ioniques des masses <45> et <46> δ S/VPDB = 13
−
contiennent 1 et δ S/VPDB = 18
−1
13
13RVPDB cc 18RVPDB
18 cc
I45 =ions 13 16 1216 16 16 12 17 16
[I44C=isotopiques:
O R R
[ 13CO] 16 +16[12 C18 O 16 O] 16 13 13
O= [[O] C+ O]I+ [C131717COO161717OO]O] +δS/VPDB [12C17=O13 16 SS
− 1 and et 18 18
δS/VPDB
S/VPDB = 18
SS
−1
différents O] O[ 16CO]O]O O] + [= 13 O]
12 17 16 13 17 16
45 II46
46 = 12
C 18 O
++ [[13 CC17O O16O] 45 [1212C O] S/VPDB
RVPDB 18
R
VPDB VPDB
VPDB
I46 = [12C18O16O] + [13C17O16O] + [12C17O17O]
16 12 16 16 13 16 16 12 17 16
O] + [12C17OCeci 17
Ceci II46
O] conduit
== [[12C
44conduit aux
C18aux rapports
O16rapports
O O] + [13C
O] isotopiques
isotopiques
17 16
O O] +suivants: suivants:
[12CI1745O=17[O]C O O]18+δ [ C O= O] RS − 1
18 c
(11.18)
This leads to the isotopic ratios: S/VSMOW 18
R
18
18VSMOW
RSScc

uivants: I 45 13 16
C16O 16 12 17 16 16 12 17 17
18
18
δ S/VSMOW
S/VSMOW = 18 −1
Ceci conduitI45 45aux rapports
46R==[ I 45
12
C18=O[[16 13
C
O] +O16[13O]
isotopiques O]
C17 ++O [[suivants:
1216C17
CO]O O+ [O] O]C O
= 13 O]
13 R + 217 R 17 18
R (11.14)
R= = = R+2 R VSMOW
VSMOW (11.14)
II 44
12 16
44 [[12 CC16O O1616O] O] 11.2.3.4 CORRECTION 18O POUR L’EQUILIBRE EAU−CO2
O] Ceci conduit aux [13rapports
C16 O16 O]isotopiques + [12 C17 O16suivants:
= 13 R45 +R 2=17IR 45 (11.14)
=
O](11.14)
= 13 R + 2 17Comme 11.2.3.4
R on CORRECTION
l’explique dans 18m
R wOlaPOUR Part.
(11.14) ’EQUILIBRE
L10.2.1.1, Rm EAU−CO
on doit appliquer2 une correction s
I 44 [ 12 16 16
C O O] 18
S

II 46
12
[[12 C
18
C18 O 16
O16 O] O] + [13 C17 O16 O] + [12 C17 O
13 17 16 12 17
OO17du
17
O] CO21818en équilibre isotopique avec un échantillon d’eau. Cette corre
12 17+ [ 16 C O O] + [ C Comme O] on
= 22l’explique
R++221313RR17dans R++la 1717 Part. (11.15)
R2 2 10.2.1.1,
values of 45Ron anddoit R appliquer une correction su
46 17
I 4546 R R [==13 C 16 = 16
46
O= O] + [ C O 12O] = R R R
measured (11.15) 46

= II 4444 12 16 16
16 16 16
45
R= [[ CC O
12 16
=O O]
13 O]
R + 2 appliquée
17
RO du COà ceenAstade
18 de la procédure
équilibre isotopique (11.14)avec de calcul. La valeur corrigée pour le CO
un échantillon d’eau. Cette correct
correc
O] + [ 12 C 17 O 17 O]
I 44 [16 C O13 O]17 16 17 (cf. Part. 4.3.2):R 1
2
R wc R cS
I 12
[ C O O] 18
R +R[ +46C RO O]13
12
(11.15)
17
+ [ C O O]appliquée (11.15) à ce13 Rstade R +de17 laR 2procédure (11.15)de calcul. La valeur corrigée pour le CO2
18 13 17 17 2
46
R = 46= =2 R + 2 45 18 17
O] En
En remplaçant 45R
I 44 remplaçant R et et[ 1246CRR16 dans
Odans 16 O]13C/ C/1212C,C, 1717O/O/1616OO= et2et 1818RO/ O/+1616218
O, nous
O, nous travaillons
18 travaillons
18 calibrated donc avec
donc 18avec4533 1846
(cf. Part. 4.3.2): Rc' = αc/w Rw0 = (1values +
45
αofc/w
46
) RRc − 18αc/w ρ 18Rc0
Rρand
inconnues.
I 46In translating
inconnues.
12
[ CD’un D’un
18
O O] autre
16 45
R+ [and
autre côté,
13 17
C 46R
côté, O nous
nous
16
pouvons12
+13[C/C
O]pouvons
into
17
12 O seulement
17
17 O]16
C,seulement
O/ O anddéterminer
déterminer 13 deux
deux rapports,
17 18 rapports,
viz. RRetet R.R.
viz. 45 46
46 18 17 182
(11.15)
OR et= I18O/ =16O, 18 =en 216 R + 218R R R α+c/w R Rw0 = + 18α 18 18
C, 17En
O/16remplaçant 18
O/
45 nous
16 R
O, et
we
46 travaillons
R
are dansthus
[ 12 13
C 16 donc
C/
dealing
O
12
16
C,
O] avec
17
O/
with
16 3 17 ou
O3 et
unknowns. O/ 18 valeurs
O, nous δ c'
: =
travaillons donc c (1
avec 3 c/w ρ) Rc − αc/w ρ 18Rc0
La relation théorique
La relation
44 théorique entre entre l’abondance
l’abondance en en OO etet OO de
17 18 de l’oxygène,
l’oxygène,R 1 est lalatroisième
est troisième
R S donnée
donnée R c
2
ons seulement
inconnues. On the other
déterminer
D’un autre deux côté, hand
rapports,
nous we can 45only
viz.
pouvons
46
et determine
Rseulement R. déterminer ou 2enra- valeurs deux18
δ
δ :' = (1
rapports,+ 18
α viz. ρ45 18 46 18
) R δ
et − R. α ρ 18
δ
nécessaire
nécessaire (Part.
(Part.
45 3.6): 3.6): 46 13 12 17 16 c c/w c c/w c0
En
17 remplaçant
e en La et 18O de
Orelation
tios,45viz. R et R46Rand
l’oxygène, estdans la
R. The third
C/ C, donnée
troisième
given required
O/
17 O et 18
18
O/16O, is nous travaillons
B donccalibrated values of 13R or 18R
avec 183
théorique entre relation
the theoretical l’abondance en the 
Techniques
between Odeet17Mesure
OOand de 18 l’oxygène,
O
18
δc' R=est (1la+ troisième
18
αc/w ρ45)R nSdonnée
18
δc −46 αc/w ρ δc0 18
n
R2
inconnues. 186
186D’un autre côté, nous pouvons seulement déterminer
11.2.3.5 deuxN rapports,
1
ORMALISATION viz. R et R.
nécessaire (Part. abundance 3.6): in natural oxygen (Sect. 3.6):
La relation théorique 17 18entre l’abondance en 17O et 18OLes de inter
11.2.3.5 l’oxygène, est la troisième
NORMALISATION
comparaisons entre normalised donnée values of 13R or 18R
laboratoires ont indiqué des différences consid
RS RS
186
nécessaire (Part. = 18
3.6): (11.16) isotopiques effectuées (11.16)
mesures sur des matériels identiques. of On a aussi montré
17
Rr Rr Les inter comparaisons Fig. 11.3.  chematic representation
entre laboratoires ont ofindiqué
procedures des différences considér considé
pouvaient êtrecalibration
réduits (A)
en and normalisation
utilisant deux standards(B) ofauisotopic lieu d’un. Les valeursq
186 mesures isotopiques effectuées sur des matériels identiques. On a aussi montré
where s and r refer to a sample and the reference, analyses.
ou s et r serespectively.
rapportent, respectivement, à l’échantillon peuvent dans
et à la référence.
pouvaient certains
être réduitsLeenplus cas être corrigées
simpledeux
utilisant est standards au lieu d’un. Les valeursR)
à partir du fait que le rapport (pour
δ)ci-dessus A . The measured R1 être values of 45Rmstandard
and 46Rm are calibrat-de la vrai (établie
d’utiliser une procédure itérative pour résoudre les équations (pour
peuvent mesurés
dans entrecas
pour
certains et le
l’échantillon deuxième
corrigées et leà partir duRfait 2 s’écarte
que (R le )rapport (pour R) o
It is the easiest to use an iterative procedure 45 to 46
ed (i.e. adjusted to the  international standards 1
standard, en partant des valeurs mesurées et corrigées de (pour R δ et
) R:
mesurés such entre
as VPDB R et
and le deuxième
VSMOW) standard
to give 45
RRc
ands’écarte
46
Rc
; de
R la vrai (établie)
solve the above equations for sample and stan- 1 2 w

dard, starting from the measured 17 13 45188 and R are corrected proportionally.

(1) On utilise l’approximation R = 0 et ainsi and R = correctedR (Eq. 11.14) S
values for R 18and R: 45 46 B. For normalisation the 13R or 18R scale is stretched
(2) Avec cela on calcule R à partir de R (Eq. 11.15) 46 188 in order to reach the  established value for a  second
(1) We17 apply the approximations 17R = 0 and standard (R2n). The corrections to the R2 and RS values
(3) Les valeurs de R13 peuvent
thus R =  R (Eq. 11.14) 45 alors être calculées (Eq. 11.16) is again proportional.
(4) En introduisant cela dans l’Eq. 11.14 on obtient de nouvelles et de meilleures valeurs de
13
R 110
(5) Cette procédure est reproduite jusqu’à ce que 13R, 17R et 18R ne changent plus.
13 18
Les valeurs de RSc et RSc ainsi obtenues pour les rapports isotopiques sont
 measuring techniques

11.2.4.2. O correction for water–CO2

18
equilibration
As was explained in Sect. 10.2.1.1, we have to
apply a correction for the 18O content of the CO2
brought in isotopic equilibrium with a water sam-
ple. This correction has to be applied at this stage
of the calculation procedure. The corrected value
for the equilibrated CO2 is (cf. Sect. 4.3.2):
18
Rc’ = 18αc/w 18Rw0 = (1 + 18αc/w ρ) 18Rc − 18αc/w ρ 18Rc0
(11.19)
or as δ values:
18
δc’ = (1 + 18αc/w ρ) 18δc − 18αc/w ρ 18δc0 (11.20)
11.2.4.3. Normalisation
Laboratory intercomparisons have shown a con-
siderable spread in isotopic results from differ-
ent laboratories on the same materials. It also has
been shown that this spread can be reduced by ap-
plying two standards instead of one. The R and δ
values may in certain circumstances be corrected
for the fact that the ratio (for R) or distance (for δ)
as measured between R1 and the second standard
R2 deviates from the true (established) value.
In this procedure of normalisation the R or δ scale
is so-to-speak stretched proportionally to reach
the established ratio or distance for R and δ. This
procedure of inter- or extrapolation is represented
by Fig. 11.3B and is mathematically written as:

TABLE 10.2.  Absolute isotope ratios needed for

the calculation procedure of calibrated and normalised
isotope ratios.

Reference material 13
R × 102 R × 104
17 18
R × 103 2
R × 106

PDB-CO2 1.12372 a  3.800 2.0790

SMOW-CO2 2.0785
VPDB-calcite 1.12372000 3.788666 2.0671607
VPDB-CO2 1.12372000 3.808033 2.0883491
NBS19-calcite 1.12591025 3.784496 2.0626129
NBS19-CO2 1.12591025 3.803842 2.0837547
VSMOW-water 3.790 2.005 b 155.76 c
VSMOW-CO2 3.867 2.0878142
SMOW-CO2 2.0879186
SLAP-water 3.683 1.8939104 89.07 c
SLAP-CO2 3.758 1.9719405
a 
[40]
b
[60]
c
[70, 71] reasonably well confirmed by [72].

Note: The 13R values are based on the original value of 13R for PDB by [30] as quoted by [40]. The 18R
value are based on the absolute measurement of 18R of VSMOW-water by [60] and known values for
the fractionations as given in Fig. 6.10. 17R values are based on the absolute measurement by [110]
and the square roots of the various 18O fractionations. The values in the shaded box are now obso-
lete. 2R values are the averages of the reported data.

The values for 45R1 and 46R1 are obtained from:

45
R = 13R + 217R (11.17a)
46
R = 218R + 213R17R + 17R2 (11.17b)

111
 INTRODUCTION

TABLE 10.3.  δ values of isotopic standards, and reference and

intercalibration samples measured on CO2 prepared by (i)
combustion of organic compounds, (ii) equilibration of CO2
with water at 25°C, or (iii) decomposition of carbonates with
orthophosphoric acid (95%).

Reference Material 13
δ (‰) 18
δ (‰) 2
δ (‰) Fourni par

NBS1 water — − 7.94 — exhausted

NBS1A water — −24.33 — exhausted
NBS16 CO2 −41.60 −35.98 — exhausted
NBS17 CO2 − 4.51 −18.61 — exhausted
NBS18 carbonatite − 5.03 −23.00 — NIST/ IAEA
NBS19 marble +1.95 −2.20 — NIST/ IAEA
NBS20 limestone −1.06 −4.14 — not distributed
NBS21 graphite −28.16 — — exhausted
NBS22 oil −29.74 — — NIST
VSMOW water — 0.00 0.00 NIST/IAEA
GISP water — −24.79 −189.7 NIST/IAEA
SLAP water — −55.50 −428.0 NIST/IAEA
IAEA-CO1 marble + 2.48 − 2.44 — NIST/IAEA
IAEA-CO8 calcite − 5.75 −22.67 — NIST/IAEA
IAEA-CO9 BaCO3 −47.12 −15.28 — NIST/IAEA
LSVEC Li2CO3 −46.48 −26.46 — NIST/IAEA
IAEA-C6 sucrose −10.43 — — IAEA
IAEA-CH7 poly-ethylene −31.83 — −100.3 IAEA
USGS–24 graphite −15.99 — — NIST
GS19 CO2 − 7.50 − 0.19 — CIO
GS20 CO2 − 8.62 − 0.99 — CIO

Note: 13δ values are relative to PDB or VPDB, 18δ of CO2 to VPDB-CO2, 18δ and 2δ refer to SMOW or VSMOW.
Certain reference samples are now obsolete and only quoted for historical interest [108].

NIST — National Institute of Standards and Technology, Atmospheric Chemistry Group, B364, Building 222,
Gaithersburg, MD 20899, United States of America

IAEA — International Atomic Energy Agency, Analytical Quality Control Services, Agency’s Laboratory,
Seibersdorf, P.O.Box 100, A –1400 Vienna, Austria, fax +43 – 1–2060 – 28222

CIO — Centre for Isotope Research, Nijenborgh 4, 9747 AG Groningen, the Netherlands,

tel. +31 – 50–3634760, fax +31 – 50–3634738

112
 Dans cette procédure de normalisation, Techniques
l’échelledede R ou δ est, pour ainsi dire, étendue pourTechniques de Mesure
Mesure
Dans cette procédure de normalisation, l’échelle de R ou δprocédure
atteindre le rapport ou la distance établis pour R et δ. Cette est, pour d’inter-
ainsi dire, étendue pour
ou extrapolation
atteindre
Dans le rapport
cette sur ou
procédure la
dedistance
normalisation, établisetpour l’échelle R et δ. Cette
de RPour ou procédure
δcalculer
est,techniques
pour d’inter-dire, ou extrapolation
est représentée la figure Fig. 11.3B s’écrit mathématiquement lesainsi
ainsi: rapports étendue pour Techniques de Mesure
measuring
Techniques de Mesure isotopiques à partir dedes
Techniques rapports des faisceaux (e
Mesure
est représentée sur la figure Fig. 11.3B
atteindre le rapport ou la distance établis pour R et δ. Cette et s’écrit mathématiquement procédure ainsi:
d’inter- ou extrapolation
utilise la même démarche que précédemment:
est représentée RSnsur R la
n
2 figure Fig. 11.3B et s’écrit mathématiquement Pour calculer ainsi: les rapports isotopiques à partir de desMesure rapports des faisceaux (ex
n = calculer les rapports isotopiques àPour calculer les rapports (11.21)
isotopiques 16à partir deson rapports des faisceaux (e
RRPourc RR2nc partir des rapports I des faisceaux [ 18(exposant
Techniques
O O] + [ 17m)
O ]
S
S= 2 utilise
(11.21) la même 34
R démarche
m
= 34
= que
( c précédemment:
/ (11.21)
c ) 2
= (c34 / c32 )(2 18 R + 17 R 2 )
Rutilise
c
R cla même démarche que précédemment: utilise la même démarche I que 34 précédemment:
32
[ 16
O ]
RSS R22
n n
32 2
= c 18 16Pour calculer 34 les m rapportsI 34 isotopiques(11.21)
[ 1818O1616àO]partir + [ 1717Odes ] rapports des faisceaux (e
Par rapport Related
au c
RS standard Rto international
2 the international I 34 et standard
écrit en[ valeurs O et
and O] δ,[ laOcomposition
+
written
17
I = (18c34 / c32
2 ] 34 R m = 34isotopique 17 ) [2 O 16O] + [ O2 2 ]= (c34 / c32 )(2 1818R + 1717R 2 )2
finale
Par rapport au
34
R =m
=et(cécrit
34 / c32 ) utilise
16 δ, la
= R(cdémarche
la composition
même = I32
34 / c
c34
)(=2 (que R+ c32R) ) [ O ]
/précédemment: = (c34 / c32 )(2 R + R )
calibrée as standard
δ values,
et normalisée est: international
the  finalI 32calibrated en
as valeurs
well [ as Onor-
2]
I3232isotopique finale [ 16 O22 ]
calibrée malised isotopic
et normalisée composition of the sample
est:international et is:δ, la composition I 33 [[ 17
18 O16 O]
16
O O] +=[(17c O/2 c] )(2 17 R)
Par rapport au standard et écrit en valeurs 34 R m = I 34 isotopique finale
33 m
et et and = ( c /
R = I = (c34 / c32 ) [ 16 O 16] (11.24)
33 c 32 ) 33 = (c34 / c32 )(2 18 R + 17 R 2 )
32
RSn
calibrée et normalisée est: R2n Rwc RSm R2n I 32
32 [
2 O ]
RRSn = (1+ δnS/ 1 ) = RR2nc RRwcI RRSmm = RR2nc (1+[δ17w/O (1 + δ S/w )
n m
1 )16 (11.22) 2
I 33 [ 1717O1616O]
1 = (1 + δ ) = 1 33 w = 2 (1 + δ w/ 1 ) (Après
1O] + δ m
)
33 m
R = I = ( c / c )
(11.22) [ O O] = (c33 / c32 )(2 17à17Rchaque )
33
R m2
c = = ( c cc )
/ = ( correction
c / c
33
R
)( 2
m
des
=
17
R )
I 32erreurs
33
= ( c 33 instrumentales
/ c 32 ) 16
32 [ 16O 2 ] =(spécifiques
(c33 / c32 )(2 R) appareil et d
16 et
m S/w
R
(11.22
n
S/ 1
R n R1 c Rwm
I
33R n 32
[ O ]
33 32
I
33
[ O ]
RS1 R2 Rw32RS
2 R22
mesure), les valeurs de δ correspondantes sont:
= c (1+ δ w/ 1 )probablement du moment de la (11.22)
32 2
= (1+ δ S/ 1 ) = c
n 2
(1 + δ S/w )
m

La procédure Rde1 normalisation

The normalisation R2 est R1souvent
procedureRwm Rappliquéeis 2 often being auxAprès analyses
ap-correction de 18mO

2
desetI 33erreurs
H de l’eau, instrumentalesdans
[ 17 O16 O] (spécifiques à17chaque appareil et dé
La Après correction des erreurs instrumentales Après correction
(spécifiques 33
R 18àdes
= chaque erreurs
2 = (c instrumentales
appareil/ c ) et16dépendant =(spécifiques
/ c32 )(2 à chaque
(c33aussi R) appareil et d
la procédure de normalisation est souvent appliquée auxéloignés
analyses de l’échelle
O34et H de33l’eau, 32 dans
mesure où plieddans tocethe  cas 18deux O and standards
2
H analyses suffisamment of water, probablementas sur (11.24)
du moment IR32 VSMOW
m de la 34sont
mesure), [R Oles 2 ] valeurs
18 17 δ2correspondantes sont:
de
2 Rs + deRsδ correspondantes sont:
ladisponibles.
mesure oùhere probablement
dans ce cas du moment de la mesure), probablement
les valeurs 34 du
de moment
δl’échelle samplede la mesure),
correspondantes sont: − 1les = valeurs
two dedeux
standards standardssont lessuffisamment
R2relatively wide 18apart 16éloignés
on2H/1sur δdu =18 2 VSMOW
et−l’eau,
1du= SLAP sont −1
s
La procédure Lesde valeurs
normalisation R1 etest souvent valeurs
appliquée O/
aux Oanalyses
et H de
After VSMOW
O 34 etm H de
correction
R for 34 dans
instrumental
R 2 18
errors
R + 17 2
R (specific
disponibles. the VSMOW
Les valeurs scale
1 et R2are
RPrecipitation)
de deux sontavailable.
lesindiqué
valeurssur The R
18
O/Après
16
1Oand
correction
2 1
et H/précédent.
H des erreurs instrumentales (spécifiques à chaque appareil et d
surdu VSMOW et du 34 SLAP
reference r r
(Standard
la mesure Light
où dans Antarctic
ce cas 18 standards suffisamment le tableau
éloignés and 34 RLa
34 m
l’échelle
probably m normalisation
VSMOWtime-dependent 34Rsont 2 18
18Rs +
for
17 2
each17Rs 2instru-
(Standard R2 values are 34the  O/Rsample
34 16 m
O or indiquéthe  H/Rsur
2 34 1
Hs 18values 2 of
18
probablement 1734
R +précédent.
134R
2
δdu= moment RLasample
de− 1la=mesure), Rs − 1 les
s
= 2valeurs Rs +17 deR2 sδ−correspondantes
1 sont:
peut aussiLight Antarctic Precipitation) le tableau samplenormalisation
disponibles. s’écrire
Les valeurs
VSMOW entièrement
and de δSLAP
R1=et en34Rtermes
msont les
2(Standard de− 1valeurs
=Light
valeurs δ−Antarctic
1 =est
et
O/
et
16
et s2H/
Oalors Hδ2sdu
approchée
17ment),
=− 34134 Rpar
VSMOW m
the corresponding
m
−et1 du = 3434SLAPRr δ− values 1 = 2 1818Rare: + 17Rr 2 − 1
peut aussi s’écrire entièrement Rreferencede valeurs 34
Rr δ et est2alors 18
R + Rr Rpar
reference Rr 2 R + Rr
as engiventermes tableauapprochée
reference
(Standard Precipitation)
Light Antarctic Precipitation) in indiqué
the above sur le table. précédent. 34 mLa normalisation
Rsample 34
Rs 2 18 Rs + 17 Rs2
Normalisation
δ S/VSMOW
peut aussi s’écrire
n
entièrement δcanm
en also
termes be de written
valeurs entirely
δ etet est in approchée
alors
34
δ = 3433 Rmpar m − 1 = 33 − 1 = 17 17− 1
34 R 18R 2 R
= δmmand is then approximated (11.23) Rsr − 1 = 22(11.25)
S/VSMOW
et
terms
δ n
of δ values et by 33
δ = Rreference
sample
− 1 = Rs +−171 R = s
−1
δ SLAP/VSMOW = δ SLAP/VSMOW
n
S/VSMOW S/VSMOW 33 m
Rreference (11.23) 33
Rr 2 17 Rr
r
17
Rr
δ SLAP/VSMOW
n
δ S/VSMOW
n δ m
δ m 33 m and 33 R m 33
SLAP/VSMOW
17 33 Rsample m 33Rs 2 1717Rs 17
17Rs
= 33 mS/VSMOW Rsample 33
Rs et(11.23) 2 17 Rs 33 33 δ = R sample − 1 =(11.23) R − 1 = 2 R − 1 = Rs− 1
Tableau 11.3.δValeurs
n
δ des standards δ = 33 isotopiques
δ SLAP/VSMOW m
− 1 =et33des références,
− 1 = 17 et −intercalibration δ
1 = 17 33 R= s
33 m
−reference
17 − 1
1 des18échantillons = 33
33R
s
− 1 = 17 s
− 1
2 17Rrde référence = 17
17Rr
−1
SLAP/VSMOW
Risotopiques Comme
Rr références, 2 Ret les valeurs R R
Rr reference
m
r et R r des échantillons
R r 2 R Rr ou standard sont c
Tableau 11.3.mesurés
Valeurs sur δ des standards et des
le CO2 préparé par (i) combustion de composés organiques,
reference r intercalibration des échantillons
(ii)18équilibration r r
(11.25) 3317 m 17 18
using
mesurés
du CO
the δ
sur avec
n
le values:
CO l’eaupréparéa par
25°C, (i) oucombustion
(iii)
calculer
de
décomposition composés facilement
de
33organiques,
carbonates
R Rsample
s et(ii)18 Rs, et33donc
équilibration
avec l’acideRs les valeurs 2 17 Rs de δ17 et Rs δ.
2
Tableau 11.3. Valeurs δ des standards17isotopiques
2 et des références,
Comme les δ =
et intercalibration 17
valeurs33 17Rmr et17des − 1 =
Réchantillons
r des33 −
échantillons 1 = − 1
17 de référence
= − 1standard sont co
ou
du Comme
CO2 avec
orthophosphorique les valeurs
l’eau RLes
a 25°C,
(95%).
18
Rr des
r et valeurs
ou (iii)
de Comme
échantillons
décomposition
13
δ sont delesréférence
exprimées valeurs
de par
Because carbonatesRou
rapportthe  etauR18
Rr standard Rand
avec
PDB r des 18R
sont
l’acide
ou échantillons
au connus,
values 2 R
on
for de peutréférence
17
the reference R ou standard sont c
2
δSLAP/VSMOW
mesurés sur le= CO − 428.0‰
2 préparé par or 18(i) combustion de composés 17
13 calculer facilement
organiques, 17 reference
(ii)
18 équilibration
r
17Rs et 18Rs, et donc les valeurs
r
r r
de 17
δ et
r
18
δ .
orthophosphorique
calculer
VPDB,
du CO lesavec
2
facilement
18
δ dul’eau (95%).
CO
17
2 par
a
Les
R25°C, et valeurs
srapport Rou de
, etVPDB-CO
sau (iii)
δles11.3
calculer
sont
doncdécomposition RADIOMETRIE
18facilement
exprimées
valeurs
2, les δ et de
desamples
2 par 18
δδsecarbonates δR. sstandards
or
rapport
etréfèrent etau RSMOW
auavec PDBs, POUR
et are
donc
ou ou
l’acide
au les
known, LES valeurs
17
RISOTOPES
s and
17
de 18δRset , andδ. RADIOAC
18

2
RSLAP
VPDB, =
les0.5720
18
δ du 2
CORSMOW
2 par rapport audeVPDB-CO les 18les
2, sont
2
thus
δ etvaleursδ sethe  17
réfèrent
17
Rδrand et au δPDB
r values
1818SMOW ou
can be easily calculated.
au VSMOW.
orthophosphorique Certains (95%). échantillons
Les valeurs de 13 Comme
référenceδPour
sont aujourd’hui
exprimées
mesurer la
obsolètes
parradioactivité,
rapport auRet des
ne ou
nombre
échantillons
sont au d’instruments de référence ou standard sont c
sont18 disponibles, chac
au VSMOW. 18 Certains leur2 échantillons de référence 11.3
11.3 sont RADIOMETRIE
aujourd’hui
RADIOMETRIE obsolètes
17
et auRset
18
Rs RADIOACTIFS ,POUR
etnedonc
POUR sont les LES
ou LES
ISOTOPESde δ et δ.RADIOACT
ISOTOPES
17
RADIOAC
and 11.3
présentés
VPDB, RADIOMETRIE
lesque δpour
du CO intérêt
par rapport historique POUR
au (données
VPDB-CO LES
calculer2, lesISOTOPES
avantages
de facilement
l’AIEA,
18
et 21995).
δspécifiques
δ se réfèrent SMOW valeurs
présentés que pour leur intérêt historique (données de l’AIEA, 1995). et leurs désavantages. Les principaux instruments do
au VSMOW. Certains échantillons de référence
18 Pour mesurer la radioactivité, nombre discuter
Poursont mesurer
sont 11.3.
aujourd’hui
(i)la lesRadiometry
obsolètes et
radioactivité,
compteurs ne for
a nombre
gaz sont radioactive
et (ii)d’instruments
les spectromètres sont disponibles,
scintillationchacu
δSLAP/VSMOW = −55.50‰ or Pour mesurer
d’instruments lasont radioactivité,
disponibles, nombrechacun d’instruments
avec leurs sonta disponibles, liqui
chac
présentés que pour leur intérêt historique (données 11.3
avantages
avantages
de RADIOMETRIE
l’AIEA, 1995).
spécifiques
spécifiques
isotopes et
et
leurs
leurs POUR
désavantages.
désavantages. LES ISOTOPES
Les
Les
principaux
principaux RADIOACT
instruments
instruments
don
do
18 avantages spécifiques et leursδ désavantages. Les deux principaux instruments dont nous allons peut être mesuré comm
13 18 2
Référence
RSLAP = 0.9445 Matériel18
RSMOW Avec δ ces δ techniques, Fourni l’échantillon
par radioactif
discuter sont (i) les compteurs a gaz et (ii) les spectromètres a scintillation liquid
Référence discuter sont Matériel
(i) les compteurs δa gaz et (ii)
13
Pour
18
discuter
les
interne, sontFor
δ spectromètres
mesurer il(i)
2
la measuring
δles compteurs
a scintillation
radioactivité, radioactivity
Fourni ila gaz par et (ii)
liquide.
nombre a number
les spectromètres
d’instruments of instru-
sontdua disponibles,
scintillation liqui
chac
(‰) (‰) i.e. ments est
(‰) mélangé
are
ou
available,
est
each
une partie
with
intrinsèque
their specific ad-
milieu de compta
Table 11.3 contains the δ values of Avec
the isotopic
avantages ces deux techniques, l’échantillon radioactif peut être mesuré comme
RéférenceAvec ces deux Matériel techniques,(‰)
13
δ
l’échantillon (‰)
Avec 18
δ ces spécifiques
fonctionnement
radioactif deux (‰) 2
peutde êtreetmesuré
l’instrument.
δtechniques, leurs
Fourni désavantages.
Cela
l’échantillon
comme par comporte une Les
radioactif
source principaux
les avantages peut être instruments
suivants:
mesuré comm do
NBS1standardseau and the available reference −− intercom-
−interne,
7,94 i.e.
discuter sont vantages
il(i)−−les
est mélangé and ou
compteurs disadvantages.
épuisé
ila estgaz une
et partie
(ii) The main
les intrinsèqueinstru-
spectromètres du amilieu de comptag
scintillation liqui
NBS1 interne,
parison eau i.e. il est mélangé ou(‰)
samples. −− il est une −partie interne,
1)(‰)7,94 Les i.e.
intrinsèque il est
particules −− mélangé
(‰) du milieu
β formées oude ilcomptage,
épuisé
par estla une partie
décroissance chargéeintrinsèque
du anddu
radioactive milieu
n’ont pas de besoin
compta
NBS1A eau −− −24,33
fonctionnement ments−− de we will discuss
l’instrument. épuisé Cela are (i) gas
comporte counters
les avantages (ii)suivants:
NBS1A fonctionnement
eau de l’instrument. −− Cela comporte fonctionnement
Avec
−24,33 les avantages
ces
parois deux
de −−de l’instrument.
l’instrument;
liquid suivants:
techniques, c’est Cela
l’échantillon
épuisé comporte
particulièrement les intéressant
radioactif avantages
peut être suivants:
pour mesuré comm
la détection
NBS16
NBS1 CO
eau2 −41,60
−− −35,98
− 7,94 −−−− scintillation épuisé spectrometers.
épuisé
NBS16 1)
interne, Les particules
i.e. β
ildésintégration
est mélangé formées ou par
ilHest la décroissance
une partie radioactive
car intrinsèque n’ont
ducas, milieu pas besoin
de comptaβ esd
1) LesCO épuisé
−41,60 −35,98 − −− 3 14
NBS1A
NBS17 11.2.5. Measurement
COparticules
eau 2
2 β formées of −−
− 4,51
18
par 1)
O/la16décroissance
O and −24,33
−18,61 β
Lesde laWith
particules
radioactive−−−− both β formées
n’ont du
pas
techniques par
épuisé et
besoin
épuisé du deCpénétrer
lathe radioactive
décroissance dans lesles
radioactive
sampledeux isn’ont l’énergie
pas besoin
NBS17 CO
17
O/ 2 dein
16
O2 −−41,60
4,51 particulièrement−18,61 parois de l’instrument;
fonctionnement −− de l’instrument. c’est épuisé particulièrement
Cela comporte lesintéressant avantages pour suivants:la détection
NBS16
NBS18 parois CO
carbonatite l’instrument; −c’est
5,03 −35,98
−23,00
2) parois
L’efficacité de l’instrument;
intéressant
measured
−−−− de comptage pour
as an lac’est
NIST/ détection
internal
épuisé
est particulièrement
AIEA i.e. intéressant
des particules
source, itl’angle
is mixed pour la détection
2 − 3 presque 14 de 100%, de détection étant de
NBS18 β de la désintégration du 3H AIEA et du 14C car dans les deux cas, l’énergie β est
NBS17
NBS19 β− carbonatite
This analysis de
COla
marbre includes, as with
2 désintégration du
−+1,95
−5,03 H et 2du 14−23,00
3 CO , two
4,51 1)C car
−18,61
−2,20 β−dans
mea-
Les departicules
laleswith,−−
désintégration
−− orβ cas,
deux
−− formées
is NIST/
du par
anl’énergie
intrinsic
NIST/ HAIEA
épuisé et
β du
la Cofcar
décroissance
part
est très dans
faible. les deux
radioactive
the counting me- cas,
n’ont l’énergie
pas besoinβ es
NBS19 surements, marbre i.e. of the ion beam +1,95 ratios for2) masses
−2,20 L’efficacité
parois de dium,−− deresponsible
comptage
l’instrument; NIST/ estfor
c’est AIEA the operation
presque
particulièrement de 100%, ofintéressant
the instru-
l’angle de détection étant de
pour la détection
NBS18
NBS202) L’efficacité carbonatite
calcaire
de comptage − est
5,03presque2)
−1,06 −23,00
−4,14
11.3.1
de 100%, COMPTEURS
L’efficacité l’angle −−−− dede comptage A GAZ
détection NIST/
non est AIEA
fourni
presque
étant de 4π. de 100%, l’angle de détection étant de
<34>/<32> and <33./<32>, while the number −of ment. This has the following
3 fourni 14 advantages:
NBS20
NBS19
calcaire −1,06 −4,14 −−
β de la désintégration non
du H et du C car dans les deux cas, l’énergie β es
unknownsmarbre is also two: 18O/16O+1,95 and 17O/16O. −2,20
Bien Thus, −−
que l’utilisation des divers compteurs
NIST/ AIEA
189 a gaz soit différente, la constructi
NBS20 contrary to CO2, no assumption
calcaire −1,06 has to be 11.3.1
made
−4,14 COMPTEURS (1) −−de The β A GAZ
particles non from
fourni 189 the radioactive decay do
11.3.1 COMPTEURS A GAZ 11.3.1
2) COMPTEURS comptage A GAZ
identique. Le principe est indiqué sur la Fig. 11.4. l’angle de détection étant de
L’efficacité est presque de 100%,
for the relation between the 18O and 17O fraction- not need to penetrate the wall
Bien que l’utilisation des divers compteurs 189 deaabase gazofsoit the instru-
différente, la constructio
ations.
Bien que Morel’utilisation
than that, from des divers these compteurs
measurementsBienaque gaz l’utilisation
soit différente,
ment; desthis divers
la is compteurs
construction
especially relevant gaz soit
est
to différente, la constructi
detecting
the relation identique.
11.3.1 Le
COMPTEURS principe est A indiqué
GAZ sur la Fig. 11.4.
identique. between Le principe the two fractionations
est indiqué sur la Fig. can11.4.
identique. be Le principe
β- particles est indiqué from sur 3
H la and Fig.14 11.4.
C decay as in both
derived.
Bien que l’utilisation casesdes the β divers
energy compteurs
is very small a gaz soit différente, la constructi
191
To calculate the isotope ratios from the measured identique. Le principe est indiqué sur la Fig. 11.4.
(superscript m) ion beam ratios a similar proce- (2) The  counting efficiency is nearly 100%,
dure is chosen as previously: the detection angle is 4p.

