Académique Documents
Professionnel Documents
Culture Documents
Mémoire
Maitrise en chimie
Maître ès sciences (M.Sc.)
Québec, Canada
iii
iv
Abstract
v
vi
Table of Contents
RÉSUMÉ ................................................................................................................ III
ABSTRACT ............................................................................................................ V
TABLES LIST ........................................................................................................ IX
PICTURES LIST .................................................................................................... XI
ABBREVIATIONS LIST ....................................................................................... XIII
ACKNOWLEDGMENTS ...................................................................................... XIX
INTRODUCTION ..................................................................................................... 1
1. RADIOSTRONTIUM ............................................................................................................................................ 5
1.1. Occurrence and radiological properties of strontium--‐90 ................................................ 5
1.2. Applications of strontium--‐90 ........................................................................................... 8
1.3. Instability of strontium--‐90 and the origin of its radioactivity .......................................... 9
1.4. Hazardous effects of strontium--‐90 ................................................................................. 10
5. EXPERIMENTAL ............................................................................................................................................... 47
5.1. Chemicals ....................................................................................................................... 47
5.2. Digestion of SrTiO3 ........................................................................................................ 47
5.3. Separation tests .............................................................................................................. 48
5.4. Omnifit® glass column preparation............................................................................... 49
5.5. Methodology ................................................................................................................... 49
viii
vi
ii
Tables List
ix
x
Pictures List
Figure 1.1 – Brief description of the origin of radioactivity in the
environment ...................................................................................................P.6
Figure 1.2 – Decay chain of strontium-90 .................................................... P.8
Figure 1.3 – Means of uptake and bioaccumulation for strontium-90........... P.11
Figure 2.1 – Number of nuclear and radioactive incidents reported by the
IAEA for the last years ................................................................................. P.13
Figure 2.2 – Forensic Science...................................................................... P.16
Figure 2.3 – Decay process of Sr-90 as function of elapsed time ................ P.19
Figure 3.1 – Basic components of ordinary mass spectrometers................. P.21
Figure 3.2 – Quadrupole mass spectrometer ............................................... P.23
Figure 3.3 – Triple quadrupole mass spectrometer mechanism................... P.25
Figure 3.4 – Mechanism of energy transfer and detection of beta particles
by liquid scintillation ..................................................................................... P.28
Figure 3.5 – Growth rate of Y-90 and secular equilibrium with Sr-90 ........... P.29
Figure 4.1 – Equilibrium in chromatographic separations ............................ P.32
Figure 4.2 – In column chromatography technique ...................................... P.33
Figure 4.3 – Experimental variables to determine resolution in
chromatography ........................................................................................... P.35
Figure 4.4 – Parameters for the determination of peak asymmetry.............. P.37
Figure 4.5 – Separation of cations and anions by IEC ................................. P.38
Figure 4.6 – Schema of extraction chromatography..................................... P.40
Figure 4.7 – D values for strontium and zirconium in the Dowex 1-X10
resin ............................................................................................................. P.44
Figure 4.8 – Capacity factor for strontium and zirconium in the DGA resin .. P.46
Figure 5.1 – AF Omnifit® Column Design .................................................... P.49
Figure 5.2 – Method applied for separation tests ......................................... P.50
Figure 6.1 – Reproducibility of SrTiO3 digestion using HNO3/HF mixture .... P.57
Figure 6.2 – Elution profile of Sr and Zr in 4M HCl (10 g AG50W-X8, 100-
200 mesh) .................................................................................................... P.58
Figure 6.3 – Elution profile of Sr and Zr in 3M HCl (10 g AG50W-X8, 100-
200 mesh) .................................................................................................... P.59
Figure 6.4 – Separation of Sr and Zr using a 2M to 6M HCl gradient (10 g
AG50W-X8, 100-200 mesh) ......................................................................... P.59
Figure 6.5 – Elution curves of Sr as function of HCl molarity (10 g
AG50W-X8, 100-200 mesh) ......................................................................... P.60
Figure 6.6 – Elution curves of Sr at 2M HNO3 and 2M HCl (10 g AG50W-
X8, 100-200 mesh)....................................................................................... P.61
Figure 6.7 – Separation of Sr and Zr using a 2M HNO3 to 6M HCl
gradient in 2 g AG50W-X8 (100-200 mesh) ................................................. P.63
Figure 6.8 – Volume of eluent for Sr elution as function of mass of
AG50W-X8 ................................................................................................... P.63
Figure 6.9 – Separation efficiency for Sr and Zr using Dowex1-X8 resin ..... P.65
xi
Figure 6.10 – Zirconium retention in Dowex1-X8 as function of HCl
concentration ................................................................................................. P.65
Figure 6.11 – Maximum recovery of Zr according to HCl concentration in
Dowex1-X8 ................................................................................................... P.66
Figure 6.12 – Comparative of separation of Sr and Zr using ion exchange
and extraction resins (a. AG50W-X8, b. DOWEX1-X8, c. Sr-Resin, d.