113
 INTRODUCTION
11.3.1. Gas counters
Although the operation of the various gas coun-
ter types is different, the basic construction is
the same. The principle is shown in Fig. 11.4.
Basically there are 3 different types of gas coun-
ters, depending on the magnitude of the high-
voltage applied between the wire and the counter
wall:
(1) the ionisation chamber,
(2) the proportional counter,
(3) the Geiger-Müller counter.
The  counters are filled with a  counter gas, re-
quired to have suitable ionisation characteristics.
11.3.1.1. Ionisation chamber
The incoming radiation, that is, a particle origi-
nating from a decay reaction inside or outside
the counter tube, looses its energy by collisions
with gas molecules in the counter. These events
cause the molecules to become ionised. In
the electric field inside the tube, the heavy posi-
tive ions slowly move towards the wall and be-
come neutral by picking up electrons. The small,
negative primary electrons set free by the colli-
sion become accelerated towards the positive cen-
tral wire. After being collected by the wire, these
electrons are observed as a small electric current
or an electric pulse in the wire. In the electronic
circuitry, attached to the counter, this pulse is reg-
istered and the pulse size measured. This is repre-
sentative for the number of primary electrons and
thus of the energy of the incoming particle. In this
way information is obtained about the radioactive
decay event.
11.3.1.2. Proportional counter
The primary electrons are accelerated in the elec-
tric field between the  wire and counter wall. If
the  voltage on the  counter wire is sufficiently
high, the primary electrons, accelerated towards
the wire, obtain enough velocity and energy to
ionise other gas molecules and so create more
free electrons. The same is true for these new
electrons and so on and so forth. In this way an
avalanche of electrons is created moving towards
and collected by the wire (Fig. 11.5). This phe-
nomenon is called gas multiplication. The re-
sulting electric pulse is proportional to this gas
multiplication (and thus depending on the high
114
10 to 50 cm
counter wall at
ground potential
counting gas
central wire
at high voltage
Fig. 11.4.  Cross section of a  gas-filled counter tube
for detection of radioactive radiation. The  ionisation
phenomena in the counter are shown in the cross-sec-
tion of Fig. 11.5.
voltage) and is still proportional to the number
of primary electrons and thus to the original
energy of the incoming particle (Proportional
Gas Counter, PGC).
11.3.1.3. Geiger Müller counter
During operation as a proportional counter
the secondary electron avalanche is very local. At
very high voltage, however, the secondary ioni-
sation process extends over the entire length of
the counter tube. The pulse size is maximal and
no longer depends on the energy of the incoming
particle or the wire voltage: in the GM counter
the existence of the particle is registered, but it
can not be recognised, as in the case of the pro-
portional counter. This is, however, essential in
order to be able to distinguish the particle (for in-
stance, a β- particle from 3H or 14C) from strange
particles.
Our conclusion, therefore, has to be that the only
suitable gas counter for our purpose is the one
which operates as a proportional counter. This
equipment was the  first established for measur-
ing the radioactivities of 3H and 14C. These atoms
have to be brought in a gaseous form suitable for
operation in a counter as sample as well as count-
ing gas. This is essential because the β radiation
can not penetrate the counter wall, the β energies
being extremely low (Fig. 8.2). Later another
technique came into use, i.e. the liquid scintilla-
tion spectrometer.
 measuring techniques

counter wall at earth potential The background of the counter, i.e. the count-

incoming
ing rate (number of counts per sec.) of the counter
primar y electrons without a radioactive source, in our case CO2 and
β− particle
C2H2 or H2 without 14C or 3H, respectively. This
secondary electrons
background has to be subtracted from the over-
all counting rate. In order to minimise the back-
gas multiplication ~10 5 ground –which would otherwise be orders of
magnitude larger than the actual (net) counting
central wire at high voltage
rate we are interested in- the counter is made of
Fig. 11.5.  Lateral cross section through a  gas coun- low-activity materials and shielded against radia-
ter. An incoming β− particle looses its energy through
tion of the surroundings (see Fig. 11.6).
primary ionisation. At low voltage only these elec-
trons reach the wire resulting in a small electric pulse Most counters are made of copper or quartz with
(ionisation chamber). If the voltage is sufficiently high, sizes ranging between 0.5 and a few litres, al-
the number of primary electrons can be multiplied by
though also mini-counters exist. An international
a factor of 105 (PGC). At very high voltage the second-
ary ionisation is maximal and the electron avalanche compilation was made by [44].
occupies the  entire length of the  counter: the  pulse In principle, the data handling of radiometric
height is no longer depending on the incoming particle
equipment is simple. After a certain measuring
energy or the voltage (GM counter).
time tm a number of Nt disintegrations in the coun-
ter have been observed. The statistical uncertainty
11.3.1.4. Counter operation or standard deviation of this number is N . This
gross counting rate of Nt/tm (counts per sec) has
At both ends of the proportional gas counter to be diminished by the background B (counts /s)
(PGC) the geometry is distorted and thus the elec-
to give the net counting rate A’ (see Sect. 13.3.3):
tric field. The detection of particles from radioac-
tive decay is, therefore, less efficient. The conse-
A’(t) = Nt /tm − B (11.26)
quence is that the overall counter efficiency is not
exactly known: routinely an absolute measure- This result has to be standardised, i.e. has to be
ment is not feasible. The solution to this problem corrected to a standard amount of sample gas
is to perform a relative measurement: the sample
in the counter, simply by applying the Law of
is to be measured under exactly the same condi-
Gay-Lussac, in other words by multiplying by
tions as a reference sample, or, finally, as an in-
ternational standard (Sect. 8.1.2), or the depen- the pressure and temperature ratios:
dence of the detected radioactivity of a sample on T p0 273.15 105
the various parameters has to be exactly known. A(t ) = A' (t ) = (11.27)
T0 p t + 273.15 p (in Pa )
Without going into detail, we mention the essen-
tial parameters [82]. Now we have obtained the standardised absolute
The amount of gas in the counter; since sample activity: 3A for 3H, 14A for 14C Chapitre
(Sect. 8.1.2).
11
and reference are being measured in the same The internationally established standard (Oxalic
counter, the counter volume (V) is not relevant,
Le standardAcid)
établi has
internationalement
to be measured (l’acide oxalique)
under exactly doit être mesuré dans
the same
so that measuring the pressure (p) and tempera-
exactement conditions. Then the activity
identiques. Alors ratio canpeut
le rapport d’activité be calcu-
être calculé comme le
ture (T) is sufficient: the  amount of gas = V.p/T
with T = t + 273.15 K. lated as the ratio
deux activités (Eq. 8.4). between these two activities
(Eq. 8.4).
The purity of the counting gas; if the gasLa con-
déviation standard de l’activité mesurée est (le standard dans l’exp
tains electronegative impurities, i.e. gas mol- The standard deviation in the measured activity is
négligeable):
ecules with a strong attraction to electrons, part (standard in B is negligibly small):
of the primary and secondary electrons are lost,
1 A+ B
decreasing the pulse size and the counting rate σA ≈σN = N = (11.28)
[111]. t m tm

115
11.3.2 SPECTROMETRE A SCINTILLATION LIQUIDE

11.3.2.1 PRINCIPE PHYSIQUE

 INTRODUCTION

iron
paraffin + boric acid

lead

‘old lead’
Geiger Müller
counters
14
C or 3H
counters

Fig. 11.6.  Cross section of a typical counter set-up with shielding against radiation from the surroundings, includ-
ing cosmic radiation. The GM counters operate in ‘anti-coincidence’ with the proportional counters in the mid-
dle. The low-mass hydrogen atoms in paraffin are very efficient in reducing the (penetrating) energy (speed) of
high-energy neutrons. Boron has a high absorbing capacity for low-energy neutrons. The high-mass lead absorbs
γ radiation. ‘Old lead’ has lost the radioactive lead isotope 210Pb (RaD), due to its short half-life (22a).

11.3.2. Liquid scintillation is needed. This is realised in a photomultiplier

spectrometer
11.3.2.1. Physical principle
This method is based on the principle that certain
materials emit light after their molecules have
been excited by collisions with high-energy par-
ticles.
This process, called luminescence, takes place in
a proper solid or liquid. Our interest is focussed
on the use of liquids, because there are methods to
transfer carbon (including 14C) to benzene which
-with some precautions- is suitable as a scintilla-
tor, whereas water (with 3H) can be mixed with
a scintillating liquid, a commercially available
cocktail of various constituents. The requirement
of this mixture is that it mixes well with water,
transfers the primary electron energies into fluo-
rescent energy, and finally into low-energy fluo-
rescent light within the secondary-emission range
of the photo-electrode of the photomultiplier.
In this way we again are dealing with internal ra-
dioactive sources, as with the gas counters. For
higher-energy β and g particles solid crystals are
available made of organic (anthracene) or inor-
ganic compounds (sodium iodide).
The result is that each incoming particle causes
a light flash in the scintillator, which can be ‘seen’
by a light sensitive detector, the photocathode.
The fact is that certain materials emit electrons
when they are hit by a  light flash, the  so-called
photoelectric effect. The number of primary elec-
trons is very small. Therefore, as with the propor-
tional counter operation, a multiplication process
tube (Fig. 11.7). Each primary electron is acceler-
ated and able to cause the emission of additional
secondary electrons in the second electrode plate
or dynode at a higher positive voltage. This pro-
cess is repeated several times, so that finally an
electric pulse arrives at the last dynode that is
easily measurable. Also here the  final pulse is
proportional to the multiplication factor — a di-
rect function of the voltage — and the energy of
the incoming particle. This allows the selective
registration of only those particles that originate
from the radioactive decay event of interest (such
as 14C or 3H).
11.3.2.2. Counter operation
In Sect. 11.2.4.2 we have mentioned the prepara-
tion of benzene from CO2 via acetylene. Typical
quantities being treated are 1 to 10 grams of
carbon, resulting in 1.2 to 12 mL of benzene.
The scintillation light emitted by excited C6H6
does not have the frequency for which the pho-
tocathode in the multiplier tube is sensitive.
Therefore, certain high-molecular compounds are
added in order to shift the frequencies to lower
energies.
Generally a large number of samples is arranged
in a liquid scintillation spectrometer or counter
(LSS), in which the samples are in turn placed in
front of the photomultiplier automatically. Also
here arrangements have been made to reduce
the background radiation as much as possible,
primarily by using an anti-coincidence arrange-

116
 measuring techniques
photocathode
secondary
photomultiplier
electrons
β− particle
from radio-
active decay
scintillator
light
primary
electrons
dynodes at increasing
high voltage
Fig. 11.7.  Schematic drawing of a  (liquid) scintil-
lation counter, the  detector part of the  LSS. An elec-
tron from β- decay in the scintillating crystal or liquid
causes a light flash that is ‘transformed’ into electrons
at the photocathode; the number of primary electrons
is multiplied by secondary emitting dynodes at in-
creasing high voltage.
ment of other scintillation counters (instead of
the use of GM counters with PGC).
The advantage of the LSS is that it can be pur-
chased automated and purchased commercially,
while a gas counter set-up has to be made by
the laboratory. On the other hand, the operation
of a PGC is more ‘transparent’, from a physical
point of view.
In principle the same type of calculations lead to
the activity of the sample, as shown for the gas
counters (Eqs.11.21 and 11.23). Related to
the problem of gas purity with the gas counters,
liquid scintillation may suffer from impurities in
the benzene + scintillator mixture. This results in
a decrease of the size of the electric output pulse.
For this effect of quenching a correction is to be
applied.
11.4. Mass spectrometry for low-
abundance isotopes
11.4.1. Principle and application of
AMS
Detecting the presence of isotopes with a very
low abundance such as the radioactive isotopes,
for instance 14C in carbonaceous material, wood,
charcoal, peat, bone, shells, groundwater, by de-
tecting the  radioactive decay is very inefficient.
Of all 14C present in a sample only one thou-
sandth decays in about 8 years, i.e. 3.8 × 10 – 12
part per sec.
A much more efficient detection method is mass
spectrometry, i.e. measuring the actual concentra-
tion of 14C. Nevertheless, only in the late seven-
ties attempts have been successful to detect single
14
C particles in carbon and separate these from
other foreign elements.
IRMS operates at a few kV and accelerates mol-
output
signal
ecules such as CO2, which are separated into
ion beams of masses 44, 45 and 46. For 14CO2
the mass is 46 which signal — due to its extreme-
ly low abundance of < 10 – 12 — is completely lost
in the 46 signal from the various stable isotopic
combinations in CO2. It appears that, by making
the step to C ions instead of CO2 ions, the ‘isobar’
problem can be solved. This means accelerating
over MV rather than kV.
Under these high-voltage conditions registration
becomes possible in a nuclear particle detector.
Contrary to IRMS single particles can then be de-
tected, rather than beam currents.
For this purpose existing nuclear accelerators
were used, specifically Tandem Van de Graaff
Accelerators. Later dedicated machines were
constructed and put into operation that are much
smaller (Fig. 11.8) [112].
The complete set-up of the accelerator with sur-
rounding equipment is called Accelerator Mass
Spectrometer (AMS). The essential features of an
AMS are the following:
(1) In the ion source negative ions are produced.
This is necessary because contamination of
carbon by nitrogen can not be avoided and
a N+ ion beam would make the detection
of 14C practically impossible, 14C having
the same position in the ultimate mass spec-
trum. Negative ions, on the other hand, have
the advantage that N- ions are extremely un-
stable and loose their charge before entering
the accelerator.
(2) The negative ions are produced by bom-
barding graphite — i.e. the sample — with
Cs atoms. Presently, only very few CO2 ion
sources are operational for AMS. This would
be less aggravating for the chemical prepara-
tion procedures, but such a source is a com-
plicated device.
(3) Ultimately, positive ions are more easily to
detect, so that inside the accelerator the neg-
ative electric charge of the carbon ions is
removed and replaced by a positive charge
by steering the ions through a stripper gas
(Ar). The stripping process especially de-
stroys molecular isobars with mass 14, such
117
 INTRODUCTION

as the beam contaminants 13CH and 12CH.
The now positive ions are again accelerated
and subsequently mass selected in a mag-
netic field so that 12C, 13C and 14C can be de-
tected separately.
(4) Before entering the accelerator, the ions
are mass separated by a  magnetic field
and the 12C beam is reduced by a factor of
100 by a fast rotating diaphragm (chopper,
Fig. 11.8). The second magnet recombines
the three ion beams.
The special advantages of the AMS technique, in
comparison with radiometry, are that:
(1) only milligram (or smaller) quantities of car-
bon are needed for one analysis, compared
to roughly grams for the radiometric tech-
niques (see Table 11.3) [113];
(2) the analysis is considerably faster, i.e. lasts
an hour instead of days.
The disadvantages are that:
(1) the capital investment is almost 100 times
larger;
(2) the AMS technique is more complicated
from a technical point of view;
(3) the precision is not yet as good as the best
counters (PGC or LSS) can manage
(Table 11.4).
11.5. Reporting 14C activities and
concentrations
11.5.1. The choice of variables
The following definitions are in use:
The absolute (specific) 14C activity, that is the 14C
radioactivity (in Bq or, conventionally, in disinte-
grations per minute (dpm) per gram of carbon) is
given the symbol
14
A (in dpm/gC) (11.29)
In general, 14C laboratories are not able to make
an absolute measurement, because the measuring
efficiency is unknown. Also, in general, the abso-
lute 14C content of a sample is generally not rel-
evant. Therefore, the sample activities are com-
pared with the activity of a reference material,
the international standard. In reality, the number
of 14C registrations (β registrations from 14C de-
cay in radiometric detectors such as proportional
counters and liquid scintillation counters, reg-
istrations of 14C concentration in AMS systems)
are related to the number of registrations from
the reference sample under equal conditions. This
results in the introduction of a 14C activity ratio or
14
C concentration ratio:
measuring efficiency × 14 Asample 14
Asample
14
a= 14
= 14
=
measuring efficiency × Areference Areference

accelerator
14 14
C decay rate in the sample C concentration in th
0
= 14 0
= 14
C decay rate in the ref . material C concentration in the re

magnet
magnet
12
C and 13C
chopper detectors
very high
voltage
magnet 14
C detector
ion source

5 × 10 m

Fig. 11.8.  Schematic and simplified drawing of an Accelerator Mass Spectrometer (AMS) [112]. The ion source
produces negative carbon ions. In order to reduce the overwhelming contribution of 12C, the number of C ions
are artificially reduced by a factor of 100 in the chopper. The C- ions are accelerated in the accelerator tube of
the left half of the accelerator by an electric field of about 3 MV. In the middle they are stripped of electrons to
C3+, so that in the right half, they are further accelerated as positive ions. In the final magnet the 12C, 13C and 14C
ion are separated and finally counted.

118
 14
measuring efficiency × 14 Asample 14
Asample
a= 14
= 14
=
measuring efficiency × Areference Areference
measuring techniques
ncy × 14 Asample 14
Asample
14
= 14
=
cy × Areference Areference In several
14
C decay rate in the sample C concentrat ion in cases
14 the differences in 14C content
the sample
= 14 14
= between samples are small. Therefore, the use
C decay rate in the ref . material
C concentration in the ref . material
of relative abundances has been adopted from
14
in the sample C concentration in the sample the  stable-isotope field, in casu the  relative 14C
= 14
he ref . material C concentration in the ref . material content (activity or concentration), 14δ, defined as
(11.30) the difference between sample and standard 14C
content as a fraction of the standard value:
Because in the numerator and denominator of
the  last two fractions, the  detection efficien-
cies are equal for sample and standard, whether (11.31)

the analytical technique applied is radiometric or
mass spectrometric. The values of δ are small numbers and there-
fore generally given in ‰ (permil), which
The use of the ratio 14a is adequate for any is equivalent to ×10 – 3. Therefore, the factor
type of measuring technique. Henceforth, 103 should not enter into mathematical equa-
the symbol 14A will be used for the 14C con- tions (as δ/103).
tent, radioactivity as well as concentration,
A14C reference material or standard was chosen
Under natural circumstances the values of to represent as closely as possible the 14C content
14
a are between 0 and 1. In order to avoid of carbon in naturally growing plants. The 14C
a large number of decimals, it is gen- content of the standard material itself does not
eral practice to report these values in % need to be, in fact is not, equal to the standard 14C
(percent), which is equivalent to ×10 – 2. content. The definition of the standard 14C activ-
Therefore, the factor 102 should not enter ity is based on the specific activity of the original
into equations (as 14a/102). NBS oxalic acid (Ox1) [78], as will be discussed
in more detail.
TABLE 10.4.  Survey of specific features of the various isotopic
techniques.

Rare isotopes Medium type Medium quantity Precision

2
H: 0.1‰
few mL gas
2
H, 13C, 18O 13
C: 0.01‰
IRMS H2, CO2, N2 to
(15N, 34S) 18
O: 0.02‰
few 0.1 mL gas 15
N: 0.02‰
3
H H2, C2H6 few mL H2O 1 TU (NE)
PGC with enrichment few 100 mL H2O 0.1 TU (E)
14
C CO2, C2H2, C3H8 1 – 50 L CO2 (equiv.) 0.5 – 0.1% *
3
H H2O few mL H2O few TU (NE)
LSS few 100 mL H2O few 0.1 TU (E)
14
C C6H6 few to 15 mL C6H6 0.5 – 0.2% *
C (graphite) 0.1 – 2  mg C 0.5% *
AMS 14
C
(CO2) few mL CO2 ?

* for carbon with 14a = 100%

Note: The 3H and 14C precisions quoted are valid for samples of roughly 10 TU and present-day activities, respectively.
The asterisks refer to the cases where larger quantities of sample allow greater precision. For the radiometric tech-
niques we have assumed a counting time of one or two days.
IRMS = Isotope Ratio Mass Spectrometer
LSS = Liquid scintillation spectrometer
PGC = Proportional Gas Counter
AMS = Accelerator Mass Spectrometer

119
 n’avons
n’avonsaucune
aucunepreuve
preuveexpérimentale
expérimentalefiable
fiablededelalavraie valeurdedeθθ, ,—
vraievaleur —ililyyaad
croire
croireque
quelalavraie valeurdedeθθest
vraievaleur estproche
prochedede1,9
1,9—,
—,etetparce
parceque
quecette
cetteincertitude
incertitud
dedegrandeur
grandeurdedelalaprécision
précisionanalytique
analytiquedes mesuresdede1414C,C,nous
desmesures nousutiliserons
utiliserons
INTRODUCTION
approximation
approximationsuffisante.
suffisante.

11.5.2. The standardisation 11.5.2.2

11.5.2.2 11.5.2.2.
LE
LEPROBLEME
PROBLEMEThe question
DE
DELA of radioactive
LADECROISSANCE
DECROISSANCE decay
RADIOACTIVE
RADIOACTIVE

Before the  definition of standards can Pour be

Pourcom-
les For radioactive
leséchantillons
échantillons radioactifs,
radioactifs, samples l’activitéa measured
l’activité mesurée activity
mesuréedépenddépenddu de-
dutemps
tempsdedemesure,
mesure
pleted, two factors have to be discussed that pends on the time of measurement, tm:
complicate the standardisation of 14C results and 1414
the respective symbols. AA(t(mt m) )==1414AA(t(0t)0 e) e− λ−ΔλtΔt ou or 1414AA==1414AA0 0eeλ (λtm(t−mt−0 t)0 )
ou
(11.33)
cecequiquiest estégalement
égalementvalable valablepour pourlelematériel
matérielstandard.
standard.Ainsi, Ainsi,quand
quandon onrepor
repo
11.5.2.1. The question of isotope fractionation1414 which is also valid for the standard material.
absolue C,C,l’année
absolue l’année pour
pour laquelle
laquelle la
la
Therefore, when reporting an absolute C con- valeur
valeur est
est correcte
correcte 14doit
doit être
êtrespécifiée.
spécifiée. LaLamm
During the transition of carbon from one com-
également
égalementvraie vraiepourpourlelestandard.
standard.L’année L’annéeAD1950 AD1950aaété étéchoisie choisiecomme
commeannéeanné
pound to another, i.e. the assimilation of CO2 by 0 0 tent, the year for which the value is valid must
plants, the exchange of CO2 from the air to sur- se
l’exposant
l’exposant be specified.
seréfère
réfère doncThe 
donc ààcettecette same"année is true
"année 0". for the  standard.
0".L’activité
L’activité standard
standardest estdonc
doncvalable
valab
face water, etc., isotope fractionation occurs1950.for
1950. Comme The year
Commelalateneur of reference
teneurenen CCdes 1414 was chosen
deséchantillons to be
échantillonsseseréduit AD1950;
réduitavec avecleletemps
tempssimult
simu
13
C as well as for 14C. Also the laboratory treat- the superscript 0 refers to this ‘year 0’. The stan-1414
celle
celledu dumatériel
matériel
dardstandard,
standard,thus
activity toute
touteiscomparaison
comparaison
valid for the year dedelalateneur
teneur
1950.enen As CCentre
entreles
lesdeux
deu
ment of sample materials may introduce an isoto-
valable
valablepour pourl’année
l’année
the  14 1950
1950(=(=of
C content t0t).0samples
). reduces in time simul-
pic change, for instance by an incomplete chemi-
cal reaction. If this fractionation were neglected, taneously with the standard 1414 material, any com-
LaLaconséquence
conséquence parisonestestbetween
que
quelalateneur teneur
the two CC absolue,
absolue,
results in a  qui
qui
14 estestbasée
C content baséesursurlalacompar
compa
samples of different chemical composition (car-
standard
standardAcide Acide
validOxalique
Oxalique
for the yearselon
selon des
1950 desprocédures
procédures
(= t 0).
standardisées,
standardisées,est estvalable
valablepour
pour
bonate and plants, C3 and C4 plants) but made of
sans
sans
the same (age) carbon (determined by atmospher- tenir
tenir compte
compte de de laladate
date de de mesure.
mesure.
ic CO2) would seem to have different ages. The consequence is that an absolute 14C con-
Therefore, in order to make 14C ages comparable,
11.5.2.3
11.5.2.3 DDEFINITION tent, which
EFINITION DELis
DE L based on1414
’ACTIVITE
’ACTIVITE a comparison
STANDARD with
CCSTANDARD
a correction has to be applied for this fraction- the Oxalic Acid standard according to stan-
Techniques de Nous
Nous
Mesure
ation effect. The theoretical relation between C pouvons
14pouvons maintenant
maintenant
dard procedures, définir
définir is l’activité
l’activité
valid for standard
standard
the year àà95%
1950, 95%dedel’activité
l’activitédudu
d’Acide
d’AcideOxalique
and C fractionations is written as (Eq. 3.43):
13 Oxaliqueirrespective
nr.1
nr.1(Ox1)
(Ox1) ofdans the time
dans AD
AD1950:of measurement.
1950:
θ
14
AN ⎛ 13 RN ⎞
=⎜ ⎟ (11.32) 1414 0 0
AA ==00,95 ,951414AA00
(11.32)
1 N==13 ,56±±00,07
13,56 dpm/gC==00,226
,07dpm/gC ,226±±00,001
,001Bq/gC
Bq/gC
14
A ⎜⎝ 13 R ⎟⎠ RNRN OxOx
1N
11.5.2.3. Definition of the  C standard 14

where A and R refer to the measured, A14 activity

N to
14 13 14
14 13 14 14
où A et the fractionation-corrected
R se réfèrent à l’activité or Cnormalised mesurée, ACN à We14 l’activité
can nowCdefine corrigée du
the standard activity as 95%
1313 13
activity, while 13
R
fractionnement ou normalisée,N tandis que R(or rather δ ) is an
N N (ou plutôt inter- δNof) the activity
est une valeur standard batch of Oxalic Acid
of the specific
nationally
internationalement adopted
adoptée. Cettestandard
valeur estvalue. 13
δN =This−25‰value versus VPDB nr.1 (Ox1)
(Eq. in AD 1950:
7.1.3). L’activité
is 13δN = −25‰ versus VPDB (Eq. 7.1.3). Also
standard doit être normalisée
the standard de la
activity hasmême to befaçon. La seuleinexception est. que — pour des
normalised . . . .
13
raisons historiques
the same — way.le vieux . standardexception
The only Acide. Oxalique . (Ox1)
is that -for est normalisé . . à sa valeur (11.34)δ
Chapitre 11
historical
réelle de −19‰. reasons- the old Oxalic Acid standard
(Ox1) is normalised to its real δ valueChapitre 13
of −19‰. 11 where R stands for ‘Reference’, N for ‘Normalised’
Toutes les valeurs 13 13
de δ sont exprimées par rapport auoùstandard R correspond for isotope
VPDB fractionation
à(Gonfiantini,
"Référence", 1984). (to 13δ = –25‰,
N à "Normalisé" pour leonly
fractionnement isot
All δ values are with respect to the VPDB in the case of Ox1 to δ = −19‰) 13
13 and dpm/gC
Pour lesoùprocessus
R correspond
standard à "Référence",
[41].
naturels, la valeur de N àθ"Normalisé"
est d’environ pour le fractionnement
2 (Craig, isotopique (avec δ
means 1954). Puisque
disintegrations nous
per minute per gram of car-
n’avons aucune preuve expérimentale fiable de la vraie valeur debon, while
il y the superscript
a des raisons de refers to the fact that
0
θ, —
For natural processes the value of θ is about 2 the definition is valid for the year AD1950 only.
croire que la[28].
vraieSince
valeur θ estno
wedehave proche
reliable de 1,9 —, et parce
experimental que cette incertitude est de l’ordre
evi-
de grandeurdence
de la about the true
précision value ofdes
analytique θ, — there are
mesures de rea-14
C, nous The definition
utiliserons θpresented
= 2 comme by Eq. 11.34 is related to
to believe that the true value of θ may be
sonssuffisante. time by:
approximation
closer to 1.9 —, and because this uncertainty is 14 A  14 A0 e − λ ( ti − t0 )  0.95 14 A0 e − λ (ti − t0 )  0.95 14 A
RN RN Ox 1 N Ox 1 N
irrelevant 14
compared14 0
to the analytical
− λ ( ti − t 0 )
precision
14 0
of
− λ ( ti − t 0 ) 14
11.5.2.2 LE ARN DE LA
C measurements,
14 PROBLEME ARN
we ewill use θ = 2
DECROISSANCE AOxa 1 Nsuffi-
0.95RADIOACTIVE
as e  0.95 AOx1 N (11.35) (11.35)
cient approximation.
Pour les échantillons radioactifs, l’activité mesurée dépend du temps t0 and tmti: refer to the year 1950 and to
de mesure,
where
the moment of the origin of the sample, respec-
14
A(t ) = 14 A(t ) e − λΔt ou 14 A = 14 A 0 e λ ( tm −t0 ) tively. (11.33)
m 0