DGA-Resin) .................................................................................................. P.67
Figure 6.13 – Proposed extraction mechanism for Sr for its separation
from Zr by EXC ............................................................................................. P.68
Figure 6.14 – Tailing effect as a function of Sr concentration (AG50W-X8) . P.69
Figure 6.15 – Separation of Sr and Zr using Dowex1-X8 for samples
containing HF ............................................................................................... P.70
Figure 6.16 – Separation of Sr and Zr using DGA for samples containing
HF (a. 0.01%, b. 0.2%) ................................................................................. P.71
Figure 6.17 – Complete methodology to separate Sr and Zr using DGA
resin.............................................................................................................. P.73
Figure 6.18 – Comparative between experimental and expected results
for the recovery of trace levels of Zr using DGA resin .................................. P.74
Figure 6.19 – Procedure for determining the age of a radiostrontium
source........................................................................................................... P.75
Figure 6.20 – Comparative between theoretical and experimental
concentrations for the analysis of Sr-90 by liquid scintillation ....................... P.76
Figure 6.21 – Zr and Sr oxides formation in mass spectrometry as
function of O2 concentration in the reaction cell............................................ P.77
Figure 6.22 – Predominant species of Zr (a) and Sr (b) at 6% O2 in the
reaction cell .................................................................................................. P.78
Figure 6.23 – Correlation between results for the analysis of Zr at m/z 90
and m/z 106.................................................................................................. P.79
Figure 6.24 – Predominant species of Y at 6% O2 in the reaction cell.......... P.79
xii
Abbreviations List
– Alpha particles
– Separation factor
– Beta particles
h – Decay constant
a – asymmetry portion of a peak
A – Final activity
AO – Initial activity
AS – Peak asymmetry
A+ – Charged analyte
AG50W-X8 – Cationic resin
AMS – Accelerator Mass Spectrometry
b – Back portion of a peak
C – Final concentration
CO – Initial concentration
Ce – Concentration of a solute in the extractant phase
Ci,M – Concentration in the mobile phase
Ci,S – Concentration in the stationary phase
cpm – Count per minute
cps – Count per second
D – Distribution ratio
DGA – Diglycolamide resin
Dowex1-X8 – Anionic resin
E – Extractant
EPA – Environmental Energy Agency
EXC – Extraction chromatography
F – Force
F- – Fluoride
G – Gas
G+ – Charged gas
H – Height of the theoretical plate
H+ – Proton
H2C2O4 – Oxalic acid
H2O – Water
H2O2 – Hydrogen peroxide
H2SO4 – Sulphuric acid
HCl – Hydrochloric acid
HEU – High-enriched uranium
HF – Hydrofluoric acid
HNO3 – Nitric acid
AHR – Enthalpy
i – Given compound
I – Interference
i.d – Internal diameter
xi
ii
I+ – Charged interference
IAEA – Internation Atomic Energy Agency
ICP-MS – Inductively Coupled Plasma Mass Spectrometry
ID – Identification
IEC – Ion exchange chromatography
IUPAC – International Union of Pure and Applied Chemistry
K – Distribution coefficient
k' – Capacity factor
ke – Coulomb’s constant
L – Length
L – Ligand
LL – Lower limit
LOD – Detection limit
LOQ – Quantification limit
m – Mass
6N – Mass difference
M – Molar
m/z – Mass-to-charged ratio
M+ – Charged metal
MM – Molar mass
MS – Mass spectrometry
M – Megaohm
N – Number of theoretical plates
N/Z – Neutron-to-proton ratio
N2O4 - Nitrogen tetroxide
NO3- – Nitrate
NÆ – Avogadro’s number
O – Atomic oxygen
O2 – Molecular oxygen
Pb – Lead
ppt – part per trillion
Psi – lbf/square inch
Pu – Plutonium
q – Charge
Q – Quadrupole
RS – Resolution
r – Distance between two charges
R2 – Correlation factor
RDDs – Radiological dispersion devices
RF – Radio-frequency
RTGs – Radiothermal generators
s – Standard deviation
S – Stationary phase
SI – International system
Sr – Strontium
SrO+ – Charged strontium oxide
xiv
SrTiO3 – Strontium Titanate
t – Age of a radioactive source
t½ – Half-life
Ti – Titanium
tN – Dead time
t'i – Adjusted retention time
TIMS – Thermal Ionization Mass Spectrometry
ti – Retention time
u – Mass unit
U – Uranium
U.S – United States
UP – Upper limit
VM – Volume of the mobile phases
VS – Volume of the stationary phases
v/v – Volume-to-volume ratio
y – Years
Y – Yttrium
wi, – Width at the base of a peak
Zr – Zirconium
Zr+ – Charged zirconium
ZrO+ – Charged zirconium oxide
xv
xvi
“Science can only be created by those who are thoroughly imbued with the
aspiration toward truth and understanding ”
Albert Einstein
xvii
xviii
Acknowledgments
My completion of this project would not have been possible without the kind
support of my director Dominic Larvière. So, I would like to thank him to be always
open to discuss and share ideas while guiding me to successfully achieve the
goals of this project.
I also would like to thank Serge Groleau for all the support in the laboratory, my
office partners Annie Michaud, Pablo Lebed, and Marie-Ève Lecavalier for their
pleasant company during all the time we spent together. Charles Labrecque,
Kenny Nadeau, Jean-Michel Benoit, Solange Schneider, Laurence Whitty-Léveillé,
Sabrina Potvin, Julien Légaré Lavergne, Justyna Florek, and Maela Choimet who I
had the opportunity to work with and, in some cases, the opportunity to struck up a
close friendship.
Likewise, I would like to thank Health Canada, the Research and Technology
Initiative, and Agilent to make this project possible. And finally, I would like to thank
Sherrod Maxwell for the interest in this project as well as for the suggestions and
the encouragement, which have been all important to the accomplishment of this
work.
xix
xx
Introduction
Before the 90s, the main concern for nuclear security was to protect only high-
enriched uranium (HEU) and plutonium in nuclear facilities. However, the
increasing number of cases implicating illegal possession, theft, or loss involving
other radioactive sources since 1995, forced authorities to establish a new concept
of nuclear security, while triggering efforts towards eliminating nuclear and
radioactive threats.
Such new concept became synonym of both protection and control over not only
nuclear but also any kind of radioactive material that could give rise to malicious
actions, including unpredictable terrorist activities and utilization of radiological
weapons known as dirty bombs.
Contrary to nuclear bombs, dirty bombs are relatively easier to fabricate and are
mainly characterized by their dispersive effect. The purpose of dirty bombs is not to
destroy but contaminate, while spreading a radioactive material through the
utilization of conventional explosives.
13
Usually, radionuclides that have long half-lives or a high specific activity are
potentially more interesting for the production of radiological dispersion devices
(RDDs). Ranked in a short list of these radionuclides, strontium-90 has a half-life of
about 29 years and a specific activity of about 518 X 10 10 Bq/g. This corresponds,
for example, to a specific activity of about 1.5 times higher than for cesium-137,
which has an equivalent half-life (i.e. 30 years) [3].
2
the decay law. Actually, Sr-90 is an unstable radioisotope that undergoes beta
decay to form Y-90 which in turn decays into Zr-90, a stable nucleus. Thus, the age
of a source containing strontium-90, for example, would be a function of the [Zr-
90]/[Sr-90] ratio, where concentrations of both isotopes could be determined,
respectively, by liquid scintillation and mass spectrometry, as demonstrated over
the present work. To be successfully used to date nuclear materials, however, this
approach requires an efficient method for radionuclide separation to isolate Sr-90
from Zr-90 from the radioactive source as well as a sensitive method of analysis to
provide accurate results while reducing age uncertainty.
Mass spectrometry has been widely used for analytical purposes because of its
sensitivity, accuracy, and possibility to discriminate isotopic species. The major
inconvenient of this technique is the isobaric interferences caused by ionic atoms
or molecules having the same m/z, as for strontium-90 and zirconium-90. Such
interferences cause peak overlap and an overestimation of compounds of interest.
Sometimes, even high-resolution devices are not sufficient to overcome this
problem and pre-treatments (e.g. separation) are often mandatory prior to analysis.
3
resins [3]. Likewise, Steeb et al. have presented a method to separate Sr-90 from
Zr-90 using the Sr Resin [8]. For this last procedure, however, no information has
been found regarding the possibility of using cationic, anionic, or DGA resins.
Actually, different distribution coefficients available in the literature for both
elements suggest that high levels of selectivity could also be achieved using those
resins [9-14].
In this context, this work aims to compare the performance of the AG50W-X8,
Dowex1-X8, DGA, and Sr Resin and, eventually, propose one or more alternatives
to separate Sr-90 and Zr-90 for nuclear forensic applications. To make a good
comparison, experimental conditions like mass of resin and volume of eluents have
been kept constant to assess recovery and resolution of peaks after
chromatographic separations. Assuming that real samples could contain high
levels of radioactivity, significant amounts of yttrium-90 could cause isobaric
interferences that should not be neglected. For that reason, the possibility to
completely isolate Y-90 has also been considered to evaluate the efficiency of
resins.
4
Chapter 1
1. Radiostrontium
As previously mentioned, potential interest in radiostrontium for nuclear threats is a
consequence of peculiar radiological characteristics of Sr-90. Thus, this chapter
aims to detail these characteristics, while explaining the radiological risks
associated to Sr-90 and its hazardous effects for humans and for the environment.
Radioactive sources can exist in the environment naturally (i.e. primordial and
cosmogenic radionuclides) or via accidental or deliberate anthropogenic activities
(Figure 1.1). According to astrophysics theories, primordial radionuclides have
been produced in the course of nucleosynthesis and have been presented on
Earth from the beginning.
5
Figure 1.1 – Brief description of the origin of radioactivity in the environment
As for any other isotopes of strontium, Sr-90 can form other chemical compounds
6
(e.g. halides, oxides, sulphides) and its dispersion through the environment would
be strongly influenced by the chemical form and solubility.
As presented in Table 1.1, the specific activity is inversely proportional to its half-
life, which means that the higher is the specific activity, the shorter is the half-life.
In practice, short-lived isotopes are less harmful to the environment than long-lived
isotopes as they decay away faster and completely. However, short-lived isotopes
can be fatal, once humans have been directly exposed to the high-energy emitted.
For Sr-90, which is considered a long-lived isotope, long-term damage is expected
due to its slower decay rate that will take years. For those radionuclides, human
7
exposure to ionizing radiation occurs over an extended period of time due to the
fact that lower but more persistent quantities of radioactivity will remain in the
environment [18,19].
Due to its capacity to produce heat, Sr-90 in the form of strontium titanate (SrTiO3),
has also been widely used in the past for the production of portable power
supplies. Known as radioisotope thermoelectric generators (RTGs), these devices
have been manufactured to provide energy in remote sites where electricity was
quite limited (i.e. navigational beacons, weather stations, and space vehicles).
8
1.3. Instability of strontium-90 and the origin of its radioactivity
In general, two factors including nucleus mass and neutron-to-proton ratio (N/Z)
contribute to nucleus instability and, in practice, to influence the mode of radiation
emitted.
It is normally observed, for example, that heavier nuclei (i.e. usually heavier than
Pb) are more likely to emit alpha particles (), while lighter nuclei tend to achieve
stability through the emission of positive beta particles or positrons (+) to
compensate repulsive forces caused by an excess of protons. Also, it is noticed
that when the number of neutrons becomes more important than the number of
protons (i.e. increase in the N/Z ratio), it is the emission of negative beta particles
(-) or electrons that are rather detected.
AX
Z ‹ Z+1AX + Q–
9OSr ‹ 9OY + þ– ‹ 9OZr + þ–
38 39 4O
Thus, to achieve stability, Sr-90 liberates the excess of neutrons in the form of
protons and very energetic - particles. Each rearrangement per second
corresponds to the activity of the radioactive source in Becquerel (Bq) according to
SI.
9
As indicated above, the proton gives rise to a decay product, in this case, Y-90, an
intermediate decay product. Yttrium-90 is also an unstable nucleus and, as for Sr-
90, it also undergoes - decay to form Zr-90, which this time is a stable non-
radioactive isotope.
10
Figure 1.3 – Means of uptake and bioaccumulation for strontium-90
1
1
12
Chapter 2
Despite international’s effort to monitor and regulate the utilization of nuclear and
radioactive materials, the number of incidents and illicit trafficking involving them is
still significant (Figure 2.1).
300
243
250 222
215
200 171 172 163 155
150
100
50
0
2007 2008 2009 2010 2011 2012 2013
13
In total, the International Atomic Energy Agency (IAEA) has already reported 2407
incidents from 1995 to 2013, including cases of illegal possession or attempts to
sell nuclear or radioactive material, theft or loss, and unauthorized activities
apparently without criminal nature [2]. Actually, millions of radioactive sources are
available worldwide and inadequate control over usage, storage, and production in
different countries seems to contribute to the number of incidents.
One of the biggest issues is probably associated to orphaned sources, that means
sources that were abandoned, lost, or misplaced in the past without authorization
and, today, are outside of regulatory control. Thousands of radiothermal generators
(RTGs) like those using Sr-90 (Chapter 1), for example, have been discovered in
the Russia coast containing extremely high levels of radioactivity. Unfortunately,
there are about nearly a hundred pieces that have not been yet recovered and
remain unprotected against unauthorized interference [22].
In practice, only a few numbers of accidents involving RTGs have been reported
(Table 2.1) [23], but authorities do not rule out the risks of nuclear threats resulting
from the lower degree of security surrounding these sources. Main concerns
started arising after the United States discovered documents in Afghanistan with
real intentions of Al Qaeda in developing radiological dispersion devices (RDDs),
vulgarly known as dirty bombs [24].
14
people to the explosion.
2001 Three radioisotope heat sources were stolen from lighthouses located in
the Kandalaksha Bay area, in Russia. After being found, the sources
were sent to Moscow.
2001 Three woodsmen have been diagnosed with radiation sickness after
finding two unshielded radioactive heat sources near the Inguri River
valley, in Georgia. Two victims have experienced nausea, vomiting, and
dizziness after hours of exposure to sources of Sr-90 containing about
30,000 Ci. They were treated for many months before recovering from
severe radiation burns. The sources were recovered in 2002.
2002 Three shepherds were exposed to high radiation doses after they
stumbled upon a number of RTGs in the Tsalenjikha region. Eight
generators were recovered.
2003 An RTG was found 200 meters in the shoals of the Baltic Sea, which
was recovered later by a team of experts.
2003 The theft of metals from an RTG has been discovered in the White Sea
region, in Russia. The six radioactive sources have not been taken.
Assuming, for example, that a terrorist attack takes place and the presence of a
nuclear or a radioactive material is confirmed, nuclear forensic experts are put in
15
charge to work in conjunction with other forensic sciences to identify the alleged
responsible (Figure 2.2).
16
To determine the age, radiochronometry is a technique often used in fields such
archaeology, anthropology, and geology to date samples like human bones, corals,
and other artefacts preserved even over a billions of years. This technique has also
been widely used in environmental research for tracing climate changes [26] and
recently started receiving increasingly attention in nuclear forensics.
The principle of the radiochronometry technique is based on the fact that activity of
a radionuclide decays exponentially with time. According to the decay law, the
activity of a radioactive source (A) is a function of three variables: the initial activity
of the radioisotope (AO), its decay constant (h) also represented by ln2/t1/2 ratio,
and the elapsed time or also called the age (t) in nuclear forensic applications
(Equation 2.1).
A = AO e–fit (2.1)
Here, the age (t) can be isolated in the equation and be expressed in terms of both
final and initial activities (Equation 2.2):
t = — 1 ln ( A ) (2.2)
fi AO
17
C×NA×ln2
A= (2.3)
MM×t1/2
Where, NÆ is the Avogadro’s number, MM is the molar mass, and t1/2 is half-life.
t = — 1 ln ( C ) (2.4)
fi CO
As in Figure 2.3, as the time passes, the radioactive species (in this case Sr-90)
tends to decay at the same time a more stable decay product (Zr-90) is build up.