ce qui est également valable pour le matériel standard. Ainsi, quand on reporte une teneur
absolue 14C,120
l’année pour laquelle la valeur est correcte doit être spécifiée. La même chose est
14 0
également vraie pour le standard. L’année AD1950 a été choisie comme AOx 2 N année
 (1.2736  0.0004) 14 AOx
de référence;
0
1N
0 14 0 14 0
AOx 2 Nà cette
l’exposant se réfère donc (1.2736  0.0".
"année 0004 ) AOx1 Nstandard est donc valable pour l’année
L’activité (11.3 6)
14
1950. Comme la teneur en C des échantillons se réduit avec le temps simultanément avec
 = –25‰, avec 13δ = −19‰ seulement pour Ox1) et dpm/gC désintégrations moyennes par
13 0
e", Noù à "Normalisé"
R minute
correspond parpourgramme le fractionnement
à "Référence", de carbone, N à tandis isotopique
"Normalisé" pour le δfractionnement
(avec
que l’exposant se réfère au faitisotopique que l’a définition 13n’est
δ
(avecTechniques de Mesure
seulement valide pour Ox1) que 13 et dpm/gC
pour l’année désintégrations moyennes par
AD1950.
= –25‰, avec δ 0= −19‰ seulement pour Ox1) et dpm/gC désintégrations moyennes Techniques par de Mesure
ne, tandis que l’exposant se réfère au fait que l’a définition 0n’est
minute Lapar définition
grammeprésentée de carbone, danstandis l’Eq. que 11.34 est reliée
l’exposant measuring ausetempsréfère par:
au fait que
techniques l’a définition n’est
950. standard déterminée avec le même rendement de détection, à environ la mê
14 14 0 − λ ( ti − t 0 ) 14 0 − λ ( ti − t 0 ) 14
valide que pour ARNl’année
 ARNAD1950. e  0.95 AOx1 N e corrigée standard  0.95déterminée A
pourOx14 1 N fractionnement isotopique. de
le avec le même (11.35)rendement Dansdétection, à environ les
ces conditions, la mê
ré
14 14 0 − λ ( ti − t 0 ) 14 0 − λ ( ti − t 0 )
l’Eq. 11.34 est reliée au A
temps = par: A e = 0 ,95 A e
corrigée = 0
pour,95 le A fractionnement (11.35)
isotopique. Dans ces conditions, les ré
La définition Because
présentée the original
RN
dans l’Eq. supply
RN
11.34 est of reliée
oxalicauacid
Ox 1 N
différents
temps haspar:laboratoires deviennent comparables. La décroissance des conce
Ox 1 N

been exhausted, a new batch of oxalic acid différents

(Ox2) laboratoires
l’échantillon The consequence
et du standard entre of
deviennent etthe relative
t0 comparables.
tm est représentée Lameasure-
décroissance des conce
par l’Eq. 11.33.
( ti − t 0 ) − λ ( ti − t 0 )
= 0,95où14tA 0
et
0 Oxis t e
se rapportent,
1 Niavailable = for0 ,95 14
A
respectivement, à (11.35)
l’année 1950 et à la ment
date is
d’originethat the resulting
de l’échantillon. value of 14
a does
14
ARN = 14 ARN 0
edistribution
− λ ( ti − tOx
0 ) 1N
= 0,95 by14the NIST
AOx0
1N e
− λ ((former-
l’échantillon
ti − t 0 )
= 0,95 14 et A
not
du standard entre(11.35)
Ox 1 N depend on the time
t0 et tm est représentée par l’Eq. 11.33.
ly US-NBS). La mesure relative a pour conséquence de of donner measurement
une valeur 14a indépendant
Comme le stock d’acide oxalique d’origine est épuisé, un nouveau is, lot d’acide
contrary to oxalique
the absolute (Ox2) 14
A value (see 14a indépendant
ctivement, à l’année 1950 etcareful à la date d’origine de by l’échantillon. La
la mesure,mesure relative au contraire a pour de conséquence
la valeur de 14 donner une valeur
A absolue (voir Part. 11.5.2.2); l’
est Through
disponible auprès
où t0 et ti se rapportent, respectivement, à l’année 1950 du measurement
NIST (anciennement a number
US-NBS). et of Sect. 
à la dateaud’origine 11.5.2.2);dede the absolute
l’échantillon. 14 activity result-
la
obtenue mesure, contraire la valeur A absolue (voir Part. 11.5.2.2); l’
ique d’origine estlaboratories [79], the lot Cd’acide
activityoxalique has become (Ox2)re- à partir ingde fromla mesure
the relative relative est valide pour
measurement l’année
is valid for 1950, si on la mu
14
épuisé, un nouveau
Comme A la le suite
stockde mesures
d’acide soigneuses réalisées par plusieurs
obtenue àlaboratoires
partir la Mann,
ded’acide mesure 1983),
ifrelative onesta relié
valide pour Bq/gC:
l’année 1950, si on la mu
T (anciennement lated US-NBS).
14
to that ofoxalique the original d’origine Ox1 by: est épuisé, Bq/gC: un nouveau 14
×lot
a the year
0,226 14 oxalique
=1950, A0 (Bq/gC) (Ox2)
multiplied by 0.226
l’activité
est disponible C à celle de
auprès du NIST (anciennement l’Ox1 original par: US-NBS). Bq/gC: 14 14
a ×a × 0.226 = 
0,226 = A A 14 14 0 0
(Bq/gC).
(Bq/gC)
14 0
uses réalisées par plusieurs AOx 214N 0 (1laboratoires
.2736  0.0004 Mann, ) 14 A1983),
0
Ox 114N 0 on Commea(11.36)
relié celaAsa was été envisagé plus (11haut,
.36) dans certaines études sur les systèm
A la suite de mesures AOx 2soigneuses
N = (1,2736réalisées ± 0,0004)parAplusieurs laboratoires Mann,anticipated
1983), above,
on certain
(11.36) studies on natu-
original par: 14 Contrary to the Old Oxalic acid (with a true
Ox 1 N Comme
concentrations cela a
ral en
été14 envisagé
systems C présentent
are
plus
concerned des relié
a
haut,
écarts
with
dans certaines
faibles.
only Dans
small
études
ces cas,sur
differ-
leshabitu
il est systèm
l’activité C à celle de l’Ox1 original par:
13
δ 14
concentrations 1413 en C14présentent des écarts faibles. Dans ces cas, il est habitu
ences in formeCdecontent. In those cases it entre is conven-
Contrairement
0 value of à−19.2‰, l’ancien H.Craig, acide oxalique pers.comm., (avecles une valeurs
[79]), valeur14 Cδsousréelle de différence
−19.2‰, H.Craig, relative l’activité mesurée de
6 ± 0,0004) 14 AOx 1N (11.36)
les valeurs C
tional sous to forme
report de
14
C différence
data as relative
the relative entre l’activité mesurée de
difference
comm.the New 14 0
AOx 2Mann,
pers. N = (1,2736
Oxalic 1983), acid± 0le,(with0004
nouvel 14
Ox2
0
AOx = −17.6‰)
)13δacide celle has
1 N oxalique (avec
de la référence:
13
δOx2 = −17,6‰) a été normalisé (11.36) (=
13 13celle
between
de la référence: the measured sample activity and that of
ide oxalique (avec
corrigé topourbe
unenormalised
levaleur fractionnementδ (= corrected
réelle de −19.2‰,
isotopique) for isotope
àH.Craig, δ =frac- −25‰, tandis
the reference: que les deux activités se
13
nouvel acide
Contrairement
oxalique
à l’ancien
tionation) (avecto13δOx2
13acide oxalique (avec une valeur
δ = –25‰,
= −17,6‰) while
a été both normalisé activities (=
δ 14réelle 14deA −19.2‰, 14 H.Craig,
A0
réfèrent à AD1950. δ = 14 − 1 = 14 0 −1=
14
a −1
comm. pers. refer
Mann, to AD1950.
1983), le nouvel acide oxalique (avec 13
δ 14 −17,6‰) 14 A a été normalisé 14 A0
Ox2 = (=
13
ent isotopique) à δ = −25‰, tandis que les deux activités se δ = 14 AR − 1 = 14 AR0 − 1 = 14 a − 1 (11.39)
Par conséquent, l’activité standard est: 13 AR deux activités AR
corrigé pourConsequently le fractionnement the standard isotopique) activityà is:δ = −25‰, tandis que les se
réfèrent 14 à0 AD1950. 0,95 14 13
to entre 13δ mes
ndard est: ARN 14 A 0 0,950.7459 14 AOx 0
214N 0 or
14
ARN14Comme 0.7459 14indiqué, AOxAs14
2N
normaliserit les
mentioned, résultats
has(11.37)
become common 14
C à partir de l’écart
practice
= = 0,7459 AOx 2 N or AComme
RN = 0,7459 indiqué, AOxnormaliser for(11.37)
les Maintenant,
résultats C laà partir de l’écart δ mesd
Par conséquent,RNl’activité
1.2736
1,2736standard est: devenu une normalise
pratique 14
2 N courante.C results deviations of the mea-
discussion sur laentre
procédure
devenu
peut êtreune pratiqueδDans
sured
complétée.
13
fromla −25‰.
courante. mesure Now
où, parthe discussion
Maintenant, la discussionlesof
convention, sur la procédure
valeurs de 13C/12d
9 14 AOx 0
or 14
A = 0 , 7459 14
A (11.37) (11.37)
peut the normalisation
être international
complétée. Dans procedure
lalesmesure can
où,stables, be
par convention, completed. les valeurs de 13C/ 12
2N
où14 les
RN
0,95 de 14A0 Oxpour
valeurs
2N
14 0 Ox1 et Ox2 se standard
réfèrent 14 à Since
l’activité pour
du matériel isotopes
13en 121950, Vienna PDB, l’Eq. 11.32 peu
0
ARN = = 0,7459 AOx 2 N or 14
ARN =standard 0,7459 international AOx 2 N conventionallypour les isotopes
C/ C values are related
(11.37) stables, Vienna PDB, l’Eq. 11.32 peu
indépendamment 1,2736 14de 0l’époque de la mesure. la manière suivante:
to the international standard for stable isotopes,
where the  A values for Ox1 and Ox2 larefer to
manière suivante:
r Ox1 et Ox2 the activity se réfèrent of à l’activité du in matériel en 1950, Vienna PDB, Eq. 11.32 can be rewritten by:
14 0
the material 1950, irrespective 2
e de laoùmesure. les11.5.3
valeurs de Aof measurement.
ofDERNIERES
the time pour Ox1 et Ox2 se réfèrent à l’activité
DEFINITIONS 14
AN / du 14 matériel
ARN ⎡ 13 Ren N/
1950,
13
RVPDB ⎤ 2
14
14A / 14 A
14 = ⎢⎡ 1313R / 1313 R ⎥⎤
indépendamment de l’époque de la mesure. A/
N ARN 14 = ⎣
RN R/
N RVPDB
VPDB
⎦⎥
Nous pouvons maintenant définir plus précisément la concentration 14 14 en C d’un
⎢ 13 échantillon
13 en
NITIONS termes de rapport d’activité ou rapport de concentration A/comme ARN ⎣ R/ RVPDB ⎦
le rapport entre la
11.5.3. Final definitions or using Eq. 11.38, with 13
δN = –25‰, and conse-
11.5.3 DERNIERES DEFINITIONS 14 ou enstandard utilisant l’Eq. 11.38, avec 13
δ = –25‰, et par conséquent 1 + 13δN =
finir plus précisément concentration la concentration
en carbone-14
We can now more carefully specify the  ouC en en
mesurée C d’un et échantillon
la valeur 14 duen
con- (qui
quently doit 1 +toujours
13
δ N  = 1 être
+ normalisé
(−25‰) = 0.975:
13
N
13 0,975: utilisant l’Eq. 14 11.38, avec δN = –25‰, et par conséquent 1 + 13δN =
té ouNous rapportpouvons
pour deδ ), maintenant
concentration
les deux définir
termes comme
se
tent of a sample in terms of the activity ratio or plus
rapportant précisément
le rapport
à la la
entre
date concentration
de lala mesure: en C d’un échantillon en
0,975: .
mesurée termes et la de valeur rapport
du standard
concentration d’activité (qui as
ratio outhe ratio
doit rapport
toujoursbetween de normalisé
être concentration
the mea- comme le rapport entre la
14 0 − λ(tm −t0 ) 2 2 . 2
rapportant concentration
à la date sureden 14 C
de carbone-14
la
14
mesure:content A mesuréeand14 Athe value eet la valeur 14 0
du A standard
of the standard 14 0 (qui 14 ⎡1 + être
14 doit toujours
13
δ ⎤ 2 14 ⎡1 + (−25 ‰) ⎤ 2 14 ⎡ 0,975 ⎤ 2
normalisé
a = 14 = 14 0 − λ(tm −t0 ) = 14 130 = a a N = a. ⎢⎡1 + 1313δ ⎥⎤ = (11.38)N
a ⎢⎡1 + (−25 13 ‰) ⎥ ⎤ = 14 a ⎢⎡10+,975 13 ⎥⎤
pour 13δ), les (which
deux termes always Asehas to be
RN rapportant ARNnormalised
e à la datefor deARN laδ), with
mesure: 14
a N = 14 a ⎣⎢ 1 + 13δN ⎦⎥ = 14 a ⎣⎢ 1 + 13δ ⎦⎥(11.40) = a ⎣⎢ 13δ ⎦⎥
A e 0 − λ(tm −t0 ) 14both
A terms referring to the time of measurement:
0
⎣ 1 + δ ⎦ ⎣ 1+ δ ⎦ ⎣1 + δ ⎦
0 − λ(tm −t0 )
= 14 0 = 14 a 0 14
(11.38) 14
ARN e A14RN
où t0 correspond 14
Aà l’année A 1950,
14 0 − λ(tm −t0 )
e A à l’activité
14 0
A de 0l’échantillon mesurée au temps tm, et ARN
a 14= 14 = 1413 0 − λ(tm −t0 ) = 14 0 = et 14 de
a14 même:and13likewise: . (11.38)
(= 0,95 × AOx1 ARNavec AδRN N e = –19‰ ou A0,746 RN
et
× A de même:
Ox2 avec δN = –25‰) à la valeur du
50, 14A à l’activité de l’échantillon mesurée au temps tm, et 14ARN . 2
(11.38) 14 14 ⎡ 0,975 ⎤ 2 (11.41)
= –19‰ 204 ou 204 0,746 × 14
A avec 13
δ =
14 –25‰) à la valeur du A = A ⎢
⎡ ⎥
⎤
0,975t , et ARN 14
où t0 correspond whereà tl’année 1950,N A. à l’activité14A de isl’échantillon mesurée14au ⎣temps
N
AN = A ⎢1 + 13δ m⎦⎥
Ox2 14 13
0 refers to the year 1950, the ac-
(= 0,95 × tivity 14
AOx1 avec of the sample
13
δN = –19‰ measured ou 0,746 14
× AOx2
at time tm, and avec δN = Eq. 11.39
13while
–25‰) 1 laδ ⎦valeur du
⎣ +à transforms into:
14
ARN (= 0.95 ×  AOx1 with 14 13
δN = –19‰ tandis or que l’Eq. 14
δN 11.39
= 14aN se − 1 transforme en: (11.42)
204 0.746 ×  AOx2 with δN = –25‰) is the value
14 13
tandis of que l’Eq. 11.39 se transforme en:
the standard determined with the same detection 14δ = 14a − 1
N N
efficiency, at about the same time tm and corrected 14 11.5.4.
δN = 14aSpecial N−1
cases
for isotope fractionation. In this way 14a results In general the presentation of 14C results depends
from different laboratories become comparable. on the type of application. For each case an ex-
The decay of sample and standard 14C content ample is given to illustrate the applicable defini-
from t0 to tm is described by Eq. 11.33. tions and equations.

121
 Chapitre 11

11.5.4 CAS PARTICULIERS INTRODUCTION

14
En général la présentation des résultats C dépend du type d’utilisation. Pour chaque cas on
va donner un exempleHydrology
11.5.4.1. pour illustrer les définitions et les équations que l’on
sample peut appliquer.
collection. Therefore, the 14a value has to
be de-normalised:
From a geochemical point of view the use of
11.5.4.1 Ha , the non-normalised 14C content at the time
14 YDROLOGIE
S
14
a = 14aN [(1 + 13δ) / 0.975]2 = 0.549 = 54.9%
of sampling, is the most meaningful,14rather S than 14
Du point dea  vue géochimique l’utilisation de a , la concentration C non normaliséeTechniques à [cf. 11.40]
δ value. Instead of applying a normalisation de Mesure
l’époque decorrection,
l’échantillonnage,
the initial est14la
C plus
contentlogique, plutôt qu’une The 
of groundwater valeur 14 δ. Au lieu d’appliquer
C content in the year of sampling (1998)
is going to be determined by
une correction de normalisation, la concentration initialespecific geochemi- en 14
C de l’eau
cal reasoning of the origin of the inorganic En hydrogéologie
car-
then is:onsouterraine
s’intéressedoit à la être concentration en 14C de l’échantillon d
déterminée à partir d’un raisonnement géochimique spécifique surC’est
de l’échantillonnage. l’origine de lalavaleur 14a doit être dé normalisée :
bon content. Furthermore, if we are dealing with a = 14aN [(1 + pourquoi,
14 S 13
δ) / 0.975]2 exp[–(1998 – 1950)
concentration en carbone
groundwater ages,inorganique.
it is irrelevant Par — ailleurs, si on s’intéresse à l’âge des eaux
from a hy- /148267]
= 14dea=N0.546
[(1 + = 13 54,6 % 2
souterraines,drological
il est sanspoint
intérêtof — view d’un
— point
whether de vue
ageshydrologique
count a— savoir siδ)l’âge
/ 0,975] doit = 0,549 = 54.9 %
être comptéback in time
en temps from
écoulé the year
à partir of sampling
de l’année (calcu-
de l’échantillonnage
La concentration en 14
( ≡ (calcul
54.6 Cbasé
pMC = % poursur
14 S
ofamodern
l’année ) ou de àl’échantillonnage
carbon = %MC) (1998) est alors:
lation based on a14) or 14from
14 S
0 1950 (calculation 14
[cf. 11.43]
partir de 1950 (calcul 14basé sur a = a ). De fait, la précision des datations C de routine est
based on a = 14a0). Moreover, the precision of 14 S
a = 14aN [(1 + 13δ) / 0,975]2 exp[–(1998 – 1950) / 8267] = 0,546
de toute façon de ± 50
routine 14
C ans
datingou plus.
is ± 50 Enyears
conséquence, on peut de manière
or more anyway. Using more équivalente utiliser la
or less sophisticated models, the 14C
14 Consequently, we can equally well use
valeur a la plus simple en % comme celle obtenue par les procédures the most ( ≡
and the  54,6 13 pMC = % de carbone moderne = %MC)
de laboratoire
C data, together simples.with information on
simple 14a value in % as is obtained in simple lab- the chemical composition of the water sample,
oratory procedures. A l’aide de modèles plus ou moins sophistiqués, les données 14C 13C
can be used to estimate the sample age (i.e.
1313 informationsthe period
sur la composition
of time since chimique
the infiltration de l’échantillon
of the wa-d’eau, peuvent ê
Without C,
Sans normalisation C lenormalisation,
rapport d’activité the activity
de l’année ratio in
d’échantillonnage est:
the year of sampling is: estimer l’âge de A straightforward
ter). l’échantillon (i.e. la ‘waterpériode age’deastemps
obtainedécoulée
by depuis l’infiltra
simply applying Eq. 11.52 is not possible.
2
⎛ 1 + 13δ ⎞ − ( ts −1950 ) / 8267 Obtenir directement un "âge de l’eau" en appliquant simplement l’Eq.
14 S 14
a = a N ⎜⎜ ⎟⎟ e (11.43)
possible. (11.43)
⎝ 0,975 ⎠ 11.5.4.2. Oceanography and atmospheric
research
11.5.4.2 RECHERCHE EN OCEANOGRAPHIE ET SUR L’ATMOSPHERE
Souvent ces valeurs sont données
Often these values are en given
pour cent de carbone
in percent of moderne The same (pMC) ou pourcent
equation holds for de the oceanographic
moderne (pM).modern De pluscarbon
bpM/100 (pMC) 14 S
(= or a )percent
est parfois Laappelé fraction moderne. Cependant, les
modern même équation
applications. est retenue
However, pour as le applications
the spread océanographiques. T
of the data
symbole pM (pM). In addition
est utilisé par lespM/100hydro ( = a ) is some-
 14 S
chimistes l’éventail
et generally
des
les océanographesdonnéesispour quite
est small, it islaassez
généralement
exprimer common practice
faible, to
on a l’habitude de prése
times called fraction modern. However, 14 report the 14C data as relative numbers,14i.e. as de-
picoMole. C’est pourquoi, pcm, pCM, pM, et les variants C sous similaires
forme de nombres ne devraient relatifs,pasi.e. être de valeurs δ corrigées pour la décroi
the symbol pM is in use by water chemists cay corrected 14δ values:
utilisées: l’expression % est appropriée
and oceanographers as picoMole. si elle est associée à un symbole bien
Therefore, 14 défini.
A
pmc, pMC,pCM
Néanmoins, l’utilisation pM, est anddevenue
similar variants should
si habituelle, δ = ad’éviter
14 S
qu’il est difficile
14 S
− 1 = 14cette −1
0 unité. (11.44)
not be used: % is adequate in combination ARN
Toutefois il paraît plus raisonnable d’utiliser le symbole %CM au lieu de pCM.
with a  well-defined symbol. Nevertheless,
En général,Inles general
résultatsresults sontareégalement
also corrected for isotope
corrigés pour le fractionnemen
the use of pMC has become so established, fractionation (= normalised):
Exemple: l’eau that this ‘unit’ is difficult to avoid. However,
souterraine normalisés):
it seems more reasonable to use the symbol .
L’activité mesurée
%MC et instead
normalisée ou rapport de concentration est :
of pMC. 2
14 S 14 S 14 −( t s − t0 ) / 8267 ⎛ 0,975 ⎞
14 δN = a N − 1 = a e ⎜⎜ 13 ⎟
⎟ −1
aN = 0,537 = 53.7 % (11.45) ⎝ 1 + δ ⎠
Example:
13 groundwater
La valeur δ mesurée sur le carbone total (comme celleThese obtenueequationspar laareprocédure
used to express the 14C con-
14
d’extraction)The measured
est: and normalised activity or concen- Ces équations tentsont utilise pour
of samples exprimer as
of oceanwater la well
teneur en atmo-
as of C d’échantillons iss
tration ratio is: spheric CO .
l’eau océanique que du2CO2 atmosphérique.
13
14 δ = –13,82 ‰
aN = 0.537 = 53.7 %
11.5.4.2.1. Example: oceanic DIC and atmos-
The measured 13δ value of the total carbon 11.5.4.2.1
con- Exemple: CID pheric océanique
CO2 et CO2 atmosphérique
tent (as is obtained by the extraction procedure) 14
La concentrationThe 14Cencontent C issue resulting
d’une from a routine
mesure measure-implique une no
de routine
206 is:
13
δ = –25‰: ment includes normalisation to 13
δ = –25‰:
13
δ = –13.82 ‰ (1) deep-ocean bottom water DIC ( = dissolved
a) le CID (= Carbone inorganic Inorganique
carbon): Dissous) d’une eau profonde du fond de l
In groundwater hydrology we are interested in 14
the 14C content of the water sample at the time of aN =14a14Na =  0
N 14=aN 0,872
0 = 87,2%
 = 0.872 = 87.2% [cf. 11.40]
d’où: 14δN = 14aN – 1 = –0,128 = –128‰
122 avec 13δ = +1,55 ‰
 14
Pour cette correction on doit de nouveau utiliser la période C “correcte”
= 1/8267a . Par ailleurs, A et a se rapportent à 1950 et A et 14ai à l’an
−1 14 0 14 0 14 i

carbone contenu dans l’échantillon.

measuring techniques
Pour les valeurs normalisées et corrigées pour l’âge nous pouvons maintenant

from which: 14δN = 14aN – 1 = –0,128 = –128‰

Chapitre 11 14
AiTechniques de Mesure
[cf. 11.42]
Chapitre 11
14
δ i = 14 a i − 1 = 14 0
−1=
ARN
Chapitre 11
with 13δ = +1.55‰
Quand on corrige du fait que la teneur 14
C obtenue
208 est 14 valide0 − ( ti −pour l’année 1950 au
1950 ) / 8267
Quand on corrige du fait que la teneur 14
C obtenue est Avalidee pour l’année
When corrected
lieu de l’année d’échantillonnage (1990): for the fact Chapitre that 11 the result- = 14 0
− 1 =195014
a eau − ( ti −1950 ) / 8267
−1
Quand 14 A
ingonde
lieu 14corrige du fait que la teneur
Cl’année
contentd’échantillonnage
is valid for the year C1950
(1990): obtenuein- est valide pourRNl’année 1950 au
lieu de stead
l’année of the year
d’échantillonnage of sampling (1990):
(1990): 14 (11.48)
Quand 14
δon S corrige
= 14 a N exp[ du fait −(1990 que −la1950 teneur ) / 8267 C obtenue
] − 1 = − 0est ,132 valide = −132‰ pour l’année 1950 au
14 S
δ
N
= 14
a exp[ − (1990 − 1950 ) / où ti ]est
8267 − 1la= date
− 0 ,132 BC=(négative) − 132‰ ou AD (positive)) et pour les valeurs normalisées:
lieu de l’annéeN Nd’échantillonnage (1990): (where ti is the date BC (negative) or AD (posi-
δ N == –0.132
14 S 14
a N exp[ =− (1990 − 1950) / 8267] − 1 = − 0,132 = −132‰
–132%
b) CO2 atmosphérique: tive)) and for the normalised values: 2
b) CO2(2) 14 S
δ N atmospheric
= 14 a N exp[−CO
atmosphérique: (1990 − 1950 ) / 8267 ] − 1 = − 0 ,13214 = i −132‰ ⎛ 0,975 ⎞
14 14 2: δ N = 14 a Ni − 1 = 14 a e −(ti −1950) / 8267 ⎜⎜ 13 . ⎟⎟ − 1
b) CO2 atmosphérique: d’où: δN = aN – 1 = 0,253 = +253‰ [cf. 11.42] ⎝ 1+ δ ⎠
from 14
d’où: δN = 1414aδN = 
which: – 114a=N0,253 – 1 = 0.253 = +253‰ = +253‰ [cf. 11.42]
13
b) CO2 atmosphérique:
d’où:avec 14δN13=δ14=a–7,96 N – 1 =‰ 0,253 = +253‰[cf. 11.42] [cf. 11.42]
(11.49)
avec δ = –7,96 ‰
d’où: with
14
Quand
13
avec δ = –7,96 δ N = δ = –7.96‰
13 14
onacorrige
N‰ – 1 = 0,253 du fait=que +253‰ teneur
Exemple:
14
C obtenue
concentration est valide enpour 14 [cf.
l’année11.42]
C atmosphérique 1950 auà partir d’un échantillon d’âg
Quand on corrige du fait que teneur 14
C obtenue Example:
est valide atmospheric
pour l’année 1950
14
Cau content from
lieu
13 de l’année C
the resulting 14 d’échantillonnage
content is validbois for(1985):
the year
caractérisé par les cernes
aveclieu
Quand δonde= corrige
–7,96
l’année ‰du fait que teneur 14(1985):
d’échantillonnage C obtenue est valide pour a known-age l’année 1950 au sample : wood from
1950 instead of the year of sampling (1985):
lieu de Le a treering
14 rapport d’activité mesuré i.e. l’activité par rapport à 0,95 fois l’activité
Quand 14 l’année d’échantillonnage (1985):
δonS corrige
= 14 a N exp[ du −fait (1985 que− 1950 teneur ) / 8267 C obtenue
] − 1 = 0,est 247valide = + 247‰ pour l’année 1950 au
[cf. 11.45]
14 SN 14 normalisée de l’acide
The measured oxalique: activity ratio i.e. the activity with
lieu de δ =
l’année a exp[ − (1985
d’échantillonnage (1985): − 1950 ) / 8267 ] − 1 = 0 , 247 = + 247‰ [cf. 11.45]
14 S =0.247 = N+247% [cf. 11.45]
N
14
δN = a N exp[−(1985 − 1950) / 8267] − 1 = 0,247 = + 247‰ respect to 0.95 times the measured
[cf. 11.45] 13 and nor-
Pour lesWith échantillons de CO atmosphérique
CO2 samples it remains prob- a =malised il reste le problème
14 14 0de savoir
a = (oxalic 14
A / acid14si la correction C
ARN)activity:
14 S atmospheric = 0,4235 13or = 42,35%
2
Pour leslematicδ = 14whether
échantillons a N exp[ de−CO (1985 2 13 atmosphérique
C− 1950 ) / 8267applied il] −reste
1 = 0le ,247problème
= + 13 247‰ de savoir si la [cf.correction
11.45] C
appliquée N(suivant l’Eq.the  11.40) correction
est correcte. La valeur (ac- de δ mesurée peut très bien 13 être
Pourappliquée
les échantillons de CO atmosphérique il reste le problème de
13 savoir
aδ=combustibles si la correction C
par(suivant l’Eq.avec 11.40) est
CO2correcte. laLa valeurδ de mesurée
a = ( Apeut / Atrès RN) =bien au être
0.4235 lieuor = 42.35%
2
affectéecording un to Eq. 11.40) isducorrect. The measured 13 14 14 0 14 14
mélange issu deLe biosphère
13
δ mesuré 13oudedes l’échantillon: fossiles,
appliquée
Pouraffectée
lesseul(suivant
value may
par un mélange
échantillons l’Eq. very 11.40) well
de CO2isotopique, avec est
be
atmosphérique correcte.
affected
du COcomme by
2 issuilde
La valeur
the admixture
reste de δ mesurée peut très bien être
13 [cf. 11.38]
du fractionnement lelasuppose
biosphère
le problème — ou
de des de
manière combustibles
savoir si laforcément
pas fossiles,
correction au
valideC lieu —
affectée of biospheric
par(suivant
un mélange or fossil-fuel
avec du CO CO
issu 2, instead
de laLa biosphère of by iso- 13
13δ =
du
appliquée seul fractionnement
la procédure del’Eq. 11.40)
correction isotopique,
(Mook, est 2correcte. comme
1980b). valeur ou
le suppose de—des δ combustibles
de –22,5‰pas
manière
mesurée
The measured
fossiles,
peutforcément au lieu
13très bienvalide
δ of the sample:être —
du seul tope
fractionnement fractionation isotopique, alone, as
comme is the —le not
suppose necessar-
— de manière pas forcément valide —
la procédure
affectée parily
un valid de correction
mélange avec du
— presumption (Mook, CO2of 1980b).
issu de la biosphère
the correction Le rapport oud’activité
proce- des combustibles normaliséfossiles, au lieu
de l’échantillon est:
la
13
δ = –22.5‰
duprocédure
11.5.4.3
seul de correction
G
fractionnement
dure [114].
EOCHIMIE (Mook, 1980b).
isotopique, comme le suppose — de manière pas forcément valide —
11.5.4.3 GEOCHIMIE 14
aNde The normalised
= 14 a [0,975 la / (1– activity
0,0225)]ratio 2 of the sample is:
= 0,4213 or = 42,13%
la procédure
Dans les deétudes
correction (Mook, 1980b).
géochimiques, il est souvent nécessaire connaître concentration 14
C
11.5.4.3 G EOCHIMIE
11.5.4.3. Geochemistry 14
Dans
initialelesd’unétudes géochimiques,
échantillon correspondant il est souvent à l’annéenécessaire d’échantillonnage de 14 connaître
aN = 14t14ia(telle la que
[0.975 concentration
/ (1– 0.0225)]
l’année 2C
 = 0.4213
11.5.4.3 G 14ou une
Dans les
initialeétudes
In
d’un géochimiques,
EOCHIMIE
geochemical
échantillon studies il
correspondant est souvent
it is à often nécessaire
l’année En utilisant
necessary de
d’échantillonnage connaître
la valeur
or = 42.13% t laa concentration
corrigée
(telle que pour
l’année ouC
l’âge une et normalisée,
[cf. 11.40]calculée ci-dessu
cerne d’arbre s’est formée), 14au lieu de l’activité en 1950, obtenue en routine. Comme la i
initiale
Danscerne d’un toéchantillon
d’arbreknow s’est the original
correspondant C content
àsouventde of
l’année a sample
d’échantillonnage
conventionnel in ti (tellelaque
est:obtenue l’année ou une
14
les études
concentration
the year
géochimiques, Cformée),
enof14the sample (activité ilau oulieu
est
origin concentration)
t (such
l’activité
nécessaire
as
en valide
est
the year
1950,
de connaître
pour the normalised,
Using
en
l’année1950, routine.
concentration elleComme
agedoit C être
corrected
la 14
a value cal-
cerne
initiale d’arbre
concentration
d’un s’est
échantillon en formée),
14
C correspondantau
(activité lieu ou de l’activité
concentration)
à i
l’année en 1950,
est
d’échantillonnage valide obtenue pour t en routine.
l’année1950,
(telle que l’annéeComme
elle
ou doit
unela être
corrigéea treering
pour14la décroissance
was formed),radioactive instead ofentre the activityl’année in d’origine culated i (ti)ln above,
et 141950: the conventional C age is: 14

concentration en Cdécroissance
(activitéauoulieu concentration) est Tpour
= – 8033 aN =elle 6943doit BP
cernecorrigée
d’arbre pour
1950,s’estlaas formée),
is routinely radioactive
obtained. Asentre
de l’activité envalide
l’année
the measured 1950, d’origine
obtenue l’année1950,
(ti)enet routine.
1950: Commeêtre la
corrigée pour
concentrationCen14 la décroissance
14 i
content (activity radioactive
i or concentration) is
entre l’année estvalid d’origine T = –
(t ) et 8033
1950:
for pour l’année1950, elle doit (11.46) ln 14
a  = 6943 BP [cf. 11.50]
14
AC =(activité
14
A e ou
0 − ( t − 1950 ) / 8267
L’activité
valide
relative
i
normalisée est:
N être
corrigée pour the year14 i
A 1950,
la décroissance = A itehas
14 0 − ( ti −1950 ) / 8267
radioactiveto be corrected entre l’année for radioac- d’origine (t The normalised
i) et 1950:
(11.46) is:
relative activity
tive
14 i decay
A = A e 14 0from − ( ti −the year
1950 ) / 8267 of origin (t ) to 1950:
i (11.46)
et de la même façon pour les valeurs normalisées: 14
δN 14=δ14 aN14–a1 –= 1 = – – 0,5787 or –578,7‰
et de la même  =  0.5787 or –578.7‰
14 i
A = façon A epour les valeurs
14 0 − ( ti −1950 ) / 8267
(11.46) normalisées: N N
(11.46)
et de la même façon [cf. 11.42]
14 ipour 14les 0 valeurs
− ( ti −1950normalisées:
) / 8267
and equally A = A e En supposant que les cernes sont datés, par dendrochronologie à 5735 calBC ("ca (11.47)
= for
14 0the normalised
14 iN N − ( t −1950 ) / 8267 values:
ANpour A Suppose the treering 14is(11.47) dated dendrochrono-
et de la même façon les N e valeurs normalisées:= corrigé selon la
i