18
Figure 2.3 – Decay process of Sr-90 as function of elapsed time
t = — 1 ln ([Zr–9O]) (2.6)
fi [Sr–9O]
19
Briefly, the decay process as that illustrated for Sr-90 could serve as a
chronometer, where the age of an unknown source could be estimated by the
determination of respective concentrations of both the radioactive and the stable
isotopes at a given time t.
20
Chapter 3
Depending on its nature, inlet systems can accommodate samples under solid,
liquid, or gas state. In typical setups, liquid samples (usually more homogeneous)
21
pass through a nebulizer to transform the sample into an aerosol that is driven
towards the ion source.
In ICP-MS, for example, inorganic materials are positively ionized the ion source.
Usually, the ionization takes place in an inert atmosphere using argon, under a set
radio frequency, and a plasma temperature of up to 8,000 K.
Argon is commonly used because its first ionization potential (15.8 eV) is higher
than the first ionization potential of almost all other elements (except fluorine, neon,
and helium), which ensure the maximum ionization of the elements of interest
during analyses. Since the energy required for the second ionization is usually too
high for most part of elements, second ionization is less likely to happen.
After elements have been converted into ions, they are sent to the mass analyser
that acts as a mass filter to separate different masses. Common mass analysers
are called quadrupoles, which are consisted of four rods operating in an oscillating
electrical field capable of guiding ions towards the detector (Figure 3.2).
22
Figure 3.2 – Quadrupole mass spectrometer [29]
Once the ions reach the detector, they are measured as a current and, then,
converted into a series of peaks that form the mass spectrum.
Mass spectrometry offers some advantages such as short analysis time, low
sample consumption, high sensitivity, reduced background interference due to the
possibility of using efficient mass analyzers as filters [30], and the ability of
discriminating different isotopes.
23
For example, isobaric interferences for the analysis of Zr-90 could be caused by
the presence of its parent isotopes like Sr-90 and Y-90 [31,32]. In this case, even
high-resolution instruments that provide resolutions of about 15,000 would not be
sufficient to discriminate between the peaks of those three isotopes (Table 3.1),
suggesting the use of a pre-treatment strategy, usually a chromatographic
separation prior to analysis to chemically separate them.
24
Figure 3.3 – Triple quadrupole mass spectrometer mechanism
Using nonreactive gases, collisions are favoured and the species are discriminated
by the difference in their kinetic energy [33]. Using highly reactive gases on the
other hand, different reactions can take place to produce different polyatomic
species that are discriminated according to their different masses (Table 3.2) [34].
25
In general, interferences can be converted into non-detectable species or in
species of different masses that are shifted from the region of interest. When the
interaction with the reaction gas is stronger with the analyte, this last can be
converted in a heavier compound to be shifted to a less overladen region of the
spectrum.
Briefly, reaction cells technology had been developed not only to improve the
performance of mass spectrometers, but also to reduce background or eliminate
isobaric interferences impossible to be removed using ordinary instruments or
high-resolution devices.
According to Eiden et al., Zr seems to react at least 200 times faster with oxygen
than Sr through addition of O2 into the reaction cell. Theoretical positive enthalpy
values (AHR) for strontium oxides formation suggest that this reaction is less
favourable than that for zirconium oxides6. Also, the covalent bond for ZrO+ seems
to be stronger than that for SrO+ due to the differences in both electronic densities
and metal–oxygen bond lengths (Table 3.3.).
26
Table 3.3 – Theoretical binding properties of Zr and Sr with oxygen
atoms [32]
OHR
(M + O2 MO+)
+
Bond length Electronic
Ion
(Å) Density*
Experimental Calculated
27
Figure 3.4 – Mechanism of energy transfer and detection of beta particles by
liquid scintillation [41]
In some cases, however, beta particles are enough energetic (i.e. energy higher
than 0.6 MeV) to cause disturbance of adjacent molecules in matter followed by a
photon emission that can be detected without the need to introduce a scintillator in
the sample. This phenomenon known as Cerenkov effect occurs when a charged
particle travels at constant velocity in a medium characterized by its index of
refraction markedly larger than 1 at a speed exceeding that of the light in that
medium. Actually, in gaseous, liquid, or solid media, the velocity of light will be less
than its velocity in a vacuum, and the beta particle will be able to travel in such
media at speeds exceeding that of light [42].
As indicated in Figure 3.5 [42], secular equilibrium between Sr-90 and Y-90 is
achieved after approximately 20 days. Once activities have been determined, they
can be converted in units of mass or concentration using equation 2.3 presented in
chapter 2.
28
Figure 3.5 – Growth rate of Y-90 and secular equilibrium with Sr-90
29
30
Chapter 4
Ci,C
K= (4.1)
Ci,M
31
Figure 4.1 – Equilibrium in chromatographic separations
In general, species having less affinity with the stationary phase (i.e. lower K
values) experience shorter retention times and tend to move faster than those
having stronger affinities (i.e. higher K values).
C V
k u = C i,C VC (4.2)
i,M M
Where, Ci,S and Ci,M are the component concentration, VS and VM are the respective
volumes of the stationary and mobile phases.
32
Figure 4.2 – In column chromatography technique
The distribution ratio (D) is commonly used to express the distribution of a solute
between two phases for a specific mobile phase. According to IUPAC, D
corresponds to the ratio of the total concentration of a solute in the extractant
phase (Ce) to the total initial concentration (CO) (Equation 4.3) [43].
D = Ce (4.3)
C0
In practice, distribution ratios are very useful to compare the degree of selectivity,
for example, of a resin for two different species dissolved in the same solvent. The
selectivity is usually expressed in terms of separation factors (α), which correspond
33
to the ratio of D values of two different compounds that should be separated
(Equation 4.4).
DA
αÆ,B = (4.4)
DB
2(tu2 –tu1 )
RS = (4.5)
w2+w1
In the above equation, t'i corresponds to the adjusted retention time (t'i = ti - tN )
of each compound and wi , the respective widths at the base of each peak. tN is
usually subtracted and corresponds to the time required for the mobile phase to
travel the length of the column without any interaction with the stationary phase.
34
Figure 4.3 – Experimental variables to determine
resolution in chromatography
The efficiency of separation, on the other hand, could be assessed through the
determination of the number of theoretical plates (N) using equation 4.6:
2
N = 16 ( ti ) (4.6)
wi
Again, ti and wi are respectively, the retention time and the width at the base of
the peak for a given compound i.
The notion of theoretical plates was introduced in 1941 by Martin and Synge
through the Plate Theory that supposes that a chromatographic column contains a
large number of imaginary and thin sections called plates within each analyte is
found to be at equilibrium between the stationary and mobile phase. As the notion
35
of the theoretical plate is now well established and it is applicable to all types of
associated to the length (L) of the column (Equation 4.7), but can be affected by
experimental factors such as: technique of column and sample preparation, solute
N= L
(4.7)
K
Normally, perfect Gaussian peaks are rarely obtained. In general, peak asymmetry
is frequently observed and the main causes include at least one of the following
conditions: nature of the packing material, nature of the analytes to be separated,
and chromatographic system [47].
36
AS= b (Equation 4.8)
a
where b and a represent, respectively, the back and the front portion at 10% of the
peak height (Figure 4.4).
In practice, symmetrical peaks have asymmetry factors between 0.9 and 1.2.
In practice, this technique allows the separation, for example, of anions from
cations in a mixture. Counter-ions tend to be attracted to the surface while co-ions
tend to be repelled (Figure 4.5).
37
Figure 4.5 – Separation of cations and anions by IEC [48]
|q1q2|
|F| = ke (4.8)
r2
In equation 4.6 ke is the Coulomb’s constant and r the distance between q1 and q2.
38
neutrality of the system [49]. Efficient separations could be achieved through the
reversible exchanges of counter-ions at the surface of the stationary phase.
Ion exchange resins are solid materials containing active and charged sites
covalently bounded to the stationary phase. Depending on the group attached,
those resins can be classified as cationic or anionic resins. Anionic resins carry
positive charges and are designed to uptake negative counter-ions, while cationic
resins, carrying negative charges, are designed to up take positive counter-ions
[30] (Table 4.1).
Structure
Normally, active sites are arranged to form cross-linked chains. Resins with high
crosslink percentages show a more rigid structure and provide a greater number of
active groups. Common resins are usually available from 2% up to 12% or even
16% of crosslink percentage. In practice, performance of resins is mainly affected
by crosslink percentage since it has an impact on the degree of selectivity.
39
4.6. Extraction chromatography (EXC)
40
Table 4.2 – Common commercial EXC resins
Resin Sr DGA
Extractant
Different models have already been proposed to describe the overall mechanism
and equilibrium processes implicated in the extraction chromatography technique
41
[51]. A first model, for example, assumes that the neutral complex is first formed in
the aqueous phase (Equation 4.9) and then transferred to the organic phase
(Equation 4.10), where the extraction process takes place.
A second model suggests that the species are first transferred to the organic phase
(Equations 4.11) under their ionic form and then they form the neutral complex in
the organic phase (Equation 4.12) to be extracted.
In both cases, however, the general equation for the extraction process can be
expressed as follows:
42
where, M+ represents a metal, L– a ligand, ML the neutral complex formed, and E
the extractant that usually has an electron donor property.
4.7. IEC and EXC for radiochemical separations and potential applications
for Sr-90 and Zr-90
Earlier studies have demonstrated the possibility, for example, of using IEC resins
to isolate fission products to evaluate their toxicity even when they are presented at
trace levels in samples [54]. Some studies have also showed the efficiency of
using ion exchange resins to separate radiostrontium from a variety of matrix [31,
36, 37].
Specifically for a given Sr-Zr system, Strelow had showed that regardless the
acidic conditions, zirconium usually experiences stronger affinity with a cationic
resin than numerous other elements, including Sr (Table 4.3) [9, 10].
43
Table 4.3 – Distribution ratios (D) for strontium and zirconium
in the AG50W-X8 resin
0.5 M 1.0 M 2.0 M 3.0 M 4.0 M
Eluent
Zr Sr Zr Sr Zr Sr Zr Sr Zr Sr
HCl 105 217 7250 60.2 489 17.8 61 10 14.5 7.5
HNO3 104 146 6500 39.2 652 8.8 112 6.1 30.7 4.7
Likewise, zirconium seems to have a stronger affinity with anionic resins while
strontium, does not have any affinity in hydrochloric or nitric acid conditions (Figure
4.7) [55].
Figure 4.7 – D values for strontium and zirconium in the Dowex 1-X10 resin
44
Recent studies, however, have demonstrated that extraction chromatography is
now starting to compete with ion exchange in many separation problems, including
radiochemical applications where trace levels of analytes are eventually implicated.
Most part of those applications has been focused on the separation and analysis of
radionuclides in environmental samples [56,62]. However, Maxwell and Culligan
have reported the separation performance of extraction resins for urine samples
containing actinides and Sr-90 [63]. Likewise, Kim et al. have presented a
separation method to isolate Sr-89 and Sr-90 from calcium, barium, and yttrium in
milk samples [64].
As for ion exchange resins, distribution ratios or also capacity factors for most part
of elements in extraction resins have already been reported [14]. As an example,
figure 4.8 presents the difference between the capacity factors of strontium and
zirconium in the DGA resin. As demonstrated, the potential to separate those two
elements using nitric acid solutions becomes possible, as the capacity factor for Sr
at 1M HNO3 is at least three times higher than that for Zr. In other words, Sr is
more likely to experience a longer retention time than Zr, while this last can be
faster eluted from the column.
45
Figure 4.8 – Capacity factor for strontium and zirconium
in the DGA resin [66]
46
Chapter 5
5. Experimental
This chapter describes the methodology and list the materials used throughout the
present work in order to determine the best condition to separate and quantify
strontium and zirconium for age-dating applications.
5.1. Chemicals
SrTiO3 (Aldrich, 99%) has been used for digestion tests to simulate true solid
samples containing radiostrontium in the titanate form. The digestion protocol has
been adapted from Parker et al [67]. The tests have been performed under high-
pressure (Easy PrepTM vials) using a microwave oven (Mars 5) from CEM
Corporation with temperature and pressure controls. The digestion program is
presented in Table 5.1.
47
Table 5.1 – Instrumental setting for SrTiO3 digestion
(Mars 5, Easy PrepTM vials)
Power Ramp Pressure Temperature Hold
Stage
Max % Min Psi °C Min
1 1600 100 30 250 160 5
2 1600 100 30 250 200 40
Precise masses of SrTiO3 were first weighed in 5 mL Teflon vials and then diluted
in concentrated nitric acid before being transferred to the microwave vessels. Poor
recoveries have been observed when SrTiO3 was weighed directly in the
microwave vessels. Actually, the strong electrostatic interactions between SrTiO3
and the surface of microwave vessels resulted in significant losses of the product
during sample preparation.
48
5.4. Omnifit® glass column preparation
5.5. Methodology
After packing, resins have been washed with water and then conditioned with an
acid solution, usually the eluent used to elute the first component from the column.
Before injecting the mixture to be separated, a blank was recovered. It consisted of
49
the same eluent used for the conditioning step. After sample injection, strontium
and zirconium were recovered in polypropylene centrifuge tubes using the
appropriate eluent (Figure 5.2).
50
5.2 summarizes optimal acquisition settings for the quantification purpose.