14 i 14 0 − ( ti −1950 ) / 8267 courbe

logically to 5735 calBCde calibration C, représentée
(stands sur la Fig. 8.5), i.e. ti = –
for ‘calibrated’
AN = AN e (11.47) (11.47)
Pour cette correction on
doit de nouveau utiliser la période 14
C “correcte”
BC = corrected (5730a)
according avec λ C calibration
latoconcentration
the  14 14
14 i
= 14 AN0 e −on
Pour cetteA−1Ncorrection
( ti −1950 ) / 8267
doit la concentration corrigée
14 pour l’âge, i.e. avec
(11.47) λ 5735 a . C originelle de l’éc
14 0 de 14nouveau 0 utiliser la périodecurve, 14 C i “correcte”
shown
14 i in (5730a)
Fig. 8.5), i.e. t  = –
= 1/8267a For−1this. Parcorrection
ailleurs, again A et the ‘correct’a se rapportent half-life
alors: à 1950of 14et 14 Ai et 14 ai à l’année d’originei du
Pour=cette correction
1/8267a . Par on doit 14de
ailleurs, A 0nouveau
et 14 0 utiliser
a se rapportent la période
à 1950 C “correcte”
A et a à (5730a) avec λ du
carbone
14
C (5730a) has
−1 contenu dans14l’échantillon.
to
0
be 14 0
used with λ = 1/8267a −1
.14 eti The age-corrected,
14 i i
l’année d’origine
i.e. the original 14C content of
=Pour
1/8267a .Furthermore,
Par
cette correction
carbone contenu ailleurs, on doit
dans 14 A
A et and
de nouveau
l’échantillon.
0 a aserefer
14 0 rapportent to 1950
utiliser àla1950
and
périodeetA δANCet=“correcte”
14 i14 14 i 14 aaNà –l’année 14
1is=(5730a) ad’origine avec du
N exp[–(–5735 λ –1950) / 8267] – 1
the sample then:
Pour lesandvaleurs
14 i normalisées
a tol’échantillon.
the year et corrigées pour l’âge nous pouvons maintenant écrire:
carbone
= 1/8267a contenu
−1
. Par
Pour lescontaining
valeurs
dans
ailleurs, 14
normalisées A et of
0 14 the origin
0
etacorrigées
se rapportent of the carbon
pour l’âge à 1950 14
et pouvons
nous
i
A= et 14
0,0674(5)
i
amaintenant
à l’année or = d’origine
+67,4(5)‰
écrire: du
sample material. δ
14 i
 =  14
a i
– 1 =  14
a exp[–(–5735 –1950)
carbone
Pour les contenu dans l’échantillon.
valeurs normalisées et corrigées 14 i pour l’âge nous pouvons maintenant écrire: N N N
For the normalised A / 8267] – 1 = 0.0674(5) or = +67.4(5) ‰
14
δ = a − 1 =and
i 14 i
14
14 A0
age i −corrected
1= values we
Pour les valeurscan now normalisées
14
δ write:
i et corrigées
= a − 114= i14 A0RN − 1 =
14 i pour l’âge nous pouvons maintenant écrire: [cf. 11.49]
A ARN
208 δ = a − 1 = 14 0 − 1 =
14 i 14 i

14A i
208 ARN
14 i
δ = 14 a i − 1 = 14 0 − 1 = 123
208 ARN
208
 INTRODUCTION
11.5.4.4. Enhanced 14C radioactivity
In studies on the extent of radioactive contami-
nation, for instance by 14C, the absolute radio-
activity of the sample is required. In such cases,
the result of the routine 14C measurement, in casu
the  14a value, has to be converted back to the ab-
solute value by:
14A = 14a × 13.56 (dpm/gC) = 14a × 0.226 (Bq/gC)
(11.50)
The measured activity as such is valid for the year
1950 (Eq. 11.38), so it has to be corrected for ra-
dioactive decay from 1950 (t0) to the year of sam-
pling (ts). Moreover, the activity in this case is not
to be normalised. If the laboratory provides only
normalised values, 14aN, these have to be ‘de-nor-
malised’ (i.e. normalisation removed) by apply-
ing Eqs.11.34, 11.38, 11.40 and 11.50:
. to −19‰, Ox2 to −25‰) (see Chapter 10);
. (3) the original (Libby) half-life of 5568 has to
. The ages are then calculated by applying:
.
. Conventional age = –8033 ln14aN (11.52)
(11.51) .
where t0 and a both refer to the year 1950, and
14 0
ts and AS to the year of sampling; λ is based on
the true 14C half-life of 5730 year; 14aN is the rou-
tinely acquired (i.e. normalised) 14C content of
the sample.
Example: fall-out contamination
The AMS measured 14C concentration ratio is:
14
aN = 2.200 or = 220.0%
The  13δ analysis obtained in the AMS system re-
sulted in:
13
δ = –32.0‰
The routinely obtained 14aN value now has to be
de-normalised according to:
a = 14aN [(0.968/ 0.975]2 = 2.168(5)
14
or = 216.8(5) % [cf. 11.40]
The absolute activity in the year 1950 would have
been:
14
A0 = 14a0 × 0.226 = 14a × 0.2260 = 0.4901 Bq/gC 14
[cf. 11.50]
124
This value has to be corrected for radioactive de-
cay, as the measured value is valid for 1950 in-
stead of the year of sampling ts = 1986:
14
AS = 14A0 exp[–(1986 –1950) / 8267]
= 0.4880 Bq/gC [cf. 11.51]
11.5.4.5. 14
C ages
In geological and archaeological dating, the ages
used are the conventional 14C ages. is repeated.
By international convention, the  definition of
the conventional 14C age is based on (Sect. 8.1.4):
(1) the  initial 14C activity (i.e. the activity of
the sample material during ‘growth’ equals
the standard activity in AD1950;
(2) the  14C activities have to be normalised for
fractionation (samples to 13δ = −25‰, Ox1
be used.
This defines the 14C time scale in years BP (Before
Present, i.e. AD1950).
This time scale needs to be calibrated in order to
obtain historical (calibrated) ages (calAD, cal-
BC, calBP). For the calibration procedures and
conventions we refer to the special Calibration
Issues, published by Radiocarbon (the most re-
cent edited by [81]).
11.5.5. Summary
The interrelation between the various definitions
and symbols, especially concerning the validity
over the time scale from past to present, is illus-
trated by Fig. 11.9. For comparison, the symbols
used by [76] are given within brackets.
In Table 11.5 all symbols used for reporting 14C
data are classified.
Table 11.6 contains the relative and absolute 14C
contents of the available 14C reference samples.
The ‘rational’ symbols introduced by [77] are
based on:
A = absolute radioactivity (in Bq/gC or in
dpm/gC)
 measuring techniques

14
Ai 14
A0 14
AS
14 i 14 0
a a = 14a
14 i 14 0
δ ( ≡ δ14C) δ = 14δ ( ≡ d14C) 14 S
δ

past AD 1950 present future

14
A iN 14
A 0N and 14 A 0RN 14
A SN
14
14
a iN a 0N = 14
aN 14
a SN
14
14
δ iN ( ≡ Δ) δ 0N = 14
δ N ( ≡ D14C) 14
δ SN ( ≡ Δ14C)

Fig. 11.9.  Illustration of the definition of symbols for reporting 14C data along the time scale from the past (for
the  data to be corrected for age/decay), via the  year 1950 to the  time of sample collection (s) and the  future.
Above the line are the non-normalised data (not corrected for isotope fractionation), below the normalised val-
ues. The bold symbols are defined in this paper, the symbols within brackets were defined by [76].

TABLE 10.5.  Review of the symbols used in reporting 14C activities.

measured decay decay age age
at t0 (1950); corrected corrected corrected corrected
normalised
a and δ at till sampling + from origin +
any time at ts normalised at ti normalised
Absolute 14
A0 14
AN 14
AS A SN
14 14
Ai A Ni
14
14
C content
of sample AS ASN
Absolute 14
ARN
14
C content
of standard AON AABS
14
C 14
a =  a 14 0 14
aN 14 S
a  14 S
a  14 i
a 14 i
a 
N N
abundance
ratio AS/AON ASN/AON AS/AABS ASN/AABS

Relative
14
δ =  14δ0 14
δN 14 S
δ 14 S
N a  14 i
δ 14 i
N a 
14
C content d C 14
D C 14
δ C
14 a 
δ C14 b
δ C
14 c
δd

Note: The upper symbol is defined in this paper. The symbols in the shaded areas refer to [76]. In the 3rd column the symbols
apply to the decay-corrected values, i.e. corrected for decay of the sample activity from 1950 to the year of sampling
(Eqs.11.43 – 44). The symbols in the 6th column refer to Eqs. 11.47 – 49. The superscript 0 assigns the value to the year
1950.

Symbols stand for: Super- and subscripts stand for:

A = absolute activity or concentration N = normalised
a = activity/concentration ratio to standard 0 = time zero ≡ AD1950
δ = relative 14C content (i.e. deviation of i = initial ≡ time of growth/formation
activity or concentration from standard s = time of sampling

The symbols proposed by [76] are shown in the shaded areas. They refer to the following fields of study:
1
in hydrology the use of the 14a value (or rather 14aS) is more common
2
in oceanography and atmospheric studies
3
in geochemical studies if age correction is possible
4
idem, such as past 14C variations from treerings.

125
 INTRODUCTION

14
a = activity or concentration ratio between sam- The symbols are prefixing the superscript “14” like
ple and standard (in %) in the isotopic symbol 14C. The superscripts “i”,
“0”, and “S” indicate the time to which A , a , or
14
δ = relative difference in activity or concentra- δ are related. The subscript “N” indicates whether
tion (in ‰) the activities and concentrations are normalised.

TABLE 10.6.  14C content and 13δ values of a number of standards and
secondary reference samples, available for distribution.

Type of material 14
aN (%) δ (‰)
13 14
A 0N  (Bq/gC) distributed by

Marine carbonate
C–1 0.00 ± 0.02 +2.42 < 0.0001 IAEA
milled Carrara Marble
Freshwater carbonate
C–2 41.14 ± 0.03 −8.25 0.0930 IAEA
travertine deposit
Cellulose
C–3 129.41 ± 0.06 −24.91 0.2925 IAEA / CIO
from 40-yr trees felled 1989
Subfossil wood
C–4 0.32 ± 0.06 −23.96 0.00072 IAEA / ANU
from peat bogs N.Zealand
Subfossil wood
C–5 23.05 ± 0.02 −25.49 0.05209 IAEA
buried bed forest USA
Sucrose
C–6 150.61 ± 0.11 −10.40 0.3404 IAEA / ANU
originally second. standard
Oxalic acid
Ox1 100.00 a  −19.20 0.2260 NIST / IAEA
primary 14C standard nr.1
Oxalic acid
Ox2 127.36 ± 0.04 −17.60 0.2878 NIST/ IAEA
primary 14C standard nr.2

a 
by definition
Note: The types of material and the ages represent the range of interest of the radiocarbon laboratories. The values are nor-
malised for their 13δ value (to –25‰). As the 14C values presented by 14a (Eq. 11.36), the time of measurement is irrel-
evant. Absolute activities are calculated according to Sect. 11.5.4.4, and refer to the year 1950. Full details are reported
by [115]

NIST = National Institute of Standards and Technology, Atmospheric Chemistry Group, B364, Building 222,
Gaithersburg, MD 20899, United States of America

IAEA = International Atomic Energy Agency, Analytical Quality Control Services, Agency’s Laboratory, Seibersdorf,
P.O. Box 100, A –1400 Vienna, Austria, fax +43 – 1–2060 – 28222

CIO = Centre for Isotope Research, Nijenborgh 4, 9747 AG Groningen, the Netherlands, tel. +31 – 50–3634760, fax
+31 – 50–3634738

126
12. natural isotopes of elements other than h, c, o

In this chapter we are dealing with the less com-
mon applications of natural isotopes. Our discus-
sions will be restricted to their origin and isotopic
abundances and the main characteristics. Only
brief indications are given about possible applica-
tions. More details are presented in the other vol-
umes of this series. A few isotopes are mentioned
only briefly, as they are of little relevance to wa-
ter studies.
Based on their half-life, the isotopes concerned
can be subdivided:
(1) stable isotopes of some elements (He, Li, B,
N, S, Cl), of which the abundance variations
point to certain geochemical and hydrogeo-
logical processes, and which can be applied
as tracers in the hydrological systems;
(2) radioactive isotopes with half-lives exceed-
ing the age of the universe (232Th, 235U, 238U);
(3) radioactive isotopes with shorter half-lives,
mainly daughter nuclides of the previous
catagory of isotopes;
(4) radioactive isotopes with shorter half-lives
that are of cosmogenic origin, i.e. that are
being produced in the atmosphere by inter-
actions of cosmic radiation particles with
atmospheric molecules (7Be, 10Be, 26Al, 32Si,
36
Cl, 36Ar, 39Ar, 81Kr, 85Kr, 129I) [116].
The isotopes can also be distinguished by their
chemical characteristics:
(1) the isotopes of noble gases (He, Ar, Kr) play
an important role, because of their solubil-
ity in water and because of their chemi-
cally inert and thus conservative character.
Table 12.1 gives the solubility values in
water [117];. The table also contains the at-
mospheric concentrations ([118]: error in his
Eq. 4, where Ti/(T−1) should read (Ti/T−1);
(2) another category consists of the isotopes of
elements that are only slightly soluble and
have very low concentrations in water under
moderate conditions (Be, Al). These are pri-
marily used for sediment studies and for dat-
ing ice sheets;
(3) two elements (N, S) have isotopic abundanc-
es revealing information on bio(geo)chemi-
cal processes in soils and associated waters;
(4) three nuclides are cosmogenically produced
isotopes from elements that occur as solutes
in aqueous systems (Si, Cl, I) and are used
for water dating;
(5) the decay series of uranium and thorium
contain several isotopes of which the rela-
tions between the parent/daughter activities
are useful pre-eminently.

TABLE 11.1.  Solubilities of noble gases in water at various

temperatures, the atmospheric concentrations and
the concentration of the noble gases dissolved in water in
equilibrium with the atmosphere at 10°C [117, 118].
Solubility in mL (STP)/L H2O Atmosph. Diss. conc.
0°C 10°C 20°C 30°C concentr. mL/L (10°C)

Helium 9.53 9.07 8.82 8.74 5.24 × 10−6 4.75 × 10−5

Neon 12.6 11.4 10.5 10.0 1.82 × 10−5 2.07 × 10−4
Argon 53.5 41.7 34.1 29.0 9.34 × 10−3 3.89 × 10−1
Krypton 111.2 81.2 62.8 50.9 1.14 × 10−6 9.26 × 10−5
Xenon 226 154 112.5 86.7 8.60 × 10−8 1.32 × 10−5
Radon 510

127
 INTRODUCTION

In the tables at the introduction of each section 12.1.2. Experimental and technical

some relevant physical information is given about
abundance and decay to finally a stable daughter
nuclide.
This chapter mainly serves to review the physical
and chemical characteristics of the isotopes. Only
a brief indication is being given of the possibili-
ties of application for studying the water cycle.
A thorough discussion is to be found in the other
volumes of this series.
12.1. Helium
Table 12.2. Natural isotopes of
helium.
3
He
2 2
aspects
In groundwater concentrations of helium are ob-
served in the range of 10 – 5 to 10 – 2 mL(STP) of
He/mL of water. With 3He/4He ratios of 10 – 8 to
10 – 7 this means that the 3He concentrations can
be as low as 10 – 13 mL/mL of water. To measure
these amounts of gas, specialised mass spec-
trometers are needed. This is even more true for
the measurement of extremely low 3H contents
(down to 10 – 2 TU) through 3He accumulation
(Sect. 12.1.5.2).
In general, water samples are collected of 5 to
500 mL — depending on the laboratory’s equip-
ment- and thoroughly sealed before being shipped
4
He
to the laboratory.
   

Stability Stable Stable

12.1.3. Sources of 3He
Natural abundance fraction 1,3 × 10 −6
100%
The main complication is that the principle of
Natural abundance in air a 6,8 × 10−12 5,2 × 10−6
3
H/3He dating is based on the assumption that
all 3He in the water sample is tritiogenic (com-
Natural abundance in ing from decay of 3H). However, part of the 3He
10−10 à 10−13 10−3 à 10−5
groundwater b may be of terrigenic origin (from in situ produc-
a
mL gaz /mL of air tion according to Eq. 12.2), part from the original
b
mL gaz /mL of water equilibration of the water with the atmospheric
gases. The latter contribution can be estimated
12.1.1. Origin and characteristics from the Ne concentration, which can not be of
terrigenic origin. A possible terrigenic contribu-
The radioactive isotope of hydrogen, formed tion is to be estimated from the concentration of
in the atmosphere by a nuclear reaction of ni- 4
He (also corrected for the atmospheric compo-
trogen atoms with neutrons in cosmic radiation nent [29]. These processes are summarised by:
(Sect. 8.3), decays through β decay to 3He:
3
Hetot = 3Heatm + 3Heterr + 3Hetrit (12.3a)
3
H → He + β
3 −
(12.1)
The  maximum β energy of 3H is 18 keV and
4
Hetot = 4Heatm + 4Heterr (12.3b)
the half-life is 12.43 a (Fig. 8.2). The daughter
product 3He is stable and chemically inert. 3He is Netot = Neatm (12.3c)
also formed in the earth’s crust (primarily in crys- where the atmospheric concentration ratio
tal rock) by the reaction: Heatm/Neatm = 0.288.
6
Li + n → 3He + 4He or Li (n, α) 3He
6
(12.2)
12.1.4. Natural abundance
The underground neutrons originate from spon-
The 3He/4He ratio in atmospheric helium is about
taneous fission of uranium or thorium isotopes
1.3 × 10 – 6, with a helium concentration of about 5
or by (α ,n) reactions in which the α particles are
ppmv (partial pressure of 5 × 10 – 6 atm.). The rel-
from decays within the uranium and thorium de-
ative constancy of this concentration is due to
cay series.
the state of equilibrium between the loss of he-
4
He originates primarily from the natural decay of lium from the crust to the atmosphere and the loss
235
U, 238U and 232Th in the earth (Sect. 12.13). from the atmosphere to outer space.

128
 natural isotopes of elements other than h, c, o
Groundwater concentrations are observed of 10 – 3
to 10 – 5 mL(STP)/mL of water, far exceeding
the equilibrium value due to relatively high un-
derground helium production. The 3He/4He ratio
in groundwater is still within a narrow range of
5 × 10 – 8 to 10 – 7.
Apart from the  infiltration of tritium contain-
ing water, 3H can be produced underground in
the aquifer, i.e. through in situ production:
14
N + n → 12C + 3H (12.4)
The presence of neutrons is due to spontaneous
fission of U and Th. Because of its short half-
life, 3H levels will be low, generally below 1 TU.
The accumulated 3He levels will then depend on
the degree of isolation of the water, and are thus
a measure of that effect.
12.1.5. Applications
12.1.5.1. Principle of 3H/3He dating
The application of 3H to obtain underground resi-
dence times (‘ages’) of groundwater was shown
to depend on our knowledge of the 3H input from
atmospheric precipitation (Sect. 8.4.2). Studying
the relation between 3H and 3He offers the possi-
bility to determine ages without knowing the tri-
tium input function. If the original 3H content of
the infiltrating precipitation is 3H0, the content af-
ter a residence time t, 3Ht, is presented by:
Ht = 3H0 e−λt
3
The amount of He formed during this time is
3
equal to the amount of 3H lost by decay:
3
Het = 3H0 − 3Ht = 3Ht(eλt − 1) (12.5)
The 3H/3He age is then:
t = (12.43/ln2) × ln[3He/3H + 1] (12.6)
Most applications are related to shallow, young
groundwater, using the bomb peak of 3H in
the precipitation during the early 1960s. The oc-
currence of 3H and 3He at great depth may be due
to fractures, cracks or leaking boreholes, or to in
situ production.
12.1.5.2. Mass spectrometric measurement of
3
H through 3He
Very low 3H abundances (theoretically down to
0.0005 TU) can be measured by thoroughly de-
gassing and storing 50 to 100 mL of water sample
for at least half a year in a tightly sealed container
and subsequently recollecting the decay product
of tritium, 3He. The amount of this inert gas can
be quantitatively measured mass spectrometrical-
ly. The 3He produced during this storage time (t)
is (Eq. 12.5):
3
Het = 3H0 − 3Ht = 3H0(1 − e−λt)
so that the original 3H content of the sample was:
3
H0 = 3He/(1 − e−λt) (12.7)
To give an impression: the amount of 3He formed
during half a year storage of 100 mL of water
with a 3H concentration of 0.5 TU is:
3
Het = 0.5 × 10−18 × 2 × (100/18)
× (1 − e−(ln2)/12.43) × 0,5) × 22.41×103 = 3.4 × 10−15 mL
12.2. Lithium
TABLE 12.3. Natural isotopes of
lithium
  Li
6
3   Li
7
3
Stability Stable Stable
Natural abundance fraction 7.5% 92.5%
12.2.1. Natural abundance
In seawater the Li+ concentration is about
0.18 mg/L. The isotopic composition varies by
about 10‰.
12.2.2. Experimental and technical
aspects
Natural variations in the 6Li/7Li ratio may be
related to a reference sample, available from
the IAEA and NIST, referred to as L-SVEC. With
respect to L-SVEC, the Li isotopic composition
of Li in seawater (δ6Li = (6Li/7Li) - 1) is −32‰.
129
 INTRODUCTION

12.2.3. Applications ratio of (2.68 ± 0.14) ± 10 – 11. Be targets are pre-

The  6Li/7Li ratio has been used to study brines pared by mixing BeO and Ag.
and their origin as evaporated (palaeo)seawater.
Li isotopes are also being applied to crystalline 12.3.3. Natural abundance
rocks.
The atmospheric production rate (flux) of 10Be is
about 300 atoms m−2s−1. This production rate var-
12.3. Beryllium ies with latitude, altitude and geologic times. It
TABLE 12.4. Natural isotopes of is (together with 27Al) rapidly washed out from
beryllium the atmosphere by precipitation, and is subse-
  Be
7
  Be
9
  Be
1 0 quently incorporated in continental and marine
4 4 4
Stability sediments. 10Be concentrations are observed of (5
radioactive stable radioactive
Natural abun- to 20) × 108 atoms/g of sediment.
100%
dance fraction In Antarctic ice concentrations have been ob-
Abundance in
107 à 10 served of 107 atoms 10Be/kg of ice [119]. The con-
air/ice/marine ~5 mBq/m3 air
sediment
atoms/kg centration in, for instance, the surface water of
the ocean largely depends on the residence time
Half-life (T1/2) 53.3 d 1.5 ×106 a
of 10Be in the surface layers. Values have been
Decay constant observed of about 7.5 × 105 atoms/L of water
1.51 × 10−7 s−1 1.5×10−14 s−1
(λ) [120], with Be concentrations of 5 pM/kg (at
Decay mode / the surface) to 30 pM/kg of seawater (at depth)
EC / 7Li β- / 10B
Daughter (pM = picomol = 10 – 12mol).

12.3.1. Origin and characteristics

The origin is cosmogenic, i.e. 10Be (together with
short-lived 7Be) is continuously being produced
in the atmosphere by the action of the high-ener-
gy proton component in cosmic radiation, caus-
ing spallation of atmospheric oxygen and nitro-
gen atoms.
10
Be decays according to:
7
Be + e− → 7Li (12.8)
12.3.4. Applications
10
Be is being applied in particular for dating ma-
rine sediments by studying the radioactive decay
in the sediment core. The especially useful meth-
od of measuring both 10Be and 26Al is mentioned
in Sect. 12.6.4. With respect to the water cycle is
10
Be being used for dating ice.
12.4. Boron

Be → 10B + β− (Emax = 560 keV, no radiation γ)

10 12.4.1. Natural abundance
(12.9) In the marine environment the element boron is
primarily found as dissolved borate (BO 3  
3 ). An
−

12.3.2. Experimental and technical important geochemical characteristic is the easy

aspects incorporation of B in marine clays during
Although in principle the radioactive decay of Table 12.5. Natural isotopes of
10
Be can be measured, the  specific activity is so boron
low that this method is not applicable. Detection 10
B   B
1 1
has become possible by the introduction of 5    5

the ultrasensitive mass spectrometers (AMS). Stability stable stable

Therefore, 10Be is only being applied since Natural abundance fraction 18.8% 81.2%
the 1970s. As usual, 10Be concentrations are com-
pared with (related to) a reference material, SRM which the boron isotopes are being fractionated
4325, available from the NIST, with a 10Be/9Be [121].

130
 natural isotopes of elements other than h, c, o

12.4.2. Experimental and technical (1) nitrification, the oxidation from ammonia to

aspects nitrite and nitrate:
4  → NO 2  → NO 3
NH  (12.12)
− − −
Measurement of the abundance ratio 10B/11B
(≈ 0.23) is carried out by Inductively Coupled (2) denitrification, the reduction of nitrate to
Plasma Mass Spectrometry [121]. molecular nitrogen:
NO 
3  → NO 2  → ( NO ) → N2O → N2
− −

12.4.3. Applications (12.13)

Rare applications have been made in the marine (3) nitrogen fixation, the conversion of dis-
system, related to boron isotope fractionation solved molecular nitrogen to organic com-
during adsorption processes of seawater and clay. pounds:
The  10B/11B ratio of brines has been used in com- N2 (aq) → N-organic molecules (12.14)
bination with 6Li/7Li to study the relation with old
seawater. These processes are carried out by bacteria.
The resulting stable nitrogen isotope fraction-
ation may be considerable, but is hard to predict.
12.5. Nitrogen Generally, the isotopically light (14N containing)
molecules are reacted more easily [122].
Table 12.6. Natural isotopes of
nitrogen
14
N 15
N 12.5.3. Applications
  
7 7  

Stability stable stable Strictly hydrological applications are not obvi-

Natural abundance fraction 99.63% 0.37%
12.5.1. Experimental and technical
aspects
The measuring technique for nitrogen has been
discussed in Sect. 11.2.2. About 2 mg of N is
needed for a 15N/14N analysis (and if necessary
the combined 18O/16O analysis).
12.5.2. Natural abundance and
isotope fractionation
The isotope ratio 15N/14N in the largest nitrogen
reservoir, atmospheric N2, is extremely constant,
ous. 15N primarily serves to study bio(geo)chemi-
cal processes in the hydrological environment.
However, 15N in dissolved compounds can be ap-
plied to tracing water masses underground.
12.5.4. 18
O/16O in nitrate
Information on the origin of nitrate is also ob-
tained from the oxygen isotopic composition
of the nitrate ion. It has been shown (quote by
[123]; see also Volume IV) that one atom is re-
lated to atmospheric O2 (18δ ~ +20‰ relative to
Atmospheric N2
,, NO x

due to the relative inert character of nitrogen. Plant N

Soil organics
The atmospheric 15N/14N value is 0.0036765.
Sedimentary NO3
Nearly all fractionation processes involv- Natural gas N2

ing 15N in nature are kinetic. Only dissolu- Soil NH 4

tion of N2 in water (equilibrium fractionation Soil NO3

Soil N2
15
εN2(dissolved)/N2(gas) = + 0.85‰), and the diffusion Synthetic fertilizer
of N2 are non-biological processes. The major Manure
components in the nitrogen cycle are NH +4   and GroundwaterNO 3−
NO −3  . Fig. 12.1 shows ranges of the most com-
15
mon N-containing compounds. δ (‰) −20 −10 0 +10 +20

The relevant biochemical processes in the water Fig. 12.1.  Survey of 15δ values of nitrogen containing
phase during which isotope fractionation occurs compounds in nature. The 15δ values are given rela-
are: tive to the isotopic composition of air-N2.

131
 INTRODUCTION

VSMOW-water). The other two atoms are de- 12.6.3. Natural abundance

rived from the ambient water (18δ < 0‰ rel. to
VSMOW-water). In synthetic fertilizers the ox-
ygen is mainly coming from air-O2. Moreover,
18
δ appears to be nicely correlated with the de-
nitrification process. In conclusion, the oxygen
isotopic composition is certainly a valuable
tracer, although the interpretations are not yet
unique [124].
12.6. Aluminium
TABLE 12.7. Natural isotopes of
aluminium
26
 Al
13  
27
13
The atmospheric production rate of 26Al is about
1 atom ∙ m−2 ∙ s−1. The production rate, however,
varies with latitude, altitude and geologic times.
This secular variation is parallel to that of 14C and
10
Be.
12.6.4. Applications
The natural occurrence of 26Al is primarily be-
ing applied to dating ocean sediments. The ad-
vantage of a parallel use of 26Al and 10Be -ac-
tually the ratio of the two activities- is that
the method then is not dependent of the varia-
tions in production rate.
Al

Stability radioactive stable

From:

Natural abundance fraction 100%

26
Al = 26Al0 e−λ(Al)t and 10
Be = 10Be0 e−λ(Be)t

Natural abundance in ~107 atoms/g we calculate the ratio:

sediment
Half-life (T1/2)
Decay constant (λ)
Decay mode / Daughter
quartz
(26Al/10Be) = (26Al/10Be)0 e−λ’t (12.18)
7.16 × 105 a
where λ’ = λAl − λBe = 0,50 × 10−6 a−1. The ratio de-
3.07 × 10−14 s−1 creases in time corresponding to this decay constant.
The other application is the dating of polar ice.
β+, EC / 26Mg

12.7. Silicon
12.6.1. Origin and characteristics Table 12.8. Natural isotopes of
silicon
Like 10Be, 26Al is being formed in the atmosphere
by spallation of argon in the air induced by cos- 1  Si
28
  
  4  Si
29
    
14  Si
30
    
14  Si
31
    
14

mic ray protons:

Stability Stable Stable Stable Radioactive
Ar (p,sp) Al (12.15)
40 26

Natural abun-
92.2% 4.7% 3.1%
The radioactive decay to 26
Mg is through two dance fraction
branches: Natural abun-
dance in rain- 5 × 10−6 Bq/L
Al →
26 26
Mg + β (85%) +
(12.16) water
Half-life (T1/2) 140 a
Al + e− →
26 26
Mg (15%) (12.17)
Decay constant
1.57 × 10−10 s−1
shows the characteristic 511 keV line from anni- (λ)
hilation of the β+ particle. Decay mode / β− / 32P,
Daughter β− / 32S

12.6.2. Experimental and technical

aspects
26
Al is measured with AMS as Al2O3 containing
less than 2 mg of Al. This is mixed with silver
powder for use as the accelerator target.
12.7.1. Origin and characteristics
The origin of 32Si is cosmogenic, i.e. it is be-
ing produced by bombardment of 40Ar atoms in
the atmosphere by neutron from cosmic radiation:

132
 natural isotopes of elements other than h, c, o

Ar (n,sp) 32Si (12.19)

40
groundwater. However, at present the abundance of
32
Si in groundwater is still problematic and 32Si dat-
It decays through β- emission (Eβmax = 100 keV) ing is hardly applied. The reason is primarily the oc-
to the radioactive daughter 32P, which in turn de- currence of disturbing geochemicalChapitre processes
12 in
cays through β- emission to stable 32S with a half- the soil, involving adsorption and exchange of dis-
life of 14.3 d: solved silicate (including dans
32
Si) with the soil matrix.
processus géochimiques perturbateurs le sol, impliquant l’échange ou l’adsor
− 32 dissous (comprenant 32Si) avec la matrice du sol.
Si → β + P → β + S (12.20)
32 + 32

12.8. Sulphur
Because the activity of 32Si itself is hard to deter-
mine, because of the extremely low activity 12.8 Studying sulphur in the water cycle especially
in na- SOUFRE
ture and the complicated decay process. The con- concerns the behaviour of dissolved sulphate. It is
L’étude du soufre dans le cycle de l’eau concerne principalement le comportement du
sequence was that as recent as 1981 the half-life often useful to study the oxygen isotopic compo-
Il est souventsition
intéressant d’étudier la
of the sulphate compositioninisotopique
compounds, en oxygène des comp
combination
was still believed to be about 650 a . The AMS 34 32
combinaison
technique has allowed better (although still some- avec le
34 rapport
with S/ S. 32 S/ S.
what uncertain) measurements, resultingTableauin val-12.9.Table 12.9.
Isotopes naturels du soufre isotopes of
Natural
ues of 140 ± 20 a . sulphur
 S  S 16 S 16 S
32 33 34 36
    
16     
16          
32
12.7.2. Natural abundance S 33
Stable16 Stable16 SStable
34
Stability Stable 16 S
The cosmogenic Si activity is about 5 mB/m of
32 3

rainwater, again depending on latitude [125, Stabilité

126]. Natural abun- Stable Stable Stable
95.02% 0.75% 4.21% 0.02%
This value decreases more rapidly in the soil, not dance fraction
because of radioactive decay but as a result Répartition
of ad- de l’abondance naturelle 95,02% 0,75% 4,21%
sorption to soil minerals. During the period of nu-
clear weapons testing in the early 1960s the 32Si 12.8.1. Experimental and technical
activity was about 4 times as high, but the natural aspects
level has most probably returned. 12.8.1 ASPECTS EXPERIMENTAL ET TECHNIQUE
Variations in the relative abundance of the sul-
Les variationsphur isotopes,relative
d’abondance
32
S anddes34S, are reported
isotopes as 3234Sδ,etde-
du soufre, 34
S, s’expriment par
12.7.3. Experimental and technical fined as:
aspects ( 34 S/ 32S) sample
34
δ = −1 (12.21)
The original method of measuring a 32Si activity is ( 34 S/ 32S) reference
by chemically separating and purifying the silicon
content of the original sample and have the radio- As the internationally adopted primary reference
La troilite du Canyon Diablo (TCD) a été choisie comme première référenc
active daughter P accumulating in this silicon
32
for or standard has been chosen the Canyon Diablo
internationalement acceptée, il s’agit de la phase FeS d’une météorite métallifère p
some months. This example of a transient equilib- Troilite (CDT), the FeS phase from an34iron 32
me-
Cratère Météor, en
teorite Arizona
collected et around
dont le Meteor
rapport absolu
Crater, S/
Arizona S est de 0,045005. Ce
rium between a parent and daughter activity was
quelques
treated in Sect. 6.6.1. it was shown in Fig. 6.5 that problèmes
with an avecabsolute
ce matériau, 34 il
S/32Sa été décidé
ratio ofde0.045005.
choisir un nouveau matériau
34
the maximum daughter (in casu P) activity
32 partir duquel
is However,
le δ est sincedéfini a few problems
relativement showed
au CDT. Uneupprocédure
with analogue à ce
reached in a period of a few daughter half-lives. this material,
stables du carbone it wasa decided
et de l’oxygène to establish
été engagée: le nouveaua new "standard", NZ1, une p
The  32P activity is relatively easy to detectd’Ag
–apart reference material, of which 34δ is carefully de-
2S, a été accepté pour définir la nouvelle échelle V-CDT qui est très proche de l’é
from the very low intensity- because of the simple fined relative to CDT. An analogous procedure
decay scheme: only one β decay with Eβmax of 1.7
- was
34
δ(NZ1followed as for= −the stable
vs / V-CDT) 0,30‰ carbon and oxy-
MeV, and no g radiation. The chemical extraction gen isotopes: the new “standard”, NZ1, a homo-
procedure is laborious since silicate is to be sepa- toutes
Désormais geneous Ag2S powder,
les valeurs de 34δ sonthas been par
données accepted
rapporttoaude- V-CDT (très proche
rated from more than a m3 of water or ice. De plus, une fine the new V-CDT scale which is very close to
série d’échantillons de référence supplémentaires est en préparation sous
the original CDT scale:
[127] applied the AMS technique to the analysis
de l’AIEA.
of 32Si. 34
δ(NZ1 vs / V-CDT) = − 030‰ (12.22)
Des mesures de spectrométrie de masse sont réalisées sur SO2 et SF6 gazeux. L’
niveau de SOFrom
2 est que la mesure
now on alldu rapport
34 du faisceau
δ values [66]/[64] = [34S16O2]/[3
d’ions rela-
are given
12.7.4. Applications une correction à cause de la présence de [32to
S18the original
O16O] dans leCDT.
faisceau de masse <66
tive to V-CDT (very close
Originally 32Si was expected to close the gap Furthermore,
préparé par oxydation de Aga series
2S forméofde
additional
composésreference sam-
initiaux tels que SO42− (dissous o
in the datable-age range between 3H andgazeux,
14
plessulfures
C inou des is in preparation
solides. Unby the care ofdethe IAEA.
inconvénient l’utilisation de SF6 est que la
fluorine nécessite des précautions de sécurité extrêmement strictes.

224 133
 INTRODUCTION
Mass spectrometric measurements are carried
out on gaseous SO2 or SF6. The disadvantage of
the first is that, measuring the ion beam ratio [66]/
[64] = [34S16O2]/[32S16O2] a correction is needed
for the presence of [32S18O16O] in the mass<66>
ion beam. SO2 is prepared by oxidation of Ag2S
made of original compounds such as SO 2   4 (dis-
−
solved or crystalline), gaseous H2S, or solid sul-
phides. A disadvantage of the use of SF6 is that
handling fluorineneeds extremely strict safety
precautions.
For a 34S/32S analysis about 100 mg of S is need-
ed, at the same time sufficient for a 18O/16O analy-
sis of the oxygen content of sulphate.
12.8.2. Natural abundance
Variations in the natural abundance are caused
by chemical and biological isotope fractionation
processes in the sulphur cycle. Isotopic exchange
4 and HS (for S isotopes)
between dissolved SO 2  − -
and between SO 4 and H2O are extremely slow
2 −
processes and can under surface conditions not
been observed.
On the other hand, biological (bacterial) process-
es cause kinetic isotope fractionation. In general,
34
S is enriched in sulphate –such as dissolved in
the oceans- and depleted in sulphide. This effect
is observed during sulphate reduction, where S6+
is reduced to S2-. The isotope fractionation in-
volved is:
ε( SO 2  
34
4 → HS ) = R(HS ) / (SO 4 ) = −22‰
− − 34 − 34   
2 −
(12.23)
Oceanic sulphate and the evaporative minerals
derived thereof have 34δ values of + 20‰. The 18δ
value of oceanic dissolved SO 2   4
−
is + 9.6‰.
Rainfall sulphate, originating from oxidation of
(CH3)S(CH3), dimethylsulphide, a product from
decomposition of marine plankton, has 34δ values
of about + 5‰.
12.8.3. Applications
A general problem with sulphur isotopes is that
isotopic values of certain compounds may vary
greatly, even if the compounds that have in prin-
ciple the same type of origin.
Despite that, many exchange processes between
S (and O) containing compounds mutually, and
between these and water is that in the aqueous
134
environment the isotopes can often be used to
identify their sources. Furthermore, 34S/32S — oc-
casionally in combination with 18O/16O — is ap-
plied to observe special biochemical processes in
surface- and groundwater [128, 129]
12.9. Chlorine
12.9.1. Radioactive 36Cl
12.9.1.1. Origin and characteristics
Production in the atmosphere goes through
the action of cosmic protons or neutrons:
40
Ar (p,sp) 36Cl (12.24)
36
Ar (n,p) 36Cl (12.25)
The cosmic-ray produced 36Cl fall-out rate from
the atmosphere is estimated to be 26 atoms
m−2 s−1.
Underground 36Cl is being formed near the sur-
face by the action of thermal (= low-energy) neu-
trons or cosmic-ray muons:
35
Cl (n,γ) 36Cl and 39K (n or µ,α)36K
(12.26)
or at large depth by:
35
Cl (n,γ) 36Cl (12.27)
This production rate largely depends on the con-
centration of uranium and thorium in the aquifer
rock or sediment.
Thermonuclear tests, especially in the Southern
Pacific ocean, have temporarily produced large
amounts of 36Cl by neutron activation of chloride:
35
Cl (n,γ) 36Cl (12.28)
12.9.1.2. Experimental and technical aspects
Although 36Cl is radioactive and decays through
energetic β- radiation (βmax ~700 keV), quantita-
tive detection is difficult because of the very low
specific activity. Measurements of the  36Cl abun-
dance in water have been carried out by liquid
scintillation [130]. Most natural 36Cl levels, how-
ever, came within reach with the introduction of
the AMS technique [131]. The detection limit for
the 36Cl/Cl ratio is about 10 – 15.
 36
N = 3,2 × 107(sec/an) × F / [P × (100 − E)/100] atomes/L

(Lehman et al., 1991). Avec F = 26 atomes m−2 s−1, on obtient, dans un climat tempéré
(0,6 à 3) × 106 atomes/L. Dans la plupart des eaux souterraines, les valeurs
natural isotopes of elements other than h, c, o
considérablement plus élevées. Cela est dû à la production in situ, i.e. souterraine de 36
Les essais nucléaires ont apporté des quantités importantes de 36Cl dans les eaux de me
Table 12.10. Natural isotopes of
partie injectées m−2sla−1.stratosphère.
omsdans This resulted in 36Clle concentrations
Durant in 1960, les retomb
début des années
chlorine water in the order of 7 × 108 atoms/L.
augmentées à des valeurs dans la gamme de 104 atomes m−2s−1. Cela résultait en des c
dans l’eauCl meanwhile
de 7 × returned to its original natural
36 37 36
 Cl
35
    
17  Cl
36
    
17
Cl Cl
    
17
de l’ordre 108 atomes/L.
level, contrary to 14C and 3H. The temporarily in-
Stability Stable Radioactif Entre-temps,
Stable le 36Cl est
creased retourné
levels à sonbe
can thus niveau
used naturel
to traced’origine,
infiltratedcontrairement au
14

niveaux temporairement
soil moistureélevés peuvent
during ainsi
recent être utilisés pour tracer l’eau d’infiltratio
decades.
Natural abundance
75.5% 10−15 to 10−13 cours
24.5%des dernières décades.
fraction
12.9.1.4. Applications
Natural abundance 4 × 105 to 12.9.1.4 APPLICATIONS
in water 5 × 108 atomes/L 12.9.1.4.1. Dating old water
Half-life (T1/2) 3.01 × 105 a
12.9.1.4.1 Datation
Due to its de long ancienne 36Cl is suitable to date
l’eau half-life,
Decay constant
7.30 × 10−14 s−1 En raison de old groundwater, i.e. water in excess of 50 000
sa longue période, 36Cl est adapté pour dater les eaux souterraines ancien
(λ) years old. For deep-underground water there
vieilles de plus de 50 000 ans. Pour 36 des eaux souterraines profondes, il y a deux source
Decay mode / are two sources of Cl, 36i.e. (i) the cosmogenic
β / Ar
− 36
la source cosmogènique, représentée R0 le rapport
par36Cl/Cl 36
Daughter source, depicted by the  ratio 36RCl/Cl
0,
36
andet(ii)
(ii) la production so
par activationthe underground
des neutrons, représentée par le rapport
production by neutron activation R se. Le rapport actuel à m
échantillons d’eaux
of 35Cl,estdepicted
alors: by the ratio 36Rse. The actual ratio
About 10 mg of chlorine is needed for an AMS 36to be36measured −λt
in the water sample is then:
analysis. It is concentrated from a water sample R = R 0e + 36
Rse (1 − e−λt)
or leached from a sediment and precipitated as
36
R = 36R0 e−λt + 36Rse (1 − e−λt)
contenant le terme de production donné dans l’Eq. 6.30.
AgCl, which is brought on the target holder. containing the production term given in Eq. 6.30.
A partir de cela, l’âge de l’eau est:
From this the water age is:
12.9.1.3. Abundance in nature 36
1 R − 36 Rse
Under natural conditions, Cl/Cl concentration
36 t=− ln (11.29)
36
λ 36
R0 − 36 Rse
ratios are observed of 10 – 15 to 10 – 13. With a chlo-
ride concentration of [Cl] mg/L of water,36 this
(3,2 × 10λ = ln2
where / (3.2 × 10 Rseanalysant
)s en has to be ob- 36Cl/Cl des roc
36 7 −1
7 −1
comes to a concentration of 36Cl atoms of:où λ = ln2 /tained )s . Rse doit être36obtenu
by analysing the  Cl/Cl ratio of the source
le rapport

rock.
N = (6×1023×10−3/35,5)×(36Cl/Cl)×[Cl] atoms/L
36

12.9.1.4.2. Infiltration of young water

which is in the order of (104 to 106) 36Cl atoms / L
of water per mg/L chloride concentration.
In order to estimate the recharge rate of 36Cl (36N)
in atoms per L of infiltrating water, the amount of
precipitation (P in mm/a ) and evaporation (E in
%) have to be known [132]:
By observing the relatively high 36Cl content of
undeep water from the era of nuclear weapons
testing, ages of infiltrated water can be deter-
mined of up to a few decades, resulting in values
for the infiltration rate [131].

36
N = 3,2 × 107(sec/an) × F / [P × (100 − E)/100]
atoms/L 
With F = 26 atoms m−2 s−1 this comes in a moder-
ate climate to a range of (0.6 to 3) × 106 atoms/L.
In most groundwaters the observed values are
considerably larger. This is due to the in situ, i.e.
underground production of 36Cl.
12.9.2. Stable 35Cl and 37Cl
12.9.2.1. Natural abundance and applications
Because the chlorine ion, Cl-, is very little reac-
tive, the isotopic variations denoted by;
δ = (37Cl/35Cl)sample / (37Cl/35Cl)seawater NaCl − 1
37

The nuclear tests produced large amounts of 36Cl
in seawater, subsequently in part injected into
the stratosphere. During the early 1960s the 36Cl
fall-out increased to values in the range of 104 at-
(12.30)
are very small. Attempts have been made to apply
chlorine isotopes to study the characteristics of
brines [133] and the degradation and distribution
of Cl containing contaminants [134].

135
 12.9.2.1 ABONDANCE NATURELLE ET APPLICATIONS
Cl STABLES
Parce que l’ion chlore, Cl−, est vraiment peu réactif, les variations isotopiques caractérisées par;
NCE NATURELLE ET
37
APPLICATIONS INTRODUCTION
37
δ = ( Cl/ Cl)sample / (37Cl/35Cl)seawater NaCl − 1
35
(12.30)
Cl−, est vraiment peu réactif, les variations isotopiques caractérisées par;
sont vraimentStable faibles.isotope
Des tentatives ont été faites
fractionation involvedpour inappliquer
Cl- dif-les isotopes
40 du chlore
Ar (n,2n) 39 à l’étude des
Ar (12.36)
/35Cl)caractéristiques
sample / ( 37
Cl/ 35
Cl)
fusion
des
seawater −
saumures
through
NaCl 1 sediments
(Eggenkamp,is 1994) equals et dethe ratio (12.30)
la dégradation et de la distribution des
contaminantsof the  diffusion
contenant du Cl (Van coefficients
Warmerdam(Sect. 3.5).
et al., 1995). Since The respective decay modes are:
Des tentatives ont the Cl été faitesions
- pourare
appliquer
hydrated,les isotopes du chlore
i.e. coupled à l’étude des
to water
desArles
+ esédiments
→ 37Cl (12.37)
37 −
aumuresLe fractionnement
(Eggenkamp, molecules,isotopique
1994) et deimpliqué
the diffusion dans la et
constant
la dégradation diffusion
of de Cl− à travers
dethe chlorine
la distribution est égal au
−
rapport
t du Cl (Van des coefficients
ion through
Warmerdam de 1995).
et al., diffusion
water is (Sect. 3.5). Puisque
determined les ions Cl sont hydratés, i.e. couplés à des
by the masses in combination with the emission of X rays, and
of the hydrated
molécules d’eau, la constante de diffusion ions (with ndeH O
l’ion
2 molecules).
chlore à dansFor l’eau est déterminée par les masses
topique impliqué dans la diffusion
the diffusion of de Cl− à travers
molecule M les sédiments est égal 39 au
des ions hydratés (avec n molécules H2O). A through
Pour la a medium
diffusion de la molécule ArM→ K + β− (12.38)
A à travers
39 un milieu de
−
s de diffusion of
(Sect. molecules
3.5). Puisque M les (* indicates
ions Cl 37 the rare
sont hydratés, isotope,
i.e. i.e.
couplés
molécules MB37(* indique l’isotope rare, i.e. Cl), le facteur de fractionnement est de (Eq.3.34):
B à des
nstante de diffusion Cl,
de the fractionation
l’ion chlore à dansfactor is (Eq. 3.34):
l’eau est déterminée par les masses with a maximum β- energy of 565 keV.
c n molécules H2O). Pour laMdiffusion de la molécule MA à travers un milieu de
A (* M A + M B ) [35 + 18n]([37 + 18n] + 18)
ue l’isotope rare, i.e.α37Cl),
37
= le facteur =
de fractionnement est de (Eq.3.34): 12.10.2. Experimental (12.31) and technical
* M A (M A + M B ) [37 + 18n]([35 + 18n] + 18)
aspects
M A (* M A + M B ) [35 + 18n]([37 + 18n] + 18) From
Pour un taux = d’hydratation de n = 4, le facteur de fractionnement résultant
(12.31)
(12.31) esta few hundred
de 0,9987; pourlitres
n = 2,of water sample the no-
(M A + M B )
* M A 37 [37 + 18n]([35 + 18n] + 18) ble gases are extracted and argon separated gas
α = 0,9972 (cf. Eggenkamp, 1994).
chromatographically. The subsequent proportion-
pour n =al 2, counting of the  Ar β decay requires at least
39 -
For a hydration
ation de n = 4, le facteur rate of n = 4
de fractionnement the resulting
résultant frac-
est de 0,9987;
12.9.2.2 A SPECTS EXPERIMENTAL ET TECHNIQUE
tionation factor is 0.9987; for n = 2, 37α = 0.9972 2 L of argon extracted from about 15 m3 of water
nkamp, 1994).
[133].à partir d’un échantillon d’eau en ajoutant AgNO3. Il [135].
AgCl est précipité
This degassing procedure is carried ouit in
est purifié et réagit avec CH3I
the field. 37 35
pour donner du méthylchlorure, CH3Cl. Ce gaz est adapté à la mesure du rapport Cl/ Cl par SMIR
EXPERIMENTAL ET TECHNIQUE
normale. 12.9.2.2. Experimental and technical aspects
artir d’un échantillon d’eau en ajoutant AgNO3. Il est purifié et réagit avec CH12.10.3.
3I Natural abundance
La référence AgCl
pour is
les precipitated
isotopes du from
chlore the water
est le sample
Standard
37
lchlorure, CH3Cl. Ce gaz est adapté à la mesure du rapport Cl/ Cl par SMIR by
35Mean Ocean Chloride (SMOC), car la
composition adding
isotopiqueAgNO 3. The resulting
en chlorure de l’eauAgCl
de meris purified
est très and The 
constante. Lenatural
rapport specific
37
Cl/35Cl activity
de ce of 39Ar in the at-
reacted with CH3I to methylchloride, CH3Cl. This mosphere is about 2 mBq/L of Ar and is re-
standard est 0,324.
isotopes du chlore gasest
is suitable for measuring
le Standard Mean Ocean the Chloride
37
ratio by car ported
Cl/ Cl(SMOC),
35
la to be constant within 7% ([136], cor-
e en chlorure de normal mer est très constante. Le rapport Cl/ Cl de responding
l’eau deIRMS. 37 35
ce to about 0.5 mBq/m3 of water.
12.10 ARGON
The reference for chlorine isotopes is Standard
Underground 39Ar is produced in the presence
of neutron from spontaneous fission of Th and
Mean Ocean Chloride (SMOC), as the isotopic U (Eq.  12.33 – 35). The  37Ar abundance is much
12.10.1 composition
ORIGINE ET in seawater chloride is very con-
CARACTERISTIQUES smaller (Table 12.11).
stant. The 37Cl/35Cl ratio of this standard
37 is 0.324.
L’isotope radioactif à courte durée de vie de l’Argon, Ar, est cosmogènique en tant que produit de
E ETspallation de l’40Ar, et est produit dans le sol par les neutrons issus des fissions
CARACTERISTIQUES du Th
12.10.4. et de U:
Applications
12.10. Argon
courte durée de vie de l’Argon, 37Ar, est cosmogènique en tant que produit With
de its half-life of 269 years, 39Ar is suitable
228
est produit dans le12.10.1.
sol par les Origin anddes
neutrons issus characteristics
fissions du Th et de U: to fill the  gap in dating range between 3H and
The short-living radioactive isotope of Ar, 37Ar, is C. The advantage is that it is chemically in-
14

cosmogenic as a spallation product of 40Ar, and is ert. However, the subsurface production of 39Ar
being produced underground by neutrons from makes it problematic. On the other hand, the pres-
Th and U fission: ence of 39Ar is being used to indicate the under-
ground production of radioisotopes.
40
Ca (n,α) 37Ar (12.32) 39
Ar has been shown an excellent isotope for dat-
ing glacier ice [137].
together with the long-living argon isotope, 39Ar:
Ar is applied in oceanography to study the large-
39

38
Ar (n,γ) Ar (12.33)
39 scale mixing and circulation.

39
K (n,p) 39Ar (12.34) 12.11. Krypton
42
Ca (n,α) Ar (12.35)
39
12.11.1. Origin and characteristics
The latter is primarily produced in the atmo- The long-living krypton isotope 81Kr is produced
sphere by the reaction: in the atmosphere by cosmic-ray induced spall-

136
 natural isotopes of elements other than h, c, o

Table 12.11. Natural isotopes of argon.

 Ar
36
    
18  Ar
37
    
18 1  Ar
38
  
  8
39
 Ar
    
18  Ar
40
    
18

Stability Stable Radioactive Stable Radioactive Stable

Natural abundance fraction 0.33% 0.06% 8.5 × 10−16 99.6%
Natural abundance in air 3.15 × 10−5 5.9 × 10−6 9.34 × 10−3
Natural abundance in water 70 atoms/m3 8500 atoms/L
Specific activity in air (Bq/L) 3 × 10 −7 to −9
1.68 × 10−5
Half-life (T1/2) 35.1 d 269 a 
Decay constant (λ) 2.31 × 10−7 s−1 8.17 × 10−11 s−1
Decay mode / Daughter EC / 37Cl β− / 39K

ation of stable krypton (primarily of 84Kr), and by
neutron activation according to:
Kr (n,γ) 81Kr (12.39)
80
The same reaction is responsible for the produc-
tion during nuclear test explosions, with addition-
ally:
Kr (n,2n) 81Kr (12.40)
82
and through fission of uranium. The  81Kr contri-
bution from bomb testing is considerably smaller
than the natural atmospheric 81Kr content [138].
The underground production of 81Kr is negligibly
small.
Kr decays by electron capture and emitting
81
13.5 keV X rays according to:
Kr + e− (K) → 81Br (12.41)
81
12.11.2. Experimental and technical
aspects
81
Kr is detected by radiometry or by AMS.
The consequence of the low 81Kr activity com-
pared to the present-day 85Kr activity is that it is
no longer possible to measure the atmospheric
81
Kr content by radiometric means.
For a 85Kr measurement about 20 mL of krypton
gas is needed, to be extracted from the water sam-
ple.
85
Kr on the other hand can be measured radiomet-
rically as a mixture of a few mL of krypton, con-
densed from the original sample by various cold
traps and a gas chromatographic separation, with
a proper counting gas in a proportional counter.
A few hundred litres of groundwater are needed
for such 85Kr analysis [135, 139].
12.11.3. Natural abundance
The natural abundance of the noble gas krypton
in the atmosphere is 1.14 × 10 – 6 ppmv. The esti-
mated pre-nuclear concentration ratio of 81Kr/Kr
is 5.2 × 10 – 13, or a specific activity of 1.5 mBq/L
of krypton. Under natural conditions 85Kr was
much less abundant, with a 85Kr/Kr value of
about 3 × 10 – 18. However, due to the emission
of this isotope as a fission product by the nuclear
industry (primarily reprocessing of plutonium as
a nuclear fuel), the present-day concentration ra-
tio amounts to 1.5 × 10 – 11.
The solubility of krypton in water is
9.3 × 10 – 5 mL(STP)/L. This means that the maxi-
mum concentration of 81Kr is 1300 atoms /L of
water.
The natural cosmogenic production rate of 85Kr is
extremely small, due to the small reaction cross
sections. However, 85Kr is an abundant fission
product of uranium and plutonium and is as such
during stages of nuclear fuel handling released to
the atmosphere. From a very low pre-nuclear lev-
el, the atmospheric content has steadily increased
to a  specific activity of about 1Bq/mL (STP) of
krypton in 1990, equivalent to a maximum 85Kr
activity of about 0.07 Bq/m3 of water.

137
 INTRODUCTION

Table 12.12. Natural isotopes of krypton

 Kr
78
    
36  Kr
80
    
36
81
 Kr
    
36  Kr
82
    
36

Stability Stable Stable Radioactive Stable

Natural abundance fraction 0.354% 2.27% ~5×10−13 11.56%

Natural abundance in air 4.0 × 10−9 2.59 × 10−8 1.317 × 10−7

Natural abundance in water 1200 atoms/L

Half-life (T1/2) 2.1 × 105 a 

Decay constant (λ) 1.05 × 10−13 s−1

Decay mode / Daughter EC / 81Br

 Kr
83
    
36  Kr
84
    
36
85
 Kr
    
36  Kr
86
    
36

Stability Stable Stable Radioactive Stable

Natural abundance fraction 11.55% 56.90% 1.8 × 10−11 17.37%

Natural abundance in air 1.316 × 10−7 6.48 × 10−7 2.1 × 10−17 1.98 × 10−7

Specific activity in air 1.1 mBq/L *

Natural abundance in water 2.5 × 10−6 Bq/L

Half-life (T1/2) 10.76 a 

Constante de désintégration (λ) 2.04 × 10−9 s−1

Mode de désintégration/Fille β− / 85Rb

* Valid for the year 1990, steadily increasing by about 0.025 mBq/L per year [140].

12.11.4. Applications non. It has also been brought into the atmosphere

Deep groundwater, isolated from the atmosphere as a fission product of uranium by nuclear bomb
more than 50 years ago, does not contain 85Kr. testing and the nuclear industry.
Consequently 81Kr with its large half-life is in It decays according to:
principle an ideal tracer for dating water with
(isolation) ages of 50 ka to 1Ma. The problem is 129
I → 129Xe + β− (Emax = 150 keV) (12.42)
the complicated experimental handling and mea-
suring procedure. The  first AMS attempts have
been promising [138]. Table 12.13. Natural isotopes of
iodine
As mentioned before, the cosmogenic origin of
85
Kr is negligibly small. Therefore, this isotope
serves to recognise young groundwaters, and  I
127
    
53  I
129
    
53

to study their infiltration and hydrodynamics in Stability stable radioactive

the soil, especially in combination with 3H.
Natural abundance fraction 100% ~10−12

12.12. Iodine Natural abundance in water 5 × 104 atoms/L

Half-life (T1/2) 15.7 × 106 a
12.12.1. Origin and characteristics
Decay constant (λ) 1.40 × 10−15 s−1
I is naturally produced in the atmosphere by
129
Decay mode / Daughter β− / 129Xe
a cosmic-ray induced spallation reaction on xe-

138
 natural isotopes of elements other than h, c, o
12.12.2. Experimental and technical
aspects
Nowadays by far the best detection technique is
AMS, using 1 to 3 mg of AgI, prepared from io-
dine extracted from the  sample and purified by
ion exchange procedures [141]. The 129I/I detec-
tion limit at present is in the order of 10 – 15.
12.12.3. Natural abundance
The natural abundance ratio 129I/I is about 10 – 12.
This level has increased locally by orders of mag-
nitude due to nuclear bomb testing and the release
of 129I as a fission product by nuclear reactors and
reprocessing plants. In off-coast ocean surface
water the 129I/I ratio is estimated to be ≤ 10 – 10.
12.12.4. Applications
Most applications are devoted to analysing
the ‘nuclear-era’ levels of 129I. Especially the high
levels in rivers and coastal waters near nuclear in-
dustries are being used for tracing oceanic mixing
processes and the vertical transport of continen-
tal water in the ocean. 129I/I values are being ob-
served of up to 10 – 9.
In groundwater the  I/I ratio is mainly deter-
129
mined by the recharge rate, the rate of leaching
from the aquifer rock, and the amount of in situ
uranium fission. The latter complicates the dating
of deep groundwater.
12.13. Decay series
In Sect. 6.6 we discussed the three radioactive
decay series. Each chain consists of a parent nu-
clide which has a half-life larger than the age of
the  universe, a  series of successive α  and β de-
cays, and finally a stable isotope of Pb. Because
the masses of the successive daughters change
only by 4 units and β decay hardly changes
the mass, we can speak of the Thorium series, or
the 4n series (232Th to 208Pb), the Uranium series,
or the 4n+2 series (238U to 206Pb), and Actinium
series, or the 4n+3 series (235U to 207Pb). The hy-
pothetical 4n+1 series (possibly 237Np to 209Pb)
no longer exists because of the relatively small
half-life. Several nuclides show branching decay
(either α or β-); the main decay mode is indicat-
ed in Fig. 12.2, showing the three decay series.
The physical information on the decay and abun-
dance of the members of the decay series is given
in Table 12.15.
In old, geochemically undisturbed rock the ura-
nium and thorium containing minerals contain all
parent and daughter nuclides in a state of equi-
librium. This means that, depending on the rela-
tion between half-lives, all members of the decay
series are directly or indirectly in secular equilib-
rium with the parent nuclide, 238U, 235U, or 232Th.
In the most abundant 238U, for instance, each 238U
is accompanied with a decay from each daugh-
ter, granddaughter, and so on. This means that for
each 238U decay, now and in the past, 7 more α de-
cays take place. The total number of 238U decays
is thus equal to the emission of 8α particles of He
atoms. The consequence is that, form the amount
of helium gas in a “closed-system” rock, the age,
i.e. the time elapsed since the rock matrix be-
came “closed”, can be determined. The calcula-
tion is a variant of the “daughter accumulation”
case, treated in Sect. 6.7. The amount of helium
in L(STP) per kg of rock produced in a period of
time T in a rock with an present-day specific 238U
activity of 238A kg−1 of rock is:
V = 8 × 238A(eλT − 1) (22.4/6 × 1023)
so that the age T of this rock is
T = (1/λ)ln{[6 × 1023V/22.4]/[8 × 238A] + 1}
(12.43)
This method is referred to as the U-He dating
method. The same holds for the other decay se-
ries, for 232Th with (232 – 208)/4 = 6 He atoms
per decay and for 235U (235 – 207)/4 = 7 He at-
oms per decay.
12.14. The uranium series
This decay series is shown as the lower series
in Fig. 12.2. All physical parameters concern-
ing the radioactive decay are given in Tables
12.14 – 12.16.
12.14.1. 238
U/234U
In a state of secular equilibrium (i.e.
λ N =  234λ234N) the abundance ratio of 234U/238U
238 238
is inversely proportional to their decay constants
or proportional to the half-lives = 5.48 × 10 – 5,
while the activity ratio 234A/238A = 1.
The solubility of uranium in water depends on
the oxidation state. The U6+ state (as UO 2 
2 ) is
+
139
 INTRODUCTION
more soluble that the reduced state U4+ (as UO +2 ).
As 234U and 238U are having the same solubility in
water, one would expect the activity ratio in dis-
solved uranium to be = 1. However, this is gen-
erally not the case, because 234U is preferentially
leached from the rock. As a consequence of the re-
coil energy given to the 234Th daughter during
the 238U decay (Sect. 5.3), the bond between 234Th
(and the subsequent daughters 234Pa and 234U)
and the crystal matrix is broken, so that the 234U
atom is more free to enter the solution than the re-
maining 238U atoms. The actual 234U/238U ratio in
the water depends on several (geo)chemical con-
ditions within the aquifer. Values of 2 to 3, and
up to 10 have been observed. The absence of an
equilibrium between the activities is referred to as
the  234U/238U disequilibrium. The growth rate of
this ratio in a closed system can be used to study
the hydrogeological and geochemical conditions
and the transport of groundwater masses [142].
In seawater the 234U/238U ratio is also larger than
one, due to the effluence of continental freshwa-
ter. Commonly values of about 1.4 are being ob-
served.
12.14.2. Th −234U dating
230
The relation between the activities of 234U and its
daughter 230Th is an example of a transient equi-
librium (Sect. 6.6.2). Because Th is extremely
insoluble in water, natural waters contain urani-
um isotopes in the absence of Th isotopes. This
is the basis for a dating method of corals [80]
and continental sediments like peat [143, 144],
referred to as U–Th disequilibrium dating. 234U
is being taken up by the organisms or sediment
without the radioactive daughter 230Th. The lat-
ter grows into the sample with increasing age.
Equations apply discussed in Sect. 6.6. Especially
the dating of corals has been very successful, be-
Table 12.14, Natural isotopes of uranium
 U
234
92
Stability radioactive
Natural abundance fraction 0.0057%
Half-life (T1/2) 2.47 × 105 a  7.038 × 108 a  4.468 × 109 a
Decay constant (λ) 8.892 × 10−14 s−1
α / 230Th (decay series →
Decay mode / Daughter 206
Pb)
140
cause under marine conditions the starting condi-
tions (no Th isotopes, constant 234U activity) are
relatively simple.
12.14.3. 226
Ra and 222Rn
Through recoil during the α decay of 230Th, 226Ra
can easily be leached from the rock matrix.
Radium is present in solution as the divalent alka-
li-earth cation and behaves chemically like Ca2+
and Ba2+. In groundwater specific activities can
be observed of up to 5 Bq/L.
The daughter of 226Ra is 222Rn, a radioactive ra-
don isotope with a half-life of 3.8 days. As a no-
ble gas, 222Rn is not being absorbed by solids.
Moreover, it is highly soluble in water, contrary
to 226Ra. Consequently, 222Rn is likely to accu-
mulate in groundwater. The  specific activity can
exceed that of its parent 226Ra by orders of magni-
tude. Because of its short half-life, 222Rn is indica-
tive for young groundwaters. As radon can easily
be removed from water, the in-growth of 222Rn in
artificially recharged water can be used to esti-
mate residence times.
12.14.4. 210
Pb
For the sake of completeness we mention the ex-
istence of a relatively long-living member of
the uranium series, the radioactive isotope of
lead, 210Pb. For hydrological applications this
nuclide has little relevance. However, it is exten-
sively used for measuring the accumulation rate
of ice or sediments. As an inert gas 222Rn escapes
from the soil and subsequently decays in the at-
mosphere by way of short-living daughters to
210
Pb (Fig. 12.2). After a short residence time in
the air it is deposited either by wet or dry precipi-
tation together with snow (to form ice) or sedi-
ment in water. The deposition rate is in the range
 U
235
92  U
238
92
radioactive radioactive
0.7200% 99.2743%
 