Lenses
Extract 1 5.3 V
Extract 2 -225.0 V
Omega Bias -200 V
Omega Lens 28.0 V
Q1 Entrance 3.0 V
Q1 Exit -2.0 V
Cell Focus 1.0 V
Cell Entrance -50 V
Cell Exit -50 V
Deflect 15.2 V
Plate Bias -50 V
Q1
Q1 Bias -6.0 V
Q1 Prefilter Bias -20.0 V
Q1 Postfilter Bias -30.0 V
Q1 Ion Guide
SLS Factor 0.40
SLG 0.90 V
Cell
Gas mode No gas
OctP Bias -8.0 V
OctP RF 180 V
Energy Discrimination 5.0 V
Wait Time Offset
Wait Time Offset 0 msec
Spectrum mode options
Replicates 3
Sweeps 100
51
Indium as internal standard. According to Kozuka et al., ideal internal standards
should have ionization energies close to that for measured elements [68]. Table
5.3 presents the ionization energy for strontium, zirconium, and indium.
Strontium 5.69
Zirconium 6.63
Indium (internal standard) 5.79
Both the detection limit (LOD) and the quantification limit (LOQ) were estimated
through the determination of the standard deviation (s) obtained for the analysis of
10 blanks in 4% nitric acid (Equation 5.1 and 5.2) .
LOD = 3s (5.1)
The potential to use oxygen in reaction cells to separate strontium and zirconium
has been assessed through the analysis of standard solutions at different gas
compositions. In this case, strontium has been monitored at m/z 88 (Sr +) and m/z
104 (SrO+) as well as zirconium at m/z 90 (Zr+) and m/z 106 (ZrO+). The interaction
between yttrium and oxygen has also been evaluated and both m/z 89 and m/z
52
105 have also been monitored. The acquisition parameters used during reaction-
cell tests are presented in Table 5.4.
Lenses
Extract 1 5.3 V
Extract 2 -225.0 V
Omega Bias -200 V
Omega Lens 28.0 V
Q1 Entrance 3.0 V
Q1 Exit -2.0 V
Cell Focus 1.0 V
Cell Entrance -50 V
Cell Exit -50 V
Deflect 15.2 V
Plate Bias -50 V
Q1
Q1 Bias -4.0 V
Q1 Prefilter Bias -22.0 V
Q1 Postfilter Bias -20.0 V
Cell
Gas mode Use gas
4th Gas Flow (O2) 0 – 100 %
OctP Bias -8.0 V
OctP RF 180 V
Energy Discrimination 5.0 V
Wait Time Offset
Wait Time Offset 60 msec
Spectrum mode options
Replicates 3
Sweeps 100
53
5.7. Analysis of Sr-90 by liquid scintillation
Counting corrections
Static Controller On
Luminescence Correction Off
Colored Samples n/a
Heterogeneity Monitor n/a
Coincidence Time (nsec) 18
Delay Before Burst (nsec) 75
Half Life Correction Off
a. lower limit
b. Upper limit
54
Chapter 6
As presented in Table 6.2, efficient digestion has been obtained using mixtures
containing HF. Even if concentrated nitric acid is considered as a strong oxidizing
agent, addition of HF is usually necessary for complete dissolution of oxide
compounds [69].
55
Table 6.2 – Digestion efficiency of SrTiO3 under different acidic conditions
HNO3 HNO3/H2O2 HNO3/HF/H2O2 HNO3/HF
Element Mixture 1 Mixture 2 Mixture 3 Mixture 4
(%) (%) (%) (%)
92 101 100 101
Sr 98 96 98 94
97 92 97 109
Average 95 ± 3 97 ± 4 98 ± 1 101 ± 8
Ti 0 31 ± 8 96 ± 1 96 ± 6
The presence of H2O2 does not improve the performance of SrTiO3 digestion.
Likewise, the appearance of the SrTiO3 solution after digestion in HNO3/HF
demonstrates that samples containing approximately 10,000 mg/L of SrTiO 3 were
very transparent, which has made the usage of H2O2 unnecessary to obtain
satisfactory results.
In general, digestion using only HNO3/HF has not only been proven to be the most
convenient and efficient method and also a very reproducible approach. For nine
replicates, obtained recovery for Sr was 102 2 %, while for Ti, 97 1 %, which
means that up to 3% of titanium could not be dissolved under those conditions
(Figure 6.1).
56
110
100
90
80
% in solution
70
60
50 Sr
40 Ti
30
20
10
0
1 2 3 4 5 6 7 8 9
Replicate ID
Figure 6.1 – Reproducibility of SrTiO3 digestion using HNO3/HF mixture
Due to the difficulty to generate SrTiO3 pellets in the laboratory, digestion tests
have been performed using only SrTiO3 under the powder form.
The method to separate zirconium from strontium using the cationic AG50W-X8
resin has been adapted from the method proposed by Strelow [70]. A similar
method has been already proven to provide good reproducibility making possible
its application in geochronology work for age determination [71].
Preliminary tests have been performed using about 10 g of AG50W-X8 resin, 100-
200 mesh, H+ form (Eichrom) poured into a 15 i.d. X 100 mm glass column.
Experimental elution curves have been obtained using weighed solutions
57
containing equivalent amounts of Sr and Zr (50 µg/mL) eluted in 2, 3 and 4M HCl.
Molarities lower than 2M have been disregarded due to the high distribution ratio
values reported in the literature [9]. In practice, extremely long retention times
would be expected for these conditions.
50
45
40
35
Recovery (%)
30
25
Sr
20
15 Zr
10
5
0
0 10 20 30 40 50 60 70 80 90 100
4M HCl (mL)
Figure 6.2 – Elution profile of Sr and Zr in 4M HCl
(10 g AG50W-X8, 100-200 mesh)
58
50
45
40
Recovery (%)
35
30
25
Sr
20
15 Zr
10
5
0
0 50 60 70 80 90 100 110 120 130 140 150
3M HCl (mL)
Figure 6.3 – Elution profile of Sr and Zr in 3M HCl
(10 g AG50W-X8, 100-200 mesh)
Briefly, 2M HCl has shown to be the most efficient condition to separate Sr and Zr
among the three scenarios tested (Figures 6.4). A separation factor of 27 has been
calculated in this case.
50
45 2M HCl 6M HCl
40
Recovery (%)
35
30
25
Sr
20
15 Zr
10
5
0
50
100
110
120
130
140
150
160
170
180
190
200
250
300
350
400
450
500
550
0
HCl (mL)
Figure 6.4 – Separation of Sr and Zr using a 2M to 6M HCl gradient
(10 g AG50W-X8, 100-200 mesh)
59
Apparently, in 2M HCl Zr is completed retained in the column during Sr elution and
Zr removal was only possible after the addition of 6M HCl. Actually, the increase in
solvent concentration increased the number of H+ ions in the system and to
displace zirconium that was then easily stripped off the column.
45
40
35
4M HCl
30
3M HCl
Sr (%)
25
20 2M HCl
15
10
5
0
0 20 40 60 80 100 120 140 160 180 200
HCl (mL)
Figure 6.5 – Elution curves of Sr as function of HCl molarity
(10 g AG50W-X8, 100-200 mesh)
Since the distribution ratio of Sr in nitric acid eluent was theoretically two times
smaller than for HCl (Table 4.3), better performance has been obtained by
replacing HCl by HNO3. As demonstrated in Figure 6.6, 2M HNO3 eluent produced
narrower peaks and it shifted the maximum peak from about 150 mL to about 80
mL.
60
25
20
15
Sr (%)
2M HCl
10 2M HNO3
0
0 50 100 150 200 250
Eluent (mL)
Figure 6.6 – Elution curves of Sr at 2M HNO3 and 2M HCl
(10 g AG50W-X8, 100-200 mesh)
In general, poor recoveries for Zr have been obtained using the AG50W-X8 resin
probably resulting from problems of resin shrinkage after increasing the eluent
concentration from 2M to 6M. To avoid sudden changes that could disturb
equilibrium in the column, the usage of stronger eluents at low molarities was also
assessed. Higher cross-linking resins, however, could also help reducing shrinkage
issues.
Tests have demonstrated that sulphuric and oxalic acids could be used as
alternative eluents of Zr. Based on results presented in Table 6.3, 2M H 2SO4, 3M
H2SO4, and 0.2M H2C2O4 have provided both peak asymmetry and reasonable
recovery.
61
Table 6.3 – Performance of alternative eluents for Zr
Zr Recovery
Eluent Peak Asymmetry
(%)
2M H2SO4 1.2 104 ± 3
3M H2SO4 1.0 101 ± 2
0.2M H2C2O4 1.2 123 ± 3
Utilization of oxalic and sulphuric acids, however, has been limited to elution tests
involving high concentrations of Zr where the evaporation steps were not required
to concentrate the analyte. Due to the high boiling point of H 2SO4, the utilization of
Teflon vials became impracticable and glass beakers have been avoided since
they could contain significant amounts of Zr able to contaminate the samples.
62
70
2M HNO3 6M HCl
60
50
Recovery (%)
40
Sr
30
Zr
20
10
0
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Eluent (mL)
Figure 6.7 – Separation of Sr and Zr using a 2M HNO3 to 6M HCl gradient in 2
g AG50W-X8 (100-200 mesh)
150
130
110
2M HNO3 (mL)
90
70
50
30
10
10g 2g 1g 0.5g
AG50W-X8 (g)
Figure 6.8 – Volume of eluent for Sr elution as function of mass of AG50W-X8
63
Reducing column beds, however, has demanded the adjustment of the volume of
loaded sample in order to prevent extra-column effects [72]. In general, compatible
loading volumes have been proved to ensure peak shape and avoid peak overlap.
Suggested loading volumes according to the mass of resin used are presented in
Table 6.4.
64
120
110 11M HCl 4M HCl
100
90
Recovery (%) 80
70
60
50 Sr
40 Zr
30
20
10
0
0 5 10 15 20 25 30 35 40 45 50
HCl (mL)
100
90
Zr uptake (%)
80
70
60
50
8 9 10 11
HCl (M)
Figure 6.10 – Zirconium retention in Dowex1-X8 as function of HCl
concentration
65
At the end, 4M HCl has been proved to be the best condition for Zr elution. Under
this condition, however, recoveries higher than 100% have been observed, which
was interpreted as possible column contaminations or interferences in mass
spectrometry caused by traces of HCl in samples (Figure 6.11).
130
120
110
100
Zr recovery (%)
90
80
70
60
50
40
30
20
0 1 2 3 4
HCl (M)
Figure 6.11 – Maximum recovery of Zr according to HCl concentration in
Dowex1-X8
The performance of ion exchange and extraction resins has been carried out using
approximately 0.5 g of resin, 250 µL of sample loading, and 40 mL of eluent (i.e. 20
mL for Sr eluent and 20 mL for Zr eluent). In general, eluents have been chosen
according to their capability to provide the best resolution and/or maximum
recovery. Optimal results for each one of the four resins tested (AG50W-X8 – 100-
200 mesh, Dowex1-X8 – 100-200 mesh, Sr – 50-100 µm, and DGA – 50-100 µm)
are presented in Figure 6.12.
66
100
2M HNO3 3M H2SO4
Recovery (%)
80
60 Sr
40 Y
20 Zr
a
0
100
11M HCl 4M HCl
Recovery (%)
80
60
40
20 b
0
100
0.05M HNO3 3M HNO3
Recovery (%)
80
60
40
20
c
0
100
0.05M HNO3 1M HNO3 H2O
Recovery (%)
80
60
40
20
d
0
0 5 10 15 20 25 30 35 40 45 50
Eluent (mL)
Figure 6.12 – Comparative of separation of Sr and Zr using ion exchange and
extraction resins (a. AG50W-X8, b. DOWEX1-X8, c. Sr-Resin, d. DGA-Resin)
67
Contrary to results obtained for IEC resins, Zr and Sr have exhibited opposite
behaviours in both Sr and DGA resins. Actually, the ability of zirconium to form
charged complexes has certainly increased its affinity with the aqueous mobile
phase, which probably contributed to reduce its retention time in EXC. Such an
effect could not be possible for Sr since it cannot form charged complexes and, for
that reason, it has shown stronger affinity with the organic stationary phase and a
longer retention time in Sr and DGA resins (Figure 6.13).
Figure 6.13 – Proposed extraction mechanism for Sr for its separation from
Zr by EXC
In practice, the possibility to recover zirconium before strontium reduced the risks
of peak overlap caused by tailing problems at high concentrations of Sr potentially
found in real samples. Results presented in Figure 6.14 show that tailing problems
started to become important once the Sr concentration increased from 10 µg/mL to
1000 µg/mL.
68
100 10 µg/mL
90 50 µg/mL
80
100 µg/mL
70
60 1000 µg/mL
Sr (%)
50
40
30
20
10
0
40 60 80 100 120 140 160 180 200
2M HNO3 (mL)
Figure 6.14 – Tailing effect as function of Sr concentration (AG50W-X8)
For the anionic resin, separation was compromised after addition of 0.01% HF to
the samples. As demonstrated in Figure 6.15, peak overlapping has been
69
observed. Repulsion forces between neutral or positive complexes of zirconium
and the active site on resin surface probably contributed to accelerate Zr elution.
100
Sr
90
80 Zr
70
Recovery (%)
60
50
40
30
20
10
0
0 5 10 15 20
Eluent (mL)
Figure 6.15 – Separation of Sr and Zr using Dowex1-X8 for samples
containing HF
For DGA resin, on the other hand, the utilization of HF in samples has not only
helped to increase Zr recovery but also ensured separation efficiency. As
demonstrated in Figure 6.16, recovery of zirconium was increased from 11 ± 1% to
102 ± 10% and no overlapping has been detected after HF concentration was
increased from 0.01% to 0.2%.