3.1208 × 10−17 s−1 4.9156 × 10−18 s−1
α / 231Th (decay series → α / 234Th (decay series →
207
Pb) 206
Pb)
 natural isotopes of elements other than h, c, o

β−
228 232
Th Th
decay 228
Ac
mode
α 224
Ra 228
Ra
minor

220
Rn 235
U

231
Pa
212 216
Po Po 227
Th 231
Th
212
Bi 227
Ac
208 212
Pb Pb 223
Ra
208
Tl 223
Fr
234 238
219
U U
Rn
234
215 219
Pa
At At
230 234
211 215
Th Th
Po Po

211 215
Bi Bi
226
207 211 Ra
Pb Pb

207
Tl
222
Rn

218
At

210 214 218

Po Po Po

210
Bi 214
Bi half-life > 1 year
206
Pb 210
Pb 214
Pb half-life < 1 year

206 210 stable

Tl Tl

206
Hg

Fig. 12.2.  The thorium, actinium and uranium decay series according to the Chart of Nuclides (cf. Figs 2.2 and
6.3). The final stable lead isotopes are represented by a black box, the long-living nuclides (T1/2 > one year) by
a shaded box. The preferential decay modes of branching decay and the resulting decay chain are indicated by
a double arrow.

of 6 to 10 mBq cm−1 a−1 [145]. In ice or in aque- The  α activity of radon isotopes is measured by
ous sediments it decays with a half-life of 22.26 proportional gas counting.
a , and can be applied for determining ages up to
about 100 years. The activity of 210Pb is measured indirectly by de-
tecting the ingrowth of 210Po in the pure Pb source
by α counting. Similarly is the activity of 226Ra
12.14.5. Experimental and technical measured by ingrowth of 222Rn in the pure radium
aspects sample.
Originally the α activities were measured by
α spectrometry [146]. A few micrograms of
uranium is needed for providing a pure metal- 12.15. The actinium series
lic, electroplated uranium source for an α detec- The information on decay and abundance is
tor. The modern mass spectrometric technique shown in Table 12.14 and Table 12.16. The decay
(Thermal Ionisation Mass Spectrometry, TIMS) scheme is presented in Fig. 12.2.
needs less sample and has a lower detection limit,
while the results are more precise and obtained This series start with the 235U parent and goes
faster. The capital investment, however, is a fac- through 7α  decays and 4β decays to stable
tor of 10 larger. 207
Pb. It is the less abundant isotope of uranium.

141
 INTRODUCTION
The concentration ratio has been internationally
established as 238U/235U = 137.88.
The daughter element of 235U, protoactinium
(231Pa), is equally insoluble in water as thorium.
This means that in an aqueous environment
the element Pa is rapidly removed from the wa-
ter. The sediment then contains ‘unsupported’
Pa, i.e. without 235U, so that the decay of 231Pa in
the sample is indicative for the age of the sedi-
ment. In the next section 230Th will turn out to
have the same characteristic [147].
12.16. The Thorium series
Physical data on the decay and abundance are
given in Fig. 12.2 and in Tables 12.15 – 16.
The abundance and the application of the long-
living member of the 238U series, 230Th, the daugh-
ter of 234U, has been discussed in Sect. 12.14.2.
Also the combination of the geochemically
analogous Pa isotope, 231Pa, both being highly
insoluble in water and therefore ‘unsupportedly’
included in a marine sediment, was mentioned
Table 12.15. Natural isotopes of thorium
Stability
Natural abundance fraction
Half-life (T1/2)
Decay constant (λ)
Decay mode / Daughter α / 226Ra (decay series)
142
earlier. Especially the combination of the two
isotopes is valuable, because the decay rates are
different. It can be shown that this information
cancels the need for knowing both specific activi-
ties at the time of sedimentation. The change of
the initial ratio of the specific activities in time is
indicative for the age.
The couple of parent nuclide 232Th and daughter
228
Ra plays a role in studying water-rock inter-
action. Important is the chemical difference be-
tween Th and Ra, the first being much less soluble
than the latter. Activity ratios that are expected to
be = 1 under conditions of decay equilibrium,
may be <1 if the rock minerals have lost 228Ra af-
ter 232Th recoil or if the sediment is accumulating
228
Ra from its parent decay, and > 1 where uptake
of 228Ra has taken place from the surrounding wa-
ter.
Direct hydrological applications of 232Th are un-
likely, due to the extremely low solubility of tho-
rium in water.
230
90  Th  Th
232
90
radioactive radioactive
100%
7.5 × 10 a  4
1.4010 × 1010 a 
2.93 × 10−13 s−1 1.5678 × 10−18 s−1
α / 228Ra (decay series)
 natural isotopes of elements other than h, c, o

Table 12.16. Nuclear data on the decay and abundance of the member

nuclides of the uranium, actinium and thorium decay series (data from
[148].

Half-life Decay Abundance Half-life Decay Abundance

218
Po 3.05 m α,(β)
238
U 4.468 × 109 a  α 99.2743%
216
Po 0.15 s α
235
U 7.038 × 108 a  α 0.7200%
215
Po 1.78 ms α(β)
234
U 2.47×105 a  α 0.0057%
214
Po 164 µs α
234
Pa 1.175 m β
Pa
212
Po 0.30 µs α
231
3.28 × 104 a  α
234
Th 24.10 d β
211
Po 0.516 s α

Th
232
1.4010 × 1010 a  α 100%
210
Po 138.4 d α

231
Th 25.52 h β
215
Bi 7.4 m β

Th
230
8.0 × 104 a  α
214
Bi 19.7 m (α),β
228
Th 1.913 a  α
212
Bi 60.6 m (α),β
227
Th 18.72 d α
211
Bi 2.15 m α,(β)
228
Ac 6.13 h β
210
Bi 5.01 d (α),β
227
Ac 21.77 a  (α),β
214
Pb 26.8 m β
228
Ra 5.76 a  β
212
Pb 10.64 h β
226
Ra 1.60 × 103 a  α
211
Pb 36.1 m β
224
Ra 3.66 d α
210
Pb 22.26 a  (α),β
223
Ra 11.44 d α
208
Pb stable −− 52.3%
223
Fr 21.8 m (α),β 207
Pb stable −− 22.1%
222
Rn 3.82 d α 206
Pb stable −− 24.1%
220
Rn 55.6 s α 210
Tl 1.30 m β
219
Rn 3.96 s α 208
Tl 3.05 m β
219
At 0.9 m α,(β) 207
Tl 4.8 m β
218
At ~2 s α 206
Tl 4.2 m β no γ
215
At 0.1 ms α 206
Hg 8.1 m β

Note: The decay of α and β is followed by one or more g emissions. Where the decay is branching, the least abundant decay
mode is given in parenthesis; a = year, d = day, m = minute, s = second

143
13. errors, means and fits
This chapter contains a choise of essential infor-
mation on the analysis of measuring uncertain-
ties, and the treatment of large numbers of data.
Starting with a discussion on ‘errors’, we arrive at
a technique of judging the probability of the truth
of a final result.
13.1. Errors
In dictionaries the word error is defined as
the difference between the approximated value –
as the result of an observation or measurement, or
a calculation- and the true value. The problem is
that in general we do not know the ‘true value’,
as this is generally the result of a measurement or
calculation. Therefore, we have to find a way of
estimating the ‘reliability’ of our result.
The  name ‘errors’ is not well specified as such.
We thus have to become more specific about
the definition. Errors can be classified as follows:
(1) Blunders or mistakes in measurement or cal-
culation are usually apparent as being far
from expectations. They are to be dealt with
by repeating the measurement or calculation.
(2) Systematic errors are more difficult to detect.
They are reproducible discrepancies, often
the result of a failure in the instrumentation
or a  consistent mathematical insufficiency.
They are to be found (and corrected for!) by
repeating the analysis with different equip-
ment or by recalculation (by a colleague or
by different means).
(3) Random errors are the most common type of
errors. They are the result of the unavoidably
limited quality of our instrumentation. They
can only be partly overcome by refining
the instrumentation or the analytical method,
and by repeating the measurements (such as
reading a temperature or pH) or extending
the observation time (for instance, of radio-
activity).
13.2. Precision and accuracy
13.2.1. Definitions
It is important to distinguish between precision of
and accuracy.
(1) The precision of a result is a measure of
the reproducibility of an observation, of how
well the result can be determined, irrespec-
tive of how close the result is to the ‘true’
value. The associated ‘error’ is better re-
ferred to as the uncertainty of a result.
(2) The accuracy is a measure of the correctness
of an observation, of how close the result is
to the ‘true’ value.
The  two sets of definitions we have given are
simply related.
●● Precision is a measure of the size of random
errors. If we are able to reduce random er-
rors, for instance by better equipment or pro-
cedures, the precision of the measurement is
better, the result is more precise, and the anal-
ysis is more reproducible. Increasing the pre-
cision by reducing random errors is a task of
each single laboratory.
●● On the other hand, a systematic error direct-
ly effects the accuracy of the measurement;
avoiding or eliminating systematic errors
makes the result more accurate and trust-
worthy. Increasing the accuracy of a result is
often the goal of international intercompari-
sons by a  number of laboratories analysing
the same set of samples, and by routinely
running standards.
For studying and eventually reducing systematic
errors it is important to dispose of data with small
random errors, with relatively high precision. On
the other hand, it is a waste to spend much effort
on increasing the precision, if the systematic er-
ror is large. Fig. 13.1 illustrates the difference be-
tween precision and accuracy.
13.2.2. Significant figures and
digits
When reporting numbers it is a common rule to
indicate the  uncertainty by the  figures and dig-
its of the number given. If a distance is given
as 5000 km, it is common sense to trust only
the leftmost figure. However, if one is also certain
about the next figure (the leftmost 0), it is better
to write 5.0 × 103 km. In general, it is preferable
to write numbers in the scientific notation, i.e. an
 INTRODUCTION

argument in decimal notation with a number of
digits, multiplied by a power of 10. The rightmost
digit contains the uncertainty. As a rule the pre-
cision of the  uncertainty (i.e. the degree of cer-
tainty of the uncertainty) is not better than 10%
of the uncertainty. For example, if the radioac-
tivity of a sample is determined as 13.56 Bq, it
may go with an uncertainty of 13.56 ± 0.12 or
13.56 ± 0.08, but giving an additional digit in
the uncertainty like 13.56 ± 0.081 would exagger-
ate the “certainty of the uncertainty”.
The uncertainty also determines the number of
digits quoted. For instance, it is right to quote
13.56 ± 0.12 Bq, but it is not consistent to write
13.564 ± 0.12 Bq.
In computer calculations all digits are to be kept;
rounding off is done only with the  final result.
Nevertheless, results written down in the course
of a mathematical calculation are to be given with
the number of digits that can be justified. The en-
tire calculation itself, however, is to be carried out
without intermediate rounding off.
13.2.3. uncertainties
There are two different types of uncertainties.
(1) Instrumental uncertainties, due to fluctua-
tions in the result of any instrumental ob-
servation, whether it concerns measuring
the outdoor temperature or weighing your
letter on a letter balance, or applying fancy
equipment to measure time in the laboratory.
An estimate of the size of the uncertainty
can be obtained by an ‘educated guess’, or
by repeating the measurement and observe
the distribution of the results.
(2) Statistical uncertainties, due to the fact
that certain processes even theoretically
show fluctuations. A proper example here is
the process of radioactive decay. Even (non-

Fig. 13.1.  Example to illustrate precision and accuracy, showing two series of results from 19 measurements of
the same radioactivity.
A . The data are imprecise but accurate, giving the proper average value of 13.56 Bq. The grey area refers to
the 1σ confidence level; i.e. 68% of the data should be within this range (example in Sect. 13.5.2).
B. The data are precise, but inaccurate probably because of a systematic error, as the average value is now 13.50
Bq, instead of the ‘true’ value of 13.56 Bq.

146
 Chapitre 13errors, means and fits

(2) Les incertitudes statistiques,

existing) dues au fait
ideal equipment que certains
would observe processus, même
tain range théoriquement
xi and xi + Dx have been observed, is
montrent des fluctuations.
the  fluctuation inLathe décroissance radioactive estreferred
activity measurement, un exemple
to as caractéristique.
the sample distribution. The mean
or the ‘statistical
Même un équipement spread’
idéal (qui in pas)
n’existe the results. In des
observerait value is:
fluctuations dans la mesure
cases like these procedures exist to deter-
de l’activité, ou une dispersion « statistique des résultats ». 1Dans de tels cas, des
mine the uncertainty beyond doubt. x = ∑ N i xi ( ∆ x) and     N = ΣNi (13.4)
procédures existent pour déterminer l’incertitude au-delà du doute. N i      

13.3. Instrumental uncertainties If in making the histogram Dx or the class width

13.3 INCERTITUDES INSTRUMENTALESis chosen to be too large, nearly all data may be
13.3.1. Mean values within one column, suggesting a good statistical
certainty, but a bad resolution; if Dx is made too
13.3.1 The 
VALEURSmean or average value of the result of
MOYENNES small the resolution is increased, but few data fall
a number of measurements is defined as the sum
La valeur moyenne résultant
of the results d’unby
divided grand nombre of
the number mesures est within
demeasure- définie one
commecolumn and the reliability
la somme des appears to
be small (scattering histogram).
ments:
résultats divisé par le nombre de mesures:
1 N The more measurements have been carried out,
x ≡ ∑ xi ≡ ( x1 + x2 + x3 + ... + x N ) / N (13.1) the better is the impression of the distribution of
N1 i =1
N

x ≡ ∑ xi ≡ ( x1 + x2 + x3 + L + x N ) / N data around a certain(13.1)
mean value. For an infinite
N is Nthe number
i =1 of measurements, i stands for number of results with random errors the sample
the serial number of an arbitrary measurement
and xdeismesures,
N est le nombre the parameter measured.
i représente We will
le nombre often d’une mesure quelconque et x le
de séries
omit N and i = 1, and simply write Sxi.
paramètre mesuré. On ignore souvent N et i = 1, pour écrire simplement Σxi.
The number of measurements is always limited.
Le nombre However,
de mesures est toujours
if we would belimité. Cependant,
able to si on peut augmenter ce nombre à
increase this
l’infini, on obtiendra
number toune meilleure
infinity, valeurend
we would de up
la moyenne, définie alors ainsi
with a better
value of the mean, then defined as
1
μ ≡ lim ( ∑ xi ) (13.2) (13.2)
N →∞ N

The median is now defined as the value of the set
La médianeofest maintenant
data définie comme
such that the results of halflathe measure-
valeur d’un jeu de données en dessous de
ments is
laquelle se situent smaller,des
la moitié half is larger
mesures, thanmoitié
l’autre the median
étant plus élevée que la médiane. Dans
value. For a symmetrical distribution the mean
le cas d’une distribution symétrique la moyenne et la médiane sont équivalentes. Nous
and the median values are equal. We will later use
utiliserons un peu plus loin la déviation (écart) d’un résultat par rapport à la moyenne (ou la
the deviations of a single result from the mean
médiane), ⎯x(or −median), –x   − x ; byl’écart
xi; par définition moyen
definition des résultats
the average de- par rapport à la valeur moyenne
i
viation
est égal à zéro : of the results from the mean value equals
zero:
______ 1 NN 1 1 Fig. 13.2.  Histogram (block-shaped), indicating
xxi −−xx== 1∑ ∑ ( x(ix− −x)x=) = 1∑ xi −x −N1xN= xx =− xx =
∑ − 0x = 0
the  irregular distribution(13.3)of measurement results
i NN i =1
i =1 i N N
i N N
within a  range of xi(∆x) i.e. between xi and xi + ∆x
(13.3) around a  mean value; the  deviations from the  mean
value (x–  ) rather than the actual results are given along
with the  number of observations (y-axis) for values
13.3.2 DISTRIBUTION
13.3.2. DES DONNÉES
Distribution of data within a  certain range. The  smooth curve illustrates
Results of a number of measurements can be pre- the Gaussian distribution, which is the hypothetical re-
Les résultats d’un grand nombre de mesures peuvent être sult présentés sous forme d’un
of an infinite number of measurements. It also rep-
sented in a histogram, a graph showing the num-
histogramme, graphe indiquant le nombre de fois (axe des y) resents
que lesthe probability
résultats indiqués sur (P) of data around
distribution
ber of times (y-axis) certain results indicated the mean value. The deviations from the average value
l’axe des x ont ététhe x-axis
along obtenus (Fig.
were13.2).
obtained (Fig. 13.2). It is are given in terms of the standard deviation (σ).
obvious that the probability of obtaining results
On top of the graph the integral or summed
further removed from the most frequent result is probabilities are shown: the  probability of observ-
246 less and less probable. The histogram (or block ing values between –x   + σ and –x   − σ is 68%, between
diagram) consisting of columns representing –x  + 2σ and –x   − 2σ the chance is 95% and finally be-
the number of times (Ni) results xi(Dx) within a cer- tween x + 3σ and x − 3σ 99.7%.

147
 Chapitre 13
bonne certitude statistique, mais une mauvaise résolution; si Δx est choisi trop petit on
augmentera la résolution, mais peu de données tomberont dans la même colonne et la fiabilité
Si lorsqu’on
sera construit l’histogramme,
faible (histogramme dispersé). on donne à Δx ou la largeur de la classe une taille trop
forte, Presque toutes les données peuvent se trouver sur une seule colonne, suggérant une
Plus on aura de mesures, meilleure sera l’impression de distribution INTRODUCTION des données autour d’une
bonne certitude statistique, mais une mauvaise résolution; si Δx est choisi trop petit on
certaine valeur moyenne. Pour un nombre infini de résultats avec des erreurs aléatoires la
augmentera la résolution, mais peu de données tomberont dans la même colonne et la fiabilité
distribution distribution
des échantillons est représentée
is represented par une distribution
by a bell-shaped nor- en cloche normale
forme dethe better
deviation, the precision, the narrower
sera faible (histogramme dispersé).
ou Gaussienne, mal sur or Gaussian
laquelle ladistribution, in which the prob-
probabilité d’observer une valeur dethe Gaussian
y = yi à x = curve. xi est:
Plus on auraability
de mesures,of observingmeilleure a value y = yi at x = x
seraofl’impression i is:
de distribution des données autour d’uneset of measurements,
If we now consider the real
certaine valeur moyenne. Pour
⎧⎪ 1 ⎛uny nombre ⎞infini
2
⎫⎪ de résultats avec des erreurs
the standard aléatoires
deviation la is:
of the set
1 i − f ( xi )
distribution desP i = exp − ⎜
échantillons⎨ est2 ⎜représentée ⎟
⎟par (13.5)
⎬ une distribution en forme de cloche normale (13.5)
σ i 2π ⎪⎩ ⎝ σi ⎠ ⎪⎭ 1
ou Gaussienne, sur laquelle la probabilité d’observer une valeur de σ≡ y = yi à x∑ − x) 2
= x( xi iest: (13.8)
N −1
yi is the measured value of the dependent variable
yi est la valeury, f(x mesurée de la variable dépendante y, f(xi) est of la valeur
The fact de ythat calculée
N−1 pour instead la of N is inserted in
i) is the y value calculated for 2 the value
1 ⎧
⎪ 1 ⎛ y i − f ( xi ) ⎞ ⎫ ⎪ 2
σi is σ
the denominator 1
is (13.5)
discussed
plus( x − xin) 2 standard texts
Pvariable
valeur de lathe independent
i = dépendante ⎨− x⎜⎜ i, σxii,est
exp variable ⎟⎟déviation
la the standard
⎬ de- de
standard σ yx 2i, =que i l’on
x
= définira ∑ i
viation σ i of2πyi, to be ⎪ 2⎝
defined σlater. ⎠ ⎪
The most prob- on statistical
N analysis.
N ( N − 1 ) The necessity can be ap-
loin. La valeur la plus probable ⎩ que l’on observera,
i
⎭ le mode, correspond au pic de distribution,
able value to be observed, the mode, corresponds preciated by considering the extreme case of only
i.e. le haut de la courbe lissée. Pour les données avec des erreurs aléatoires σ xi la distribution 1A single est
to the peak of the distribution, i.e. to the top of one measurement. ( xmeasurement can give
ysymétrique
i est la valeur mesurée
autour du sommet.
the smooth
de la
curve. For
variable
La Fig. dépendante
data13.2withmontre random
y, f(x
la courbe ) est
errors deno
i σ
la Gauss
x
=
valeur de
ideaNavec
= y calculée
l’histogramme
N ( N − 1)
on the precision
∑
pour i − x)
la
2

of the measurement.
valeur
issu d’undenombre
lathe distribution
variable limité dépendante
de mesures. xi, σi est laaround
is symmetrical déviation the top. de yi, que the fraction
standardTherefore, l’on définira may plus not be a real number.
loin. La valeur la plusshows
Fig. 13.2 probable que l’on observera,
the Gaussian curve together le mode,
withcorrespond au pic de distribution, –
The possibility of calculating x   and σ is included
i.e. le haut dethe histogram
la courbe lissée. resulting Pourfrom a limitedavec
les données number of
des erreurs
13.3.3 DÉVIATION STANDARD inaléatoires
modern pocket la distribution
calculators. est
measurements.
symétrique autour du sommet. La Fig. 13.2 montre la courbe de Gauss avec l’histogramme
In Fig. 13.2 various confidence levels are indi-
issu d’un nombre
13.3.3.1 PRÉCISION limitéDES de DONNÉES
mesures.
cated. The probability that a random result of
13.3.3. Standard deviation
a measurement lies between –x   + σ and –x   − σ is
Il est évident que si les erreurs aléatoires sont faibles, les valeurs de la déviation (xi −⎯x) sont
13.3.3 DÉVIATION
13.3.3.1. STANDARD
Precision of data calculated to be 68%. This means that a repeated
petites et la distribution des résultats autour de la moyenne sera plus resserrée.will
measurement La déviation
result in a new result within ±σ
It is obvious that
moyenne est une mesure de l’étendue des données if random errors are
autoursmall,
de la moyenne,
of the mean:ce que l’on appelle deviation is the 68%
the standard
13.3.3.1 the values
PRÉCISIONofDES DONNÉES (x − –
the deviation x  ) are small and
la dispersion du jeu de données. L’ Eq. 13.3 a montré que l’on neconfidence
i
peut pas utiliser level, 2la σ simple
is the 95% confidence level,
the distribution of the results around the mean is
Il est évident
moyenne denarrower. que si
toutes les les erreurs aléatoires
déviations,deviation sont
une conséquence faibles, les
de la valeurs and
de 99.7%
la is
déviation the 3 (x σ confidence
−⎯x) sont level.
The average is a measure of définition de la moyenne. La i
petites et des
moyenne lathe spread
distribution
valeurs absolues of des
the datarésultats
desaround autour
déviations,the mean dei.e.laindépendamment
moyenne
or the so- sera plus resserrée.
de leur signe, La déviation
caractérise
moyenne
mieux estcalled
une mesure
la dispersion dispersion
: de l’étendue
of the data des données
set. Eq. autour 13.3 has de la moyenne, ce que l’onofappelle
13.3.3.2. Precision the mean
shown that we can not use the simple
la dispersion____du jeu de données. L’ Eq. 13.3 a montré que l’on In average of ne the preceding
peut pas utiliser la simplewe have been deal-
discussion
all
moyenne ded toutes deviations,
1 a consequence
lesx déviations, of the definition
une conséquence de la définition of
≡ ∑ i −x
ing with de la moyenne.
the precision (13.6)of La data, as characterised
the mean. The average
N absolues of the absolute values of
moyenne des valeurs des déviations, i.e. indépendamment by the standard
de leur signe, deviation.
caractérise It is equally important
the deviations, i.e. irrespective of their sign, char-
mieuxdes
Pour la dispersion
raisons
acterises :the dispersion
mathématiques cependant,
better: utiliser les valeurs absolues to reportn’est the pas uncertainty
approprié. in the  final outcome of
a number of measurements. Therefore, we have to
C’est pourquoi, ____ on1prend les carrés des déviations pour caractériser la distribution. La valeur
d ≡ 1 ∑ xxi − −x (13.6) calculate the precision of the mean value or, more
ainsi obtenuedest≡appelée N ∑ la x
i variance: specifically, the standard (13.6) deviation of the mean.
N
For mathematical reasons however, using ab- Below we will briefly discuss the propagation of
Pour des raisons mathématiques
⎡1 cependant, ⎛ 1utiliser
⎤ appropriate. 2 ⎞ les valeurs absolues n’est pas approprié.
σ ≡ lim ⎢ ∑ ( xi − μ )⎥ = lim ⎜ ∑ xi ⎟ − μ
solute
2 values is not Therefore,2
errors; i.e. the overall (13.7) uncertainty obtained from
C’est pourquoi, on
the squares N →prend
∞ N
⎣ of les carrés⎦ desN →déviations
the deviations ∞⎝ N
are taken to pour caractériser
⎠ charac- a number la distribution.
results, each La valeur
with its own uncertainty.
terise the distribution. The resulting value is re- σThe conclusion 1
ainsi obtenue
248
est appelée
ferred to as the variance:
la variance: ≡ ∑ i ( xis − that
x ) 2
the variance
N − 1 of the data set divided by the number
of a mean is
the variance 1
⎡1 ⎤ ⎛1 2⎞
σ measurements:
of ≡
N −1
∑ ( xi − x ) 2
σ ≡ lim ⎢ ∑ ( xi − μ )⎥ = lim ⎜ ∑ xi ⎟ − μ
2 2
(13.7)
N →∞ N
⎣ ⎦ N →∞ ⎝ N ⎠ σ xi 2 1
σ = ∑
2
= ( xi − x ) 2 (13.9)
(13.7)
x
N
σ 2 N ( N − 1)

1
248
∑ ( xi − x )
2 x
σx = i
= 2
The variance is thus the average of the squares σ xi N deviation
The standard N 1( N − 1)of the mean is then:
minus the square of the averages. The quantitative σ x = =
N ( N 1− 1)
∑ ( xi − x ) 2
measure of the size of the random errors, i.e. of σNx
the statistical spread of the data around the mean,
σx = i =
N N ( N − 1)
∑ ( xi − x ) 2 (13.10)

or in other words of the precision is now given
by the standard deviation σ, which is the square As an example we will calculate the mean
root of the variance. The smaller the standard and standard deviations of the data shown in

148
 Chapitre 13errors, means and fits
Erreurs, Moyennes et Ajustements
Erreurs, Moyennes et Ajustements
A titre d’exemple
TABLEnous calculerons
12.1.  Set of data la moyenne et les déviationsItstandards
is obvious pour
thatlesthe relative
données precision is bet-
corresponding to Fig. 13.1A. σ
ter 1
the higher
indiquées sur la Fig. 13.1A et le Tableau 13.1. On suppose que = 1 les données ont la rate and the larger
σ Rtoutes
R the counting
–   –   the measuring
R = Rt time.
même incertitude/précision.
No. xi xi − x Nr. xi xi − x R Rt
The  matter of confidence levels with observ-
1 13.55 −0.01 11 13.51 −0.05
Il est évident ingque data with statistical
la précision relativeuncertainties
est meilleureissisimilar
le taux de comptage es
2 13.45 −0.11 12 13.63 Il+0.07
est évident to que la précision relative
the instrumental est meilleure
uncertainties as si le taux
discussed inde lorsqu’on
comptage est
temps de mesure plus long. Le cas des niveaux de confiance
Tableau 13.1. Jeu de données correspondant à la Fig.13.1A. obs
3 13.57 +0.01 13 13.52
temps
−0.04
de mesure plus long.
the previous Le cas
section. des niveaux de
The probability confiance
that a ‘true lorsqu’on obser
avec les incertitudes statistiques est similaire à celui des incertitudes instru
value’ observed
avec les incertitudes in anest
statistiques infinite period
similaire of time
à celui des lies
incertitudes instrum
4 13.68 +0.12 14 13.55 −0.01 en avons discuté dans la partie précédente. La probabilité pour qu’un
nous between xi + σ and x i − σ of the measured
nous en avons discuté dans la partie précédente. La probabilité pour qu’une value
5
Nr. 13.63
xi xi+0.07
−⎯x Nr.
15
x13.45 −0.11
xi observée
−⎯x suris une
Nr.sur 68%: the standard
période
xi périodexi −⎯xde temps deviation is the 68%
infinie se situe entre confi-
x + σ et x − σ de l
i observée une de temps infinie se situe entre xi i+ σ et xi −i σ de la
6 13.47 −0.09 16 13.62 +0.06
est dence level, 2 σ is the 95% confidence
de 68%: la déviation standard est le niveau de confiance level, and 68%, 2σ
est de 68%:99.7% la déviation
is the 3 σ standard
confidence le niveau de confiance 68%, 2σ es
estlevel.
17 13.55
13.69 −0.01
+0.13 817 13.40 +0.18 15 95%,
13.74 −0.16
confiance 13.45
et 99,7%
99,7%−0.11correspondau auniveau
niveaude deconfiance
confiance3σ 3σ
confiance 95%, et correspond ..
28 13.45
13.40 −0.11
−0.16 918 13.56 +0.09 16
13.65 +0.00 13.62 +0.06
13.5. error Propagation
39 13.57
13.56 +0.01
+0.00 1019 13.52 13.5
−0.11 17
13.45 −0.04
13.5 PROPAGATION
13.74 +0.18 DEL’ERREUR
PROPAGATION DE L’ERREUR
410 13.68
13.52 −0.04 11
+0.12 13.51 −0.05 18 13.5.1.
13.65 Standard
+0.09 deviation
–  x = 13.56 We often want to determine a quantity A that is
5 Mean
Note: 13.63 +0.07 12 13.63 13.5.1
+0.07 DÉVIATION
13.5.1 19 a function
13.45
DÉVIATION STANDARD
−0.11STANDARD
Standard deviation σx = {Σ(xi − 13.56)}½/18 = ±0.095 of one or more variables, each with
6 σ of13.47
mean = σ−0.09 13 13.52 −0.04
On its own uncertainty. The uncertainty estof each of d’une
x/19 = ±0.022
On veut souvent déterminer une quantité
quantitéAAqui quiest une fonction d’uneououplus
plu
½
veut souvent déterminer une une fonction
7 13.69 +0.13 14 13.55 chacune
−0.01 these
avec sa variables
sa propre contributes
propre incertitude. to the overall
incertitude. L’incertitude
L’incertitudede uncer-
dechacune
chacunededeces cesvariab
varia
chacune avec
tainty. We will limit ourselves to give the math-
Moyenne ⎯x = 13,56 l’incertitude totale. Nous
l’incertitudeematical
totale. Nous nous limiterons
nous
expressions limiterons
for σ 2 àinà donner
donner
variouslesles expressionsmathéma
expressions
cases. mathém
Fig. 13.1A and Table 13.1. All data ½ are assumed
dans différents cas. Les
Les équations
équations repose surlalarelation
relation généralededelalafonction
fonctio
Déviation standard σx = {Σ(xi − 13,56)} /18 = ±0,095 The equations
dans différents cas. are based on sur
repose the general relation
générale
to have the same uncertainty/precision.
½
σ de la moyenne = σx/19 = ±0,022 for the function:
A == ff (x, y, z)
(x, y, z)
13.4. Statistical uncertainties A = f (x, y, z)
13.4 INCERTITUDES
Statistical uncertainties,STATISTIQUES Dans le
defined in Sect. 13.2.3, des
casIndes incertitudes
incertitudes
the case statistiques
statistiques
of statistical lala déviation
uncertainties déviation standarddedeAAdépend
standard
the standard dépe
arise from the random fluctuations in the number indépendantes deviation
x, yy et
x, deA depends
et zzofde manièreon
la manière
la the independent vari-
suivante:
suivante:
Les incertitudes statistiques,
of events, définies
for instance dans la
the number Part. 13.2.3, proviennent
of radioactive ables x, y anddes z as:fluctuations
aléatoires dudisintegrations per unit time,
nombre d’événements, rather than
par exemple from de désintégrations22 radioactives2 2
le nombre 22
a limited precision of the measuring equipment. 22⎛⎛∂ ∂AA⎞⎞ 22⎛⎛∂∂ AA⎞⎞ 2 2⎛⎛∂∂ AA⎞ ⎞
par unités de temps, plutôt que d’une précision limitée des instruments σ AA22 ==σσ xde
x ⎜⎜ mesure.
⎟⎟ +
+ σσPour⎜⎜
yy ⎜⎜ ⎟
ces⎟
⎟⎟ ++σ σzz ⎜ ⎜ ⎟ ⎟ (13.14)
For these statistical fluctuations the  theory of ⎝⎝ ∂∂xx ⎠⎠ ⎝⎝∂∂yy⎠⎠ ⎝⎝∂∂zz⎠ ⎠
fluctuations statistics
statistiques la théorie
provide des statistique
the mathematical fournit for
technique une technique mathématique pour
décrire la distribution
describing des données
the data et la déviation
distribution standard. Le Ifrésultat
and the standard the uncertainties
est que la déviation are estimated instrumental
Si les incertitudes
incertitudes sont
sont considérées
uncertainties, considérées
similar comme
commeare
equations instrumentales,
to be used fordes
instrumentales, deséquations
équationssims
standard de deviation. The result is
plusieurs comptages M that the standard
détectés durant undeviation
intervalle de temps t est simplement :
of a number of counts M detected duringêtre utiliséescalculating
a time pour
pour calculer
calculer l’incertitude
the uncertainty
l’incertitudein du résultat
résultatfinal.
duthe final final.Pour
result. Forlalarelation
Pour relationgénéra
géné
the general relation:
σ = M½ t is simply:
interval (13.11)
A f(x, y,
A == f(x, y, z)z)
σ = M½ (13.11) A = f(x, y, z)
Pour un taux de comptage R, i.e. le nombre de coups par seconde, la déviation standard est
For the counting rate R, i.e. the number ofavec avec les
les incertitudes
counts instrumentales
with the estimated
incertitudes instrumentales Δx,
Δx,Δy
instrumental Δz,
Δyetetuncertainties
Δz,l’incertitude
l’incertitudeDx,enenAAestest: :
alors: Dy and Dz, the uncertainty in A is:
per second, the standard deviation then is:
2 2 2
1 1 R 2 2 ⎛⎛∂ ∂AA⎞⎞ 2 2 ⎛⎛∂∂ AA⎞⎞ 2 2 ⎛⎛∂∂ AA⎞ ⎞ 2
σ R = M = Rt = (13.12) Δ A = Δ x
ΔA = Δx ⎜⎜ ∂x ⎟⎟ + (13.12)
2 2 + Δ y ⎜ ⎟ + Δ z
Δy ⎜⎜⎜∂y ⎟⎟⎟ + Δz ⎜⎜∂z ⎟ ⎟
2 2
t t t ⎝⎝ ∂x ⎠⎠ ⎝⎝ ∂y⎠⎠ ⎝⎝ ∂z⎠ ⎠

Erreurs,
of Moyennes et Ajustements
L’incertitudeThe relative uncertainty
relative du taux de comptage the counting
est donnée rate is
par: (13.15)
given by: débouchant sur
débouchant sur les les équations
équations équivalentes
équivalentes pour
pourfor ΔAΔADA etet σσ
A (Eqs. 13.16–13
resulting in the equivalent equations as A (Eqs. 13.16–1
σR 1 exemples aa et
exemples et bbσsont
sont des des coefficients,
coefficients, xxetetyysont des
desvariables
variablesindépendante
for A in the Eqs.13.16  – 13.19. Insont these exam- indépendant
= (13.13)
dépendante. (13.13)
R Rt dépendante. ples a and b are constant coefficients, x and y are
250 the independent variables, A the dependent vari-
able.
Il est évident que la précision relative est meilleure si le taux de comptage est plus élevé et le
temps de mesure plus long. Le cas des niveaux de confiance lorsqu’on observe les données
avec les incertitudes statistiques est similaire à celui des incertitudes instrumentales comme 149
nous en avons discuté dans la partie précédente. La probabilité pour qu’une valeur “réelle”
observée sur une période de temps infinie se situe entre xi + σ et xi − σ de la valeur mesurée
 Erreurs, Moyennes et Ajustements

Chapitre 13 σx2 = 1 / Σ(1/σi)2 = 1 / [N(1/σi)2] = σi2 / N or σx = σi / N½

Chapitre 13INTRODUCTION

(1) A = ax + by et A = ax − by avec les incertitudes σx et σy; dans les deux cas:

(1) A = ax A =
(1) + by ax et A+ =byaxand − by A =avec
ax -lesbyincertitudes σx et σy; 13.6. Least-squares
with uncertain- dans les deux cas: fit
2 ties 2 σ 2 and2σ ;2 in both cases:
σA = a σxx + b σyy 13.6 AJUSTEMENT
A measured quantity PAR
(13.16)
is often LES MOINDRES
related to some CARRES
σA2 = a2σx2 + b2σy2 other variable, for instance (13.16) y = f(x). This func-
Une quantité tionmesurée estany souvent reliéeasà linear,
une autre variable, par exempl
(2) A = ± a σ xy et AA ==±aaσx/y x + b σy (13.16)
2 2 2 2 2
may have form such quadratic,
(2) A = ± a xy et A = ± a x/y fonction peut harmonic, arbitrary, et
être de n’importe cetera.
qu'elle forme,The subject
linéaire,ofquadratique,
this harmoni
(2) A = ± a xy et2 A = ± a x/y section is to briefly discuss methods
cetera. L’objet de cette partie est de discuter brièvement des méthod to obtain
σ A2 σ x
2
σy the most probable graphical and algebraic adjust-
2 σ
= 2
2 σ
+ 2
2 σy
2
l’ajustementment graphique et algébrique (13.17)le plus probable d’une fonction aux d
A A x = y+ x (13.17) of a function to the data.
(13.17)The major interest
A 2
x 2
y 2
intéressant est
is l’ajustement
the adjustment des
of données
a straight à droite
line d’un grand
to a number of nombre de d
bx data, which
suppose reliées linéairement. are expected to be linearly related.
(3) A = a e±(3) A
± bx= a e
± bx
(3) A = a e
σA/A σ =x± bσx (13.18) 13.6.1 13.6.1.
AJUSTEMENT Fit to a straight
LINÉAIRE line
=A ±/Abσ (13.18)
σA/A = ± bσx (13.18) fitting is to mini-
Le principeThe  principle ofpar
de l’ajustement least-squares
les moindres carrés est de minimiser la somm
(4) A = a ln(± bx) mise the sum of the squares of the deviations of
(4) A = a ln(± bx) déviations des variables dépendantes (y) (l’incertitude en x est supposée nég
(4) A = a ln(± bx) the dependent variable (y) (the uncertainty in x is
σA = a σx/x (13.19) d’une droiteassumed
présentant to des coefficientsfrom
be negligible) a et b: the straight line
σA = a σx/x with coefficients a and b: (13.19)
σA = a σx/x (13.19)
y = a + bx
13.5.2. Weighted mean y = a + bx (13.22)
13.5.2 MOYENNE PONDÉRÉE La déviation de toute valeur from de y (yiany ) à la value
droite est
13.5.2 Till now,MOYENNE when calculatingPONDÉRÉE average values, we The deviation of donnée
y (yi) par
to
Jusqu’à présent
havelorsqu’on
considered a calculé
all numbers les valeurs
to havemoyennes,
the same the straight line
nous avons considéré que tous lesis given by
Jusqu’à présent lorsqu’on a calculé les valeurs moyennes, nous avons considéré que tous les
precision
nombres avaient la même and thus to have et
précision the same weight.
ainsi qu’ils Δyi = ypoids
If we le même
avaient i − f(x. i)Si= yon a − bxi à
i − affecte
nombres avaient la même précision et ainsi qu’ils avaient ∆y = yi − f(x
le i même i) =. ySi
poids i − ona − affecte
bxi (13.23) à
assignnombre
chaque à chaque to each sa number
propreitsdéviation
own standard deviation,
standard, la moyenne doit alors être calculée de
chaquethe mean
à chaqueisnombre then tosa bepropre déviation
calculated standard,
according la moyenne
Ento:minimisant doit alors
la somme
Minimising êtreof
de ces
the sum calculée
déviations deon obtient:
these deviations results in:
la façon suivante:
la façon suivante: xi
∑ σx2i x ΣΔyii == 0
Σ∆y 0 (13.24)
x = ∑ σi∑ 2 i
(13.20)
1i σ 2 while applying the absolute values of Dyi does
x=∑ xσ =12 i (13.20)
(13.20)
Tandis not
qu’utiliser result
les into
valeurs a useful
absolues mathematical
de Δyi ne fournitproce- pas une approche ma
∑ σi∑ 2
1
dure. Therefore, we are looking for a procedure
i σ i2 C’est pourquoi, nous recherchons une démarche pour trouver les coef
while the standard deviation of the meancaractérisant is ob- to find the  coefficients a and b, characterising
tandistandis
que laquedéviation la
dedroite,
: de : par laquelle la somme
the sumdes of carrés des déviations:
tained from:standard
la déviation standard de lade moyenne
la moyenneest obtenue
est obtenue à the straight
à partir
partir line, by which the squares
of the deviations:
1 1 ⎛ 1 ⎛⎞ 1 ⎞ Σ(Δyi)2 = Σ(yi − a − bxi)2
= ∑ ⎜⎜= 2 ⎜⎟⎟ ⎟
σ x σ 2 ⎝ σ∑
2
⎜ 2⎟
i ⎠σ
Σ(∆yi)2 = Σ(yi − a − bxi)2 (13.25)
x ⎝ i ⎠
est minimisée. Les conditions
is minimised. d’ajustement
The matching sont: are:
conditions
ce quicedonne:resulting
qui donne: in:
∂
1 1 Σ( yi − a − bxi ) 2 = 0 and
et
σ x =σ x = (13.21) ∂a (13.21)
(13.21)
∑ (1∑ / σ i(1) 2/ σ i ) 2
∂
∂b ∑ i
( y − a − bxi ) = 0 2
(13.26)
Le poids de chaque résultat est inversement proportionnel au carré de la déviation
standard; Chapitre 13
Le poids de chaqueofrésultat
The weight each result est inversement proportionnel au carré de la déviation standard;
is inversely proportion- Chapitre 13
2
1/σ est 2 al to the square of the standard deviation;Les
1/σappelé le facteur
est appelé le facteurde pondération.
de pondération. 1/σvaleurs
2
is The resulting
de a et de b obtenues values ofont: a and b are:
referred to as the weighting factor. 1 ⎛⎜⎛ xxi 2
2
yyi xxi xy ⎞
Si lesSidéviations
les déviations standard standard σi sont égales,
σi sont l’expression
égales, l’expression σade
pourpour = de⎜ ∑
σ 1la i ∑ se
moyenne
la moyenne ∑
i réduit
se
− ài2 ∑
réduit à xii y2ii ⎟⎞⎟ (13.27a)et
If the standard deviations σi are equal, the expres- a = Δ ⎜ ∑σ 2 ∑σ 2 − ∑σ 2 ∑ σ 2 ⎟
2 2 et
l’Eq. l’Eq.
13.10:13.10: Δ ⎝⎝ σ ii σ ii σ ii σ ii ⎠⎠
sion for σ of the mean reduces to Eq. 13.10:
and
252 252 1⎛ 1 xy x y ⎞
σx2 = 1 / Σ(1/σi)2 = 1 / [N(1/σi)2] = σi2 / N bb == 1 ⎜⎜⎛ ∑ 12 ∑ xii y2ii −− ∑ xii2 ∑ yii2 ⎟⎟⎞ (13.27b)
Δ
Δ ⎝⎝⎜ σ
∑ σ i 2 ∑ σσ i 2 ∑ σσ i 2 ∑ σσ i 2 ⎠⎟
or σx = σi / N½ i i i i ⎠

tandis
tandis queque
150 xxi 2 ⎛⎛
2
xxi ⎞⎞ 2
2
11
Δ =∑∑ σσ i 22 ∑
∑ σσ i 22 − ⎜⎝⎜∑
Δ = − ⎜ ⎟
i
∑ σσ ii22 ⎟⎠⎟
i i ⎝ i ⎠
 a = Δ1 ⎜⎝⎛⎜⎜ ∑ σxii 2 ∑ σy − ∑ σxiii2 ∑ x y ⎟⎞⎟
2 i2 2 i 2i
σ et (13.27a)
a = Δ ⎜∑σ 2
Δ ⎝⎝ σ ii
∑ σσ i i2
i2
− ∑σ 2
σi
∑ σσ ⎠⎟⎠⎟
i i 2i
i2
fonction et de probabilité de Gauss (13.27a) de l’Eq. 13.5, i.e. de la somme des déviations
i i i ⎠
entre les valeurs y observées (yi) et les valeurs y calculées à partir de la relati
1 ⎛⎜ 1 xi y i xi yi ⎞ y = f(xi).
b = 1 ⎜⎛ ∑ 12 ∑ xi y2i − ∑ xi2 ∑ yi2 ⎟⎟⎞ (13.27b)
b = Δ1 ⎝⎜⎛⎜ ∑ σ1i 2 ∑ σ xi iy2i − ∑ σxii2 ∑ σyi i2 ⎠⎟⎞errors, means and fits (13.27b)
b = Δ ⎜∑σ 2 ∑ σ 2 − ∑σ 2 ∑σ 2 ⎟ ⎟ (13.27b)
Δ ⎝⎝ σ ii σ ii σ ii σ ii ⎠⎠
tandis que
tandis que while computer programmes. These also exist for com-
tandis que
x
2
⎛ x ⎞2
2
posite curves, consisting of the superposition of
1
Δ = ∑ 12 ∑ xii 22 − ⎜⎜⎛ ∑ xii2 ⎟⎟⎞ 2 (13.27c) more than one curve. (13.27c)
Even through data points,
Δ = ∑ σ1i 2 ∑ σxi 2 − ⎝⎜⎛⎜ ∑ σxii2 ⎠⎟⎞⎟ (13.27c)
Δ = ∑σ 2 ∑σ 2 − ⎜∑σ 2 ⎟ which are not theoretically (13.27c) related to the indepen-
σ ii σ ii ⎝ σi ⎠ dent variable, curves can be fitted. One example
⎝ i ⎠
If the standard deviations of y are equal, the val-
Si les déviations standards de y sont égales, les valeurs de a et de isb sont: the cubic spline. In principle cubic (3rd order)
ues a and b are:
Si les déviationsofstandards de y sont égales, les valeurs de a et defits b sont:
Si les déviations standards de y sont égales, les valeurs de a et de b sont: through successive group of data are adjusted
a = (Σxi222 Σyi − Σxi Σxiyi) / Δ to each other. The resulting (13.28a)curve can be chosen
a = (Σx
(Σxii2 ΣyΣyii −− ΣxΣxii ΣxΣxiyiyi)i)//∆ (13.28a)
Δ to fit all data points, (13.28a)
as well as chosen to smooth
a = (Σx Σy − Σx Σx y ) / Δ (13.28a)
b = (N Σi xiyi i− Σxi iΣyi)i /i Δ irregularities as much as wanted. (13.28b)
b = (N(N ΣxΣxiyi −− Σx Σxi Σy Σyi)) // ∆ (13.28b)
Δ (13.28b)
b = (N Σx2iiyii − Σxii 2Σyii) / Δ (13.28b)
Δ = N Σx − ( Σx )
∆ = N Σxii 2 − (Σxii) 2 (13.28c)
2 2 (13.28c)
Δ = N Σxi2 − (Σxi)2 (13.28c)
Δ = N Σxi − (Σxi) 13.7. Chi-square(13.28c) test
Beaucoup de calculateurs de poche
Many modern pocket calculators have the pos- récents ont la possibilité de calculer l’ajustement des
Beaucoup de calculateurs de poche récents ont la possibilité The  de calculer
least-squares l’ajustement fit is des
based on minimising
Beaucoupcarrés
moindres de calculateurs
sibilityà une ofdroite. de Un
calculatingpocheexemplerécents
the  se ont la sur
trouve
least-squarespossibilité de calculer
lafitFig. 13.3. Les déviationsl’ajustement standard des
moindres carrés à une droite. Un exemple se trouve sur la Fig. 13.3. Les déviations standard
moindres
des to the straight
carrés
coefficients aàetune droite.
b sont: line.Un An exempleexample se trouve sur lainFig. 13.3. Les déviations standard probability func-
is shown the exponential of the Gaussian
des coefficients a et b The 
Fig. 13.3. sont:standard deviations of the  coeffi- tion of Eq. 13.5, i.e. of the sum of the (quadratic)
des coefficients a et b sont:2 Fig. 13.3. Ajustement linéaire des moindres carrés sur de nombreuses données (x,y), à
cients a and 1 b x are: deviations between the observed y values (yi) and
σ a = 1 ∑ xii 22 les
the y variables
values indépendantes
calculated (13.29a) et dépendantes
from the relation sont reliées par l’équation
between
σ a = Δ1 ∑ σxi 2 valeurs).y ont(13.29a)(13.29a)
σa = Δ ∑σ 2 (13.29a)
Toutes
y and x:lesy = f(x i
la même précision.
Δ σ ii
et For the  straight line fit this comes to calcu-
et
et and Pour l’ajustement the 
lating coefficients
linéaire ceci revient of the  linear les
à calculer relation
coefficients de la r
1 1 y = a + bx for which the sum S(y – a – bxi)2 is
σ b = 1 ∑ 12 (13.29b)
y = a + bx pour laquelle la somme Σ(yi − a − bxi) est minimale (Eq. 13.25). En
i 2
σ b = Δ1 ∑ σ1i 2 minimal (Eq. 13.25).(13.29b) In view of the definition of
σb = Δ ∑σ 2 (13.29b)
définition de la probabilité, P (13.29b)
i, itil logical
est logique de the same
prendre lasum même somme t log
Δ σi i the probability, P i, to take
same sum of the squaredeviations
of the square deviationsinenrelation relation avec la déviation standard
to the standard
13.6.2 AJUSTEMENT NON LINÉAIRE deviation asdeviation
a measureasfor a measure
the goodness for the goodness
of fit: of fit:
13.6.2 AJUSTEMENT
13.6.2. NON LINÉAIRE
Fit to non-linear curves
13.6.2 AJUSTEMENT NON LINÉAIRE
L’ajustement des moindres carrés, par exemple, les courbes quadratiques ou polynomiales 2 de
L’ajustement desleast-squares
The  moindres carrés, fit to,parforexemple,
instance, lesquadratic
courbes quadratiques N
⎛ ou a − bxi ⎞
yi −polynomiales de
L’ajustement
second degré,des
or
moindres carrés,
exponentielles
second-degree
par exemple,
et arbitraires,
polynomial,
ne les courbes
seront
harmonic, expo-
second degré, exponentielles et arbitraires, ne seront pas traitées quantitativement.
traitées2
pas quadratiques ∑
χ = quantitativement.
⎜⎜ ou polynomiales
i =1 ⎝ σ
⎟⎟ Elles
Elles
de (13.30)
second degré,
peuvent exponentielles
êtrenential
calculées et curves
analytiquement, arbitraires, maisne la seront
démarchepas normale
traitées quantitativement. i
consiste à utiliser ⎠ Elles
les
peuvent être and arbitrary
calculées analytiquement, will
maisnot la be treated
démarche normale consiste à utiliser les
peuvent être
programmes calculées analytiquement,
informatiques
quantitatively. appropriés.
These can beIls mais la démarche
existent
calculated également
analyti-
Pour normale
le jeu pour
For
de consiste
les
the set
données courbes àFig.
deofladata utiliser
combines,
in Fig. 
13.3 etles13.3
du and Table 
Tableau 13.2 le χ2 est calculé.
13.2
programmescally, informatiques
but the normal appropriés. isIls existent également the  pour χ2 les courbes combines,
programmes
consistant en lainformatiques
superposition deroutine
appropriés.
plus d’une Ilsto courbe.
apply
existent the proper
également
Même à partirpourdes is
les calculated.
points,courbes
qui necombines, sont pas
consistant en la superposition de plus d’une courbe. Même à partir des points,optimum
En résumé l’ajustement qui ne sont auxpas données est celui qui minimise χ2. L
consistant
reliés en la superposition
théoriquement à une variable de plus d’une courbe.
indépendante, lesMême
courbes à partir
peuvent desêtre points, qui
ajustées.
2
ne Le sont pas
spline
reliés théoriquement à une variable indépendante, lespermet courbesdepeuvent
minimiser être χajustées.
est la Le méthode spline des moindres carrés. Le résultat du
reliés théoriquement
cubique en est un exemple. à une variable En principe indépendante, les courbes
les ajustements peuvent
cubiques (3ème
2
être ajustées.
ordre) à Le partir spline
de
cubique en est un exemple. En principe les ajustements rassurant si le χ(3ème
cubiques divisé par le
ordre) nombre
à partir de de données (=19) moins le degré d
cubique successifs
groupes en est un de exemple.
données, Ensont principe
ajustésleslesajustements
uns aux autres. cubiques
La courbe(3èmerésultante
ordre) à peut partirêtre de
groupes successifs de données, sont ajustés les uns aux nombre
autres.de La
paramètres à déterminer,
courbe résultante peuticiêtre = 1) est environ égal à un (dans ce cas
groupespour
choisie successifs
ajusterde tousdonnées,
les points, sontouajustés
choisielespour unslisser
aux autres. La courbeautant
les irrégularités résultante
que désiré. peut être
choisie pour ajuster tous les points, ou choisie pour lisser les irrégularités autant que désiré.
choisie pour ajuster tous les points, ou choisie pour lisser les irrégularités autant que désiré.

254
254
254

Fig. 13.3.  Linear least-squares fit through a number of (x,y) data sets, of which the independent and dependent
variables are related by the equation y = 2.5 + 0.5x. All y values have the same precision.

151
 INTRODUCTION

TABLE 12.2.  Series of (xi, yi) data sets In summary, the optimum fit to data is that which
obeying the relation y = a + bx, minimises χ2. The method by which χ2 is mi-
resulting in a value of c2. nimised is the least-squares method. The result
of a χ2 test is reassuring, if the χ2 divided by
x yi ± σ y = 2.5 + 0.5xi [y − f(xi)]2/σ2 the number of data ( = 19) minus the degrees of
1 2.9 ± 0.8 3.0 0.016 freedom (= the number of parameters to be de-
termined, here = 1) is about equal to one (in this
2 2.4 ± 0.8 3.5 1.891
case = 12/18).
3 4.1 ± 0.8 4.0 0.016
4 5.7 ± 0.8 4.5 2.250
5 5.7 ± 0.8 5.0 0.766
6 4.6 ± 0.8 5.5 1.266
7 7.3 ± 0.8 6.0 2.641
8 4.9 ± 0.8 6.5 4.000
9 7.0 ± 0.8 7.0 0.000
10 7.1 ± 0.8 7.5 0.250
11 7.5 ± 0.8 8.0 0.391
12 9.2 ± 0.8 8.5 0.766
13 8.6 ± 0.8 9.0 0.250
14 9.4 ± 0.8 9.5 0.016
15 8.9 ± 0.8 10.0 1.891
16 11.1 ± 0.8 10.5 0.563
17 12.8 ± 0.8 11.0 5.063
18 12.4 ± 0.8 11.5 1.266
19 10.9 ± 0.8 12.0 1.891
χ2 12.094

Note: The graph for these data is shown in Fig. 13.3. The op-

timum fit to the data is that which minimises χ2.

152
Symbols and units

a [CO2aq] = concentration GM Geiger Müller counter

dissolved CO2 g gamma “particle”/radiation
a year h relative humidity
y
a activity ratio (y mass number, e.g. h hour
14
a) I electric current
aq dissolved IAEA International Atomic Energy Agency
A (atomic) mass number IRMS isotope ratio mass spectrometer
A absolute (radio)activity (e.g. 14A) J Joule
AMS accelerator mass spectrometer keV kiloelectronvolt = 103 eV
αl/v fractionation factor (l rel. to v) K equilibrium/acidity constant
αk kinetic fractionation factor K degree Kelvin
α alpha particle LSS liquid scintillation spectrometer
b [HCO!] = concentration l (radioactive) decay constant
dissolved bicarbonate m mass
B magnetic field m meter
B background counting rate min minute
Bq Becquerel = 1 disintegration×s-1 mol symbol for mole
b beta particle mole number of grams equal to molar
c [CO  3 ] = concentration
 -
2
weight
dissolved carbonate ions M molar weight, mole
0
C degree centigrade MeV millionelectronvolt = 106 eV
CT concentration dissolved inorganic MS mass spectrometer
carbon MWL meteoric water line
C3 Calvin photosynthesis m reduced mass
C4 Hatch-Slack photosynthesis n neutron
CAM Crassulacean Acid Metabolism N neutron number
Ci Curie = 3.7 × 1010 dps N amount
Cl chlorinity (in g of chloride per kg of NBS National Bureau of Standards
water = ‰) NIST National Institute of Standards
d deuterium excess of MWL and Technology, USA
d day = 8.6400 × 105 s n neutrino
dpm disintegrations per minute n frequency
dps disintegrations per second Ox oxalic acid (14C standard)
D diffusion constant/coefficient p pressure
DIC dissolved inorganic carbon p proton
DOC dissolved organic carbon pH = -10log [H+]
x
δ relative isotope ratio (e.g. 13δ) pCi picoCurie = 10-12 Ci
(defined from xR) pMC percent Modern Carbon
y
δ relative activity ratio (e.g. 14δ) P probability
(defined from yA or ya) PDB PeeDee Belemnite
E energy PGC proportional gas counter
EB binding energy q partition function
EC electron conversion q electric charge
ε fractionation (constant) (enrichment/ Q nuclear reaction energy
depletion) r radius
εk kinetic fractionation (constant) x
R isotope ratio (x mass number, e.g.
f fraction 13
R)
F force s second
g gram s slope of MWL = 8

153
sp spallation
S salinity (in g of salt per kg of water
= ‰)
SLAP standard light Antarctic precipitation
SMOW standard mean ocean water
STP standard temperature and pressure
(0oC, 1 atm)
s standard deviation
S total inorganic carbon
concentration = CT
t time
t temperature (in oC)
T absolute temperature (in K)
T1/2 half-life
TU tritium unit ≡ [3H]/[1H] = 10-18
= 0.118 Bq/L
q exponent in fractionation factor ratio
for (DM=2)/(DM=1)
t mean life
v velocity
V volume
V volt
VPDB Vienna-PDB
VSMOW Vienna-SMOW
Z atomic number

154
Literature

Moser, H., Rauert, W.,  Isotopenmethoden in der Hydrologie, Gebr. Borntraeger, Berlin, Stuttgart. (in German
language) (1980).

Fritz, P.,  Handbook of Environmental Isotope, Elsevier Science.

Fontes, J.Ch., Geochemistry ISBN, Amsterdam, Oxford, New York, Tokyo, Vol. 1. The Terrestrial
Environment A (1980).

Fontes, J.Ch., Geochemistry ISBN, Amsterdam, Oxford, New York, Tokyo, Vol. 2. The Terrestrial
Environment B (1986).

Fontes, J.Ch., Geochemistry ISBN, Amsterdam, Oxford, New York, Tokyo, Vol. 3. The Marine
Environment A (1989).

Pearson, F.J.,  et al., Applied Isotope Hydrogeology: A case study in Northern Switzerland, Elsevier Science
Publ., New York, Tokyo (1991).

Clark, I., Fritz, P.,  Environmental Isotopes in Hydrogeology, Lewis Publishers, Boca Raton, New York (1997).

F.Gasse, Causse, Ch.,  Hydrology and Isotope Geochemistry, Editions de l’Orstom, Paris.

Kaess, W.,  Tracing in Hydrogeology, Balkema (1998).

Kendall, C., McDonnell, J.J.,  Isotopes in Catchment Hydrology, Elsevier/North, Holland Publ.Comp.,
Amsterdam (1998).

Mazor, E., Chemical and Isotopic Groundwater Hydrology — The applied approach, Marcel Dekker Inc.,
(1998).

Cook, P.G., Herczeg, A.L.  (Eds), Environmental Tracers in Subsurface Hydrology, Kluwer Acad. Publ., (2000).

Friedlander, G., Kennedy, J.W., Macias, E.S., Miller, J.M., Nuclear and Radiochemistry, John
Wiley & Sons, New York, Chichester, Brisbane, Toronto (1981).

Faure, G.,  Principles of Isotope Geology, John Wiley & Sons, (1986).

IAEA publications

IAEA Conference Proceedings

Radioisotopes in Hydrology, Tokyo, 5–9 March 1963, IAEA, Vienna (1963) 459 pp.

Isotopes in Hydrology, Vienna, 14–18 November 1966, IAEA, Vienna (in co-operation with iugg, (1967) 740 pp.

Isotope Hydrology, Vienna, 6–13 March 1970, IAEA, Vienna (in co-operation with unesco), (1970) 918 pp.

Isotope Techniques in Groundwater Hydrology, Vienna, 11–15 March 1974, IAEA, Vienna, 2 volumes (1974) 504
and 500 pp.

Isotope Hydrology (in 2 volumes), Neuherberg, Germany, 19–23 June 1978, IAEA, Vienna, (in co-operation with
unesco), 2 volumes (1979) 984 pp.

Isotope Hydrology, Vienna, 12–16 September 1983, IAEA, Vienna, (in co-operation with unesco), (1983) 873
pp.

155
Isotope Techniques in Water Resources Development, Vienna, 30 March–3 April 1987, IAEA, Vienna, (in co-
operation with unesco), (1987) 815 pp.

Isotope Techniques in Water Resources Development, Vienna, 11–15 March 1991, IAEA, Vienna, (in co-operation
with unesco), (1992) 790 pp.

Isotope Techniques in the Study of Past and Current Environmental Changes in the Hydrosphere and the
Atmosphere, Vienna, 19–23 April 1993, IAEA, Vienna (1993) 624 pp.

Isotopes in Water Resources Management (in 2 volumes), IAEA, Vienna, 20 – 24 March 1995, IAEA, Vienna, 2
volumes (1995) 530 and 463 pp.

Isotope Techniques in the Study of Environmental Change, Vienna, 14 – 18 April 1997, IAEA, Vienna (1998)
932 pp.

Isotope Techniques in Water Resources Development and Management, 10 – 14 May 1999, IAEA, Vienna (1999)
CD-ROM.

Special IAEA symposia

Radioactive Dating and Methods in Low-Level Counting, Monaco, 2 – 10 March 1967, STI/PUB/152, IAEA,
Vienna (1967) 744 pp.

Behaviour of Tritium in the Environment, San Fransisco, USA, 16 – 20 October 1978, STI/PUB/498 (1979) 711 pp.

Methods of Low-Level Counting and Spectrometry, Berlin, Germany, 6 – 10 April 1981, STI/PUB/592, IAEA,
Vienna (1981) 558 pp.

IAEA Reports and Technical documents (tecdocs)

Environmental Isotope Data No.1 – No.10: World Survey of Isotope Concentration in Precipitation, Data from
network of IAEA and WMO over period 1953 – 1991 (1969 – 1994).