70
100
1M HNO3 0.05M HNO3
80
Recovery (%) 60
40
20
a
0
100
80
Recovery (%)
60
40
20 Sr
b Zr
0
0 5 10 15 20 25 30 35 40 45 50
Eluent (mL)
71
Table 6.5 – Recovery of Zr in DGA Resin according to
HNO3/HF ratio in samples
HNO3/HF [HNO3] [HF] Recovery
Ratio (M) (M) (%)
5 1 0.2 100
5 0.5 0.1 112
10 1 0.1 52
10 2 0.2 59
Table 6.6 summarizes the performance of the fours resins tested to separate
strontium from zirconium. The respective recoveries for each element under all the
experimental conditions tested over this work can be find in the Annexe 1.
72
In general, DGA resin has proven to be the most efficient alternative to obtain
satisfactory separation and acceptable zirconium recovery. As presented in Table
6.6, DGA was the only resin able to eliminate both potential interferences from Sr
and Y at m/z 90 even under conditions where HF was present. Due to its superior
performance over other resins, a complete methodology using DGA resin for
isolating zirconium prior to MS analysis has been proposed (Figure 6.17).
Before starting the separation, the resin was usually cleaned with 50 mL of water
and conditioned with 5 mL 1M nitric acid. A blank was then recovered before
loading the sample. The sample load solution, was prepared in a mixture of 1M
HNO3 / 0.2M HF and finally, zirconium was recovered using a 10 mL 1M HNO 3 as
the eluent.
The method presented in Figure 6.17 has been tested in standard solutions
73
containing zirconium concentrations at ppt levels and concentrations for strontium
100 times higher than those for Zr (Figure 6.18).
20
Expected values Experimental Results
Zr (ng/mL)
15
10
0
1 2 3 4 5 6
Sample ID
Figure 6.18 – Comparative between experimental and expected results for the
recovery of trace levels of Zr using DGA resin
Except for samples 1 and 2, other samples exhibited a good correlation with
expected values. Average recovery obtained for zirconium was 94 ± 6%. The
detection limit for zirconium has been determined as being 92 pg/mL. No strontium
has been detected in the zirconium fractions. The detection limit for strontium has
been determined as being 48 pg/mL.
74
Figure 6.19 – Procedure for determining the age of a radiostrontium source
As the exact concentration of Zr-90 was not available, blanks and standard
solutions have been used to ensure the quality of results for Zr analysis. For Sr-90,
it was observed that the experimental concentration was about 30 % lower than the
theoretical concentration (Figure 6.20).
75
40 y = 220.5756x
R² = 0.9993
30
cpm
20
10
Theoretical [Sr-90]
Experimental [Sr-90]
0
0.00 0.05 0.10 0.15 0.20
Bq/mL
Figure 6.20 – Comparative between theoretical and experimental
concentrations for the analysis of Sr-90 by liquid scintillation
Although the true age of the radiostrontium source was unknown, an age of 68 ±
11 years was proposed. Calculations have been based on the principles of the
decay law treated in section 2. The error of 11 years, however, has been
considered too high for nuclear forensic applications. Problems associated to the
quality of Sr-90 solution have been considered as the main cause to the lack of
accuracy encountered.
76
6000
5000
Signal (cps)
4000
3000
SrO+
2000
ZrO+
1000
0
0 10 20 30 40 50 60 70 80 90 100
O2 (%)
The formation of ZrO+ (m/z 106) showed to be favoured at 10% oxygen, where a
maximum peak was detected. At this point, a decontamination factor of about 80%
against strontium was obtained.
77
100
90 90Zr+
80
Zr species (%)
70 90Zr16O+
60
90Zr16O1H+
50 90Zr16O2+
40
30 90Zr16O1H2+
20
10 a
0
85 90 95 100 105 110 115 120 125
100 88
90 Sr+
80
Sr species (%)
70
60 88
50 Sr16O+ 88
Sr16O2+
40 88
30 Sr16O1H+
20
10 b
0
85 90 95 100 105 110 115 120 125
78
100 R² = 0.997
90
Zr at m/z = 106
80
(ng/mL)
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100
Zr at m/z = 90
(ng/mL)
Figure 6.23 – Correlation between results for the analysis of Zr at m/z 90
and m/z 106
100 89 +
90 Y
80
Y species (%)
70
60 89 16
Y O+ 89 16
Y O2+
50 89 16
Y O1H+
40 89 1
30 Y H+
89 16
Y O1H2+
20
10
0
85 90 95 100 105 110 115 120 125
m/z
79
80
Conclusions
The present work, demonstrates that the utilization of collision cells in MS without
prior chromatographic separation does not provide sufficient resolution to
completely isolate Zr from all its isobaric interferences. However, the results
suggest that triple quadrupole instruments (ICPQQQ-MS) have a potential to
significantly minimize the level of isobaric interferences while reducing both the
duration and the complexity of sample preparation procedures.
Among four commercial resins tested, DGA has been proved to provide the best
performance for the radiological separation. Recoveries higher than 99% for Zr
have been obtained. The DGA approach has also been demonstrated to be the
faster approach and the more efficient to eliminate both the isobaric interferences
from Strontium and Yttrium. None of these two elements have been detected by
mass spectrometry after the chromatographic separation.
Finally, the proposed method using DGA combined to MS and liquid scintillation for
the respective analysis of Zr-90 and Sr-90 has been applied to determine the age
of an aqueous solution of radiostrontium. Although the true age of the radioactive
81
source was unknown, an age of 68 ± 11 years was calculated. The uncertainty of
11 years observed, however, has been considered too high for nuclear forensic
applications. Problems associated to the quality of Sr-90 solution have been
considered as the main cause to the lack of accuracy encountered.
More tests using sources of radiostrontium having well known ages would help to
identify the major sources of error. They would also validate the proposed method
while helping to determine the precision of the age determined experimentally.
Likewise, the utilization of Teflon material and ultra-pure acidic solutions would
help to minimize systematic errors by preventing any trace of unwanted
contamination.
82
References
[1] Mayer, K.; Wallenius, M.; Fanghaenel, T. Journal of Alloys and Compounds
2007, 444, 50-56.
[2] International Atomic Energy Agency. Nuclear Security Report 2013, 1-16.
[3] Charbonneau, L.; Benoit, J.-M.; Jovanovic, S.; St-Amant, N.; Kiser, S.;
Cooke, M. W.; Mercier, J.-F.; Nielsen, K.; Kelly, D.; Samuleev, P.; Galea, R.;
Moore, K.; Saull, P. R. B.; Chamberlain, D. B.; Steeb, J. L.; Graczyk, D. G.;
Tsai, Y.; Sullivan, V. S.; Dimayuga, I. C.; Shi, Y.; Rao, R.; Larivière, D.
Analytical Methods 2014, 6, 983-992.
[4] Amano, H.; Yanase, N. Talanta 1990, 37, 585-590.
[5] Froidevaux, P.; Geering, J.-J.; Valley, J. F. Science of the Total Environment
2006, 367, 596-605.
[6] Grahek, Z.; Eskinja, I.; Kosutic, K.; Lulic, S.; Kvastek, K. Journal of
Radioanalytical and Nuclear Chemistry 1999, 241, 617-626.
[7] Maxwell, S. L.; Culligan, B. K.; Utsey, R. C. Journal of Radioanalytical and
Nuclear