Interpretation of Environmental Isotope and Hydrochemical Data in Groundwater Hydrology, Proc. Adv. Group
Meeting, Vienna, 27 – 31 January 1975, STI/PUB/429, IAEA, Vienna (1976) 230 pp.

Isotopes in Lake Studies, Proc. Adv. Group Meeting, Vienna, 29 August – 2 September 1977, IAEA, Vienna (1979)
290 pp.

Arid Zone Hydrology: Investigations with Isotope Techniques, Proc. Adv. Group Meeting, Vienna, 6 – 9 November
1978, STI/PUB/547, IAEA, Vienna (1980) 265 pp.

Stable Isotope Standards and Intercalibration on Hydrology and Geochemistry, (Gonfiantini, R., Ed.), Report
on Consultants’ Meeting, Vienna, 8 – 10 September 1976, IAEA, Vienna (1977).

Stable Isotope Hydrology Deuterium and Oxygen-18 in the Water Cycle, (Gat, J.R., Gonfiantini, R., Eds),
Monograph by Working Group, STI/DOC/10/210, IAEA, Vienna (1981) 340 pp.

Palaeoclimates and Palaeowaters: A Collection of Environmental Isotope Studies, Proc. Adv. Group Meeting,
Vienna, 25 – 28 November 1980, STI/PUB/621, IAEA, Vienna (1981) 207 pp.

Guidebook on Nuclear Techniques in Hydrology, by Working Group IAEA, STI/DOC/10/91/2, Vienna (1983)
439 pp.

Stable Isotope Reference Samples for Geochemical and Hydrological Investigations, (Gonfiantini, R., Ed.),
Report by Advisory Group’s Meeting, Vienna, 19 – 21 September 1983, IAEA, Vienna (1984).

156
Stable and Radioactive Isotopes in the Study of the Unsaturated Soil Zone, Proc. Meeting on IAEA/GSF Progr.,
Vienna, 10 – 14 September 1984, TECDOC-357, IAEA, Vienna (1985) 184 pp.

Isotope Techniques in the Study of the Hydrology of Fractured and Fissured Rocks, Proc. Adv. Group Meeting,
Vienna, 17 – 21 November 1986, TI/PUB/790, IAEA, Vienna (1989) 306 pp.

Stable Isotope Reference Samples for Geochemical and Hydrological Investigations (Hut, G., Ed.), Report on
Consultants’ Meeting, Vienna, 16 – 18 September 1985, IAEA, Vienna (1987).

Use of Artificial Tracers in Hydrology, Proc. Adv. Group Meeting, Vienna, 19 – 22 March 1990, TECDOC-601,
IAEA, Vienna (1990) 230 pp.

C-14 Reference Materials for Radiocarbon Laboratories, (Rozanski, K., Ed.), Report on Consultants’ Meeting,
Vienna, 18 – 20 February 1981, IAEA, Vienna (1991).

Guidelines for Isotope Hydrology, Manuel for Operation of an Isotope Hydrology Laboratory IAEA, Vienna
(1999).

Isotopes of Noble Gases as Tracers in Environmental Studies, Report by Consultants’ Meeting, Vienna, 29 May–2
June 1989, STU/PUB/859, IAEA, Vienna, 305 pp.

Statistical Treatment of Data on Environmental Isotopes in Precipitation, STI/DOC/10/331, AEA, Vienna (1992)
781 pp.

Isotope and Geochemical Techniques applied to Geothermal Investigations, Proc. Res. Coord. Meeting, Vienna,
12 – 15 October 1993, TECDOC-788, IAEA, Vienna (1995) 258 pp.

Reference and Intercomparison Materials for Stable Isotopes of Light Elements, Proc. Cons. Meeting, Vienna,
1 – 3 December 1993, TECDOC-825, IAEA, Vienna (1995).

Manual on Mathematical Models in Hydrogeology, TECDOC-910, IAEA, Vienna (1996) 107 pp.

157
References

[1] Kotwicki, V., Water in the universe, Hydrol. Sci. J. 36 (1991) 49–66.

[2] Baumgartner, A., Reichel, E., The World Water Balance (Gleick, P.H., Ed.), Elsevier,
Amsterdam (1975) 179 pp.
[3] Shiklomanov, I.A ., “World freshwater resources”, Water in Crisis, Oxford University Press, New
York, Oxford (1993) 473 pp.
[4] Penman, H.L., “Natural evaporation from open water, bare soil and grass”, Proc. Royal Soc. London
A 139 (1948) 120–145.
[5] Monteith, J.L., “Evaporation and environment”, Proc. Symp. Experimental Biology 19, Cambridge
(1965) 205–234.
[6] Barry, R.G., “Evaporation and transpiration”, Introduction to Physical Hydrology (Chorley, R.J.,
Ed.), Methuen, London (1969) 82–98.
[7] Budyko, M.I., “The heat balance of the Earth”, Climate Change (Gribbin, J., Ed.), Cambridge
University Press, London, New York (1978) 85–113.
[8] BOSATLAS, De Grote Bosatlas, Wolters-Noordhof bv, Atlas Productions, Groningen, The Netherlands,
50e druk (1988).
[9] Barry, R.G., “The world hydrological cycle”, Introduction to Physical Hydrology (Chorley, R.J., Ed.),
Methuen, London (1969) 8–25.
[10] L’Vovich, M.I., The water balance and its zonal characteristics, Sov. Geogr. 3 (1962) 37–50.
[11] Lamb, H.H., Climate, History and the Modern World, Methuen, New York (1982) 387 pp.
[12] Jones, J.A .A ., Global Hydrology, Longman, Harlow (1997) 399 pp.
[13] Eagleson, P.S., The emergence of global scale hydrology, Water Resour. Res. 22 (1986) 6–14.
[14] Bruijnzeel, L.A ., “Predicting the hydrological impacts on land cover transformation in the humid
tropics: the need for integrated research”, Amazonian Deforestation and Climate (Gash, J.H.C., Nobre,
C.A ., Roberts, J.M., Victoria, R.L., Eds), Wiley, Chichester (1996) 15–57.
[15] Friedman, I., Deuteriun content of natural water and other substances, Geochim. Cosmochim. Acta 4
(1953) 89–103.
[16] Dansgaard, W., Stable isotopes in precipitation, Tellus 16 (1964) 436–468.
[17] Münnich, K.O., Messung des 14C-Gehaltes von hartem Grundwasser, Naturwiss. 44 (1957) 32–39.
[18] Vogel, J.C., Ehhalt, D., “The use of carbon isotopes in ground-water studies”, Proc. Conf. on
Isotopes in Hydrology, IAEA, Vienna (1963) 383–396,
[19] Vogel, J. C. , Grootes, P.M., Mook, W.G., Isotope fractionation between gaseous and dissolved
carbon dioxide, Z. Phys. 230 (1970) 225–238.
[20] Bigeleisen, J., Wolfsberg, M., Theoretical and experimental aspects of isotope effects in chemical
kinetics, Adv. Chem. Phys. 1 (1958) 15–76.
[21] Bigeleisen, J., The effects of isotopic substitutions on the rates of chemical reactions, J. Phys. Chem.
56 (1952) 823–828.
[22] Urey, H.C., The thermodynamic properties of isotopic substances, J. Amer. Chem. Soc. (1947) 562–581.
[23] Broecker, W.S., Oversby, V.M., Chemical equilibria in the earth, McGraw-Hill, New York, London
(1971) 318 pp.
[24] Richet, P., Bottinga, Y., Javoy, M., A review of hydrogen carbon, nitrogen, oxygen, sulphur
and chlorine stable isotope fractionation among gaseous molecules, Ann. Rev. Earth Planet. Sci. Lett. 5
(1977) 65–110.
[25] Kerstel, E.R.Th., van Trigt, R., Dam, N., Reuss, J., Meijer, H.A .J., Simultaneous determination
of the 2H/1H, 17O/16O, and 18O/16O isotope abundance ratios in water by means of laser spectrometry, Anal.
Chem. 71 23 (1999) 5297–5303.
[26] Skaron, S., Wolfsberg, M., Anomalies in the fractionation by chemical equilibrium of 18O/16O
relative to 17O/16O, J. Chem. Phys. 72 (1980) 6810–6811.
[27] Meijer, H.A .J., Li, W.J., The use of electrolysis for accurate δ17O and δ18O isotope measurements in
water, Isot. Environ. Health Stud. 34 (1998) 349–369.
[28] CRAIG, H., Carbon–13 in plants and the relationships between carbon–13 and carbon–14 variations in
nature, J. Geo. 62 (1954) 119–149.

159
[29] Schlosser, P., Shapiro, S.D., Stute, M., Aeschbach-Hertig, W., Plummer, N.,
Busenberg, E., “Tritium/3He measurements in young groundwater”, Proc. Symp. Isotope Techniques
in the Study of Environmental Change, IAEA, Vienna (1998) 165–189.
[30] Nier, A .O., A redetermination of the relative abundances of the isotopes of carbon, nitrogen, oxygen,
argon and potassium, Phys. Rev. 77 (1950) 789–793.
[31] Mook, W.G., Bommerson, J.C., Staverman, W.H., Carbon isotope fractionation between
dissolved bicarbonate and gaseous carbon dioxide, Earth Planet. Sci. Lett. 22 (1974) 169–176.
[32] Thode, H.G., Shima, M., Rees, C.F., Krishnamurty, K.V., Carbon–13 isotope effects in systems
containing carbon dioxide, bicarbonate, carbonate and metal ions, Canad. J. Chem. 43 (1965) 582–595.
[33] Rubinson, M., Clayton, R.N., Carbon–13 fractionation between aragonite and calcite, Geochim.
Cosmochim. Acta 33 (1969) 997–1002.
[34] Emrich, K., Ehhalt, D., Vogel, J.C., Carbon isotope fractionation during the precipitation of
calcium carbonate, Earth Planet. Sci. Lett. 8 (1970) 363–371.
[35] Mook, W.G., 13C in atmospheric CO2, Neth. J. Sea Res. 20 2/3 (1986) 211–223.
[36] Baertschi, P., Die Fraktionierung der Kohlenstoffisotopen bei der Absorption von Kohldioxyd. Helv.
Chim. Acta 35 (1952) 1030–1036.
[37] Siegenthaler, U., Munnich, K.O., “13C/12C fractionation during CO2 transfer from air to sea”,
SCOPE 16: Carbon Cycle Modelling (B. Bolin, Ed.), John Wiley, New York (1981) 249–257.
[38] Inoue, H., Sugimura, Y., Carbon isotope fractionation during the CO2 exchange process between
air and sea water under equilibrium and kinetic conditions, Geochim. Cosmochim. Acta 44 (1985)
2453–2460.
[39] Wanninkhof, R., Kinetic fractionation of the carbon isotopes 13C and 12C during the transfer of CO2
from air to seawater, Tellus 37B (1985)128–135.
[40] Craig, H., Isotopic standards for carbon and oxygen and correction factors for mass-spectrometric
analysis of carbon dioxide, Geochim. Cosmochim. Acta 12 (1957) 133–149.
[41] Gonfiantini, R., “Stable Isotope Reference Samples for Geochemical and Hydrological
Investigations”, Report Adv. Group Meeting, Vienna, September 1983 (1984) 77 pp.
[42] Zhang, Q., Li, W., “Mass spectrometric determination of the absolute isotopic abundance of carbon in
NBS–20”, Proc. 2nd Beijing Conf. and Exhib. on Instr. Analysis, (1987) 391–392.
[43] Keeling, C.D., The concentration and isotopic abundances of atmospheric carbon dioxide in rural
areas, Geochim. Cosmochim. Acta 13 (1958) 322–334.
[44] Mook, W.G., International comparison of proportional gas counters for 14C activity measurements,
Radiocarbon 25 2 (1983) 475–484.
[45] Mook, W.G., Vogel, J.C., Isotopic equilibrium between shells and their environment, Science 159
(1968) 874–875.
[46] Lerman, J.C., “Carbon–14 dating: origin and correction of isotope fractionation errors in terrestrial
living matter”, Proc. 8th Int. Conf. on Radiocarbon Dating, New Zealand, (1972) 612–624.
[47] Throughton, J.H., “Carbon isotope fractionation by plants”, Proc. 8th Int. Conf. Radiocarbon
Dating, New Zealand, (1972) 420–438.
[48] Deines, P., “The isotopic composition of reduced organic carbon”, Handbook of Environmental Isotope
Geochemistry, Vol. I: The Terrestrial Environment (Fritz, P., Fontes, J.C., Eds), Elsevier, Amsterdam,
New York (1980) 329–407.
[49] Roeloffzen, J.C., Mook, W.G., Keeling, C.D., “Trends and variations in stable carbon isotopes
of atmospheric carbon dioxide”, Proc. IAEA Conf. on Stable Isotopes in Plant Nutrition, Soil Fertility and
Environmental Studies, IAEA ,Vienna (1991), 601–618.
[50] MOOK, W.G., “Stable carbon and oxygen isotopes of natural waters in the Netherlands”, Isotope
Hydrology (Proc. Symp. of IAEA and UNESCO, Vienna, March 9–13, 1970), Vienna, IAEA (1970)
163–190.
[51] Majoube, M., Fractionnement en oxygen–18 et en deuterium entre l’eau et sa vapeur, J. Chim. Phys.
68 (1971) 1423–1436.
[52] Horita, J., Wesolowski, D.J., Liquid-vapor fractionation of oxygen and hydrogen isotopes of
water from the freezing to the critical temperature, Geochim. Cosmochim. Acta 58 16 (1994) 3425–3437.
[53] Friedman, I., O’Neil, J.R., Compilation of stable isotope fractionation factors of geochemical
interest, USGS Prof. Paper 440-KK (1977).
[54] Brenninkmeijer, C.A .M., Kraft, P., Mook, W.G., Oxygen isotope fractionation between CO2
and H2O, Isot. Geosci. 1 (1983) 181–190.

160
[55] Epstein, S., Mayeda, T., Variations of O18 content of waters from natural sources, Geochim.
Cosmochim. Acta 4 (1953) 213–224.
[56] Epstein, S., A revised oxygen paleotemperature scale, Geol. Soc. Amer. Bull. (1976), pers. comm .
[57] Merlivat, L., Molecular diffusivities of H216O, HD16O, and H218O in gases, J. Chem. Phys. 69 (1978)
2864–2871.
[58] Craig, H., Standards for reporting concentrations of deuterium and oxygen–18 in natural waters,
Science 133 (1961) 1833–1834.
[59] International Atomic Energy Agency, Consultants’ meeting on stable isotope standards and
intercalibration in Hydrolgy and in Geochemistry, Internal report., IAEA, Vienna (1977) 35 pp.
[60] Baertschi, P., Absolute 18O content of Standard Mean Ocean Water, Earth Planet. Sci. Lett. 31 (1976)
341–344.
[61] International Atomic Energy Agency, Report of the Consultants’ Meeting on Stable isotope
reference samples for geochemical and hydrological investigations, internal report, IAEA, Vienna (1986)
48 pp.
[62] Craig, H., Gordon, L.I., “Deuterium and oxygen–18 variations in the ocean and the marine
atmosphere”, Stable Isotopes in oceanographic studies and Palaeotemperatures, Spoleto (1965) 1–22.
[63] Epstein, S., Buchsbaum, R., Lowenstam, H.A ., Urey, H.C., Revised carbonate water isotopic
temperature scale, Bull. Geol. Soc. Am. 64 (1953) 1315–1325.
[64] Emiliani, C., “The amplitude of pleistocene climatic cycles at low latitudes and the isotopic composition
of glacial ice”, The Late Cenozoic Glacial Ages (Turekian, K.K., Ed.), Yale University Press, New
Haven, London (1971) 183–197.
[65] Olaussen, E., On the  isotopic composition of Late Cenozoic sea water, Geografiska Annaler 63A
(1981) 311–312.
[66] Van der Straaten, C.M., Mook, W.G., “Stable isotopic composition of precipitation and climatic
variability”, Palaeoclimates and Palaeowaters (Panel Proc. Series, 1983.), IAEA, Vienna (1983) 53–64.
[67] Lorius, C., Oeschger, H., Palaeo-perspectives: reducing uncertainties in Global Change?, Ambio
23 1 (1994) 30–35.
[68] Veizer, J., Hoefs, J., The nature of O18/O16 and C12/C13 secular trends in sedimentary carbonate rocks,
Geochim. Cosmochim. Acta 40 (1976) 1387–1396.
[69] Urey, H.C., Brickwedde, F.G., Murphy, G.M., A Hydrogen Isotope of Mass 2 and its Concentration,
Phys. Rev. 40 (1932) 1–15
[70] Hagemann, R., Nief, G., Roth, E., Absolute isotopic scale for deuterium analysis of natural waters,
Absolute D/H ratio for SMOW, Tellus 22 (1970) 712–715.
[71] De Wit, J.C., Van der Straaten, C.M., Mook, W.G., Determination of the absolute D/H ratio of
VSMOW and SLAP, Geostandards Newslett. 4 (1980) 33–36.
[72] Tse, R.S., Wong S.C., Yuen, C.P., Determination of deuterium/hydrogen ratios in natural waters by
Fourier transform nuclear magnetic resonance spectrometry, Anal.Chem. 52 (1980) 2445.
[73] Craig, H., Isotopic variations in meteoric waters, Science 133 (1961) 1702–1703.
[74] Libby, W.F., Atmospheric helium three and radiocarbon from cosmic radiation, Phys. Rev. 69 (1946)
671–672.
[75] Godwin, H., Half life of radiocarbon, Nature 195 (1962) 984.
[76] Stuiver, M., Polach, H., Reporting of 14C data, Radiocarbon 19 3 (1977) 355–363.
[77] MOOK W. G., VAN DER PLICHT J., Reporting 14C activities and concentrations, Radiocarbon 41 3
(1999) 227–239
[78] Karlén, I., Olsson, I.U., Kållberg, P., Killiççi, S., Absolute determination of the activity of
two 14C dating standards, Arkiv f. Geofysik 6 (1966) 465–471.
[79] Mann, W.B., An international reference material for radiocarbon dating, Radiocarbon 25 2 (1983) 519–
522.
[80] Bard, E., Arnold, M., Hamelin, B., Tisnerat-Laborde, N., Cabioch G., Radiocarbon
calibration by means of mass spectrometric 230Th/234U and 14C ages of corals, Radiocarbon 40 3 (1998)
1085–1092.
[81] Stuiver, M., Van der Plicht, J. (Eds), Special Calibration Issue, Radiocarbon 40 3 (1998)
1041–1164.
[82] Mook, W.G., Streurman, H.J., Physical and Chemical Aspects of Radiocarbon Dating, PACT Publ.
8 on 14C and Archaeology (1983) 31–55.

161
[83] Mook, W.G., Waterbolk, H.T., Handbooks for Archaeologists 3: Radiocarbon Dating, European
Science Found., Strasbourg (1985) 65 pp.
[84] Ingerson, E., Pearson, F.J.Jr., “Estimating of age and rate of motion for groundwater by the C14-
method”, Recent Researches in the Fields of Hydrosphere, Atmosphere and Nuclear Chemistry, Maruzen
Comp., Tokyo (1964) 263.
[85] Geyh, M.A ., Wendt, I., “Results of water sample dating by means of the model of Münnich and
Vogel”, Proc. Int. Conf. on Radiocarbon and Tritium Dating, Pullman, USA (1965) 597–603.
[86] Pearson, F.J.Jr., “Use of C13/C12 ratios to correct radiocarbon ages of materials initially diluted by
limestone”, Proc. Int. Conf. on Radiocarbon and Tritium Dating, Pullman, USA (1965) 357–366.
[87] Gonfiantini, R., Notes on Isotope Hydrology, internal publication, IAEA, Vienna (1971).
[88] Mook, W.G., “The dissolution-exchange model for dating ground water with 14C”, Interpretation of
Environmental Isotope and Hydrochemical Data in Ground-Water Hydrology, IAEA, Vienna (1976)
213–225.
[89] Mook, W.G., “Carbon–14 in hydrological studies”, Handbook of Environmental Isotope Geochemistry
1A (Fritz, P., Fontes, J.Ch., Eds), Elsevier Science Publ., Amsterda, New York (1980) 49–74.
[90] Fontes, J.Ch., Garnier, J.M., Determination of the initial activity of the total dissolved carbon,
A review of the existing models and a new approach, Water Resour. Res. 12 (1979) 399–413.
[91] Geyer, S., Wolf, M., Wassenaar, L.I., Fritz, P., Buckau, G., Kim, J.I., “Isotope investigations
on fractions of dissolved organic carbon for 14C groundwater dating”, Isotope Techniques in the Study of
Past and Current Environmental Changes in the Hydrosphere and the Atmosphere, IAEA Symp. Vienna
1993, IAEA, Vienna (1993) 359–380.
[92] UNTERWEGER, M.P., COURSEY, B.M., SCHIMA, F.J., MANN, W.B., Preparation and calibration of
the 1978 National Bureau of Standards tritiated-water standards, Int. J. Appl. Radiat. Isot. 31 (1980) 611.
[93] Lucas, L.L., Unterweger, M.P., Comprehensive review and critical evaluation of the half-life of
tritium, J. Res. Natl. Inst. Stand. Technol, (in press).
[94] Roether, W., “Estimating the tritium input to ground water from wine samples: ground-water and direct
run-off contribution to central European surface waters”, Proc. IAEA Conf. on Isotopes in Hydrology,
IAEA, Vienna (1967) 73–90.
[95] Millero, F.J., Roy, R.N., A chemical equilibrium model for the carbonate system in natural waters,
Croatia Chemica Acta 70 (1997) 1–38.
[96] Harned, H.S., Davis Jr., R., The ionisation constant of carbonic acid in water and the solubility
of carbon dioxide in water and aqueous salt solutions from 0° to 50°C, J. Am. Chem. Soc. 65 (1943)
20–2037.
[97] Harned, H.S., Scholes, S.R., The ionisation constant of HCO! from 0° to 50°C, J. Am. Chem. Soc.
63 (1941) 1706 – 1709.
[98] Dickson, A .G., Riley, J.P., The estimation of acid dissociation constants in seawater from
potentiometric titrations with strond base. I. The ion producy of water-Kw, Marine Chemistry 7 (1979)
89–88.
[99] Weiss, R.F., Carbon dioxide in water and seawater: the solubility of a non-ideal gas, Marine Chemistry
2 (1974) 203–205.
[100] Mehrbach, C., Culberson, C.H., Hawley, J.E., Pytkowicz, R.M., Measurement of
the apparent dissociation constants of carbonic acid in seawater at atmospheric pressure, Limnology and
Oceanography 18 (1973) 897–907.
[101] Dickson, A .G., Millero, F.J., A comparison of the equilibrium constants for the dissociation of
carbonic acid in seawater media, Deep-Sea Research 34 (1987) 1733–1743.
[102] STUMM,W., MORGAN, J.J., Aquatic Chemistry, Wiley-Interscience, New York (1970).
[103] Mucci, A ., The solubility of calcite and aragonite in seawater at various salinities, temperatures and one
atmosphere total pressure, Am. J. of Science 283 (1983) 780–799.
[104] Mook, W.G., Koene, B.K.S., Chemistry of dissolved inorganic carbon in estuarine and coastal brackish
waters, Estuar. Coastal Mar. Science 3 (1975) 325–336.
[105] O’Neil, J.R., Epstein, S., A method for oxygen isotope analysis of milligram quantities of water and
some of its applications, J. Geophys. Res. 71 20 (1966) 4955–4961.
[106] Edwards, T.W.D., Huhay, W.M., Elgood, R.J., Jiang, H.B., “A  modification on the  batch
process for direct conversion of water and organic oxygen into CO2 for 18O analysis”, Isotope techniques
in the Study of past and current environmental changes in the hydrosphere and the atmosphere, IAEA,
Vienna (1993) 574–579.

162
[107] Coplen, T.B., Wildman, J., Chen, J., Improvement in the gaseous hydrogen — water equilibration
technique for hydrogen isotope ratio analysis, Anal. Chem. 63 (1991) 910–912.
[108] INTERNATIONAL ATOMIC ENERGY AGENCY, Reference and Intercomparison materials for stable
isotopes of light elements (Proc. Consultant Mtg 1–3 Dec. 1993), IAEA-TECDOC–825, IAEA, Vienna
(1995).
[109] Böhlke, J.K., Coplen T.B., Interlaboratory comparison of reference materials for nitrogen-isotope-
ratio measurements, IAEA-Tecdoc–825, IAEA, Vienna, 1–3 December 1993 (1995) 51–66.
[110] LI et al., Measurement of the absolute abundance of oxygen–17 in VSMOW, Chin. Sci. Bull. 33 (1988)
1610–1613.
[111] Brenninkmeijer, C.A .M., Mook, W.G., “The effect of electronegative impurities on CO2
proportional counting: an on-line purity test counter”, Proc. 9th Intern. Radiocarbon Conf., Los Angeles
and La Jolla, 1976, Univ. of California Press (1979) 185–196.
[112] Purser, K.H., A high throughput 14C accelerator mass spectrometer, Radiocarbon 34 3 (1992) 458–457.
[113] Mook, W.G., “Archaeological and geological interest in applying 14C AMS to small samples”, Proc. 3rd
Intern. Symp. on Accelerator Mass Spectrometry, Zürich, Nucl. Instr. Meth. B5 (1984) 297–302.
[114] Mook, W.G., The effect of fossil fuel and biogenic CO2 on the 13C and 14C content of atmospheric carbon
dioxide, Radiocarbon 22 2 (1980) 392–397.
[115] Rozanski, K., Stichler, W., Gonfiantini, R., Scott, E.M., Beukens, R.P.,
Kromer, B., Van der Plicht, J., The IAEA 14C intercomparison exercise 1990, Radiocarbon 34 3
(1992) 506–519.
[116] Lal, D., Peters, B., “Cosmic-ray produced radioactivity on the Earth”, Handbuch der Physik 46
(Sitte, K., Ed.), Springer Verlag, Berlin (1967) 551–612.
[117] Benson, B.; Krause, D., Empirical laws for dilute aqueous solutions of nonpolar gases, J. Chem.
Phys. 64 (1976) 689.
[118] Andrews, J.N., “Mechanisms for noble gas dissolution by groundwaters”, Isotopes of Noble Gases as
Tracers in Environmental Studies, IAEA Symp., Vienna 1989, IAEA, Vienna (1992) 87–110.
[119] Raisbeck, G.M., Yiou, F., Fruneau, M., Lieuvin, M., Loiseaux, J.M., Measurement of 10Be
in 1000- and 5000-year-old Antarctic ice, Nature 275 (1978) 731–732.
[120] Raisbeck, G.M., Yiou, F., Fruneau, M., Loiseaux, J.M., Lieuvin, M., 10Be concentration and
residence time in the oceans surface layer, Earth Planet. Sci. Lett. 43 (1979) 237–240.
[121] Gregoire, D.C., Determination of boron isotopic ratios in geological materials by inductively coupled
plasma mass spectrometry, Anal. Chemistry 59 (1987) 2479–2484.
[122] Létolle, R., “Nitrogen–15 in the natural environment”, Handbook of Environmental Geochemistry 1A
(Fritz, P., Fontes, J.C., Eds), Elsevier Science Publ., Amsterdam (1980) 407–434.
[123] Clark, I., Fritz, P., Environmental Isotopes in Hydrogeology, Lewis Publishers, Boca Raton, New
York (1997).
[124] Révész, K., Böhlke, J.K., Yoshinari, T., “δ18O and δ15N determination in nitrate”, Proc. Symp. on
Isotope Techniques in the Study of Environmental Change, Vienna, 1997, IAEA, Vienna (1998) 851–854.
[125] Dansgaard, W., Clausen, H.B., Aarkog, A ., The Si32 fallout in Scandinavia: A new methd for
ice dating, Tellus 18 (1966) 187–191.
[126] Morgenstern, U., Gellerman, R., Hebert, D., Börner, I., Stolz, W.,
Vaikmäe, R., Putnik, H., 32Si in limestone aquifers, Chem. Geol. 120 (1995) 127–134.
[127] Heinemeier, J., Hornshøj, P., Nielsen, H.L., Rud, N., Thomsen, M.S., Accelerator mass
spectrometry applied to 22,24Na, 31,32Si, and 14C, Nucl. Instr. and Methods B 29 (1987) 110–113.
[128] Pearson, F.J.Jr., Rightmire, C.T., “Sulphur and oxygen isotopes in aqueous sulphur compounds”,
Handbook of Environmental Geochemistry, Vol. 1A (Fritz, P., Fontes, J.C., Eds), Elsevier Science
Publ., Amsterdam (1980) 227–258.
[129] Krouse, H.R., “Sulphur isotopes in our environment”, Handbook of Environmental Geochemistry I
A (Fritz, P., Fontes, J.C., Eds), Elsevier Science Publ., Amsterdam, New York (1980) 435–471.
[130] Roman, D., Airey, P.L., The application of environmental chlorine–36 to hydrology. I. Liquid
scintillation counting, Int. J. Appl. Rad. Isot. 32 (1981) 287–290.
[131] Bentley, H.W., Fillips, F.M., Davis, S.N., “Chlorine–36 in the terrestrial environment”, Handbook
of Environmental Isotope Geochemistry Vol. 2 (Fritz, P., Fontes, J.C., Eds), Elsevier Science Publ.
Comp., Amsterdam, New York (1986) 427–480.

163
[132] Lehmann, B.E., Loosli, H.H., Balderer, W., Fontes, J.Ch., Michelot, J.L., Soreau, S.,
“Chlorine–36”, Applied Isotope Hydrology, Studies in Environmental Science 43 (Pearson, F.J., et al.,
Eds) Elsevier Science Publ. Amsterdam, New York (1991) 250–265.
[133] Eggenkamp, H.G.M., δ37Cl, the geochemistry of chlorine isotopes, Doct. Thesis, Fac. Earth Sciences,
Utrecht Univ. (1994) 150 pp.
[134] Van Warmerdam, E.M., Frape, S.K., Aravena, R., Drimmie, R.J., Flatt, H., Cherry, J.A .,
Stable chlorine and carbon isotope measurements of selected chlorinated organic solvents, Appl.
Geochem. 10 (1995) 547–552.
[135] Loosli, H.H., Oeschger, H., “Argon–39, carbon–14 and krypton–85 measurements in groundwater
samples”, Isotope Hydrology II, IAEA Symposium Neuherberg, Vienna, 1978. IAEA, Vienna (1979)
931–997.
[136] Forster, M., Maier, P., Loosli, H.H., Current techniques for measuring the activity of 37Ar and
39
Ar in the environment, Isotopes of Noble Gases as Tracers in Environmental Studies, IAEA, Vienna
(1992) 63–72.
[137] Oeschger, H., Loosli, H.H., “New developments in sampling and low level counting of natural
radioactivity”, Proc. High Tatras Conf. 1975 on Low Radioactivity Measurements and Applications
(1977) 13–22.
[138] Collon, P., Antaya, T., Davids, B., Fauerbach, M., Harkewicz, R., Hellstrom, M.,
Kutschera,  W., Morrissey,  D., Pardo,  R., Paul,  M., Sherrill, B., Steiner, M.,
Measurement of 81Kr in the atmosphere, Nucl. Instr. and Meth. B 123 (1997) 122–127.
[139] Ekwurzel, B., Schlosser, P., Smethie, W.M., Plummer, N., Busenberg, E.,
Weppernig, R.L., Stute, M., Dating of shallow groundwater: comparison of the transient tracers
3
H/3He, chlorofluorocarbons and 85Kr, Water Resour. Res. 30 (1994) 1693–1708.
[140] Weiss, W., Sartorius, H., Stockburger, H., “Global distribution of atmospheric 85Kr”, Isotopes
of Noble Gases as Tracers in Environmental Studies, IAEA Symp., Vienna, 1989 IAEA, Vienna (1992)
29–62.
[141] Sharma, P., Elmore, D., Miller, T., Vogt, S., The 129I program at PRIME Lab., Nucl. Instr. and
Meth. B 123 (1997) 347–351.
[142] Pearson, F.J., Applied Isotope Hydrogeology, a case study in Northern Switzerland, Elsevier Science
Publ, Amsterdam, Oxford, New York, Tokyo (1991).
[143] Vogel, J.C., Kronfeld, J., A new method for dating peat, S. Afr. J. Sc. 76 (1980) 557–558.
[144] Van der Wijk, A., Mook, W.G., Ivanovich, M., Correction for environmental 230Th in U/Th
disequilibrium dating of peat, Sci. Total Environ. 70 (1988), 19–40.
[145] Van der Wijk, A., Mook, W.G., 210Pb dating in shallow moorland pools., Geol. Mijnb. 66 (1987)
43–55.
[146] Van der Wijk, A., Radiometric dating by alpha spectrometry on uranium series nuclides, Thesis
Groningen University (1987) 145 pp.
[147] Faure, G., Principles of Isotope Geology, John Wiley & Sons (1986).
[148] Lederer, C.M., Shirley, V.S., et al., Table of Isotopes, John Wiley and Sons, New York (1978).

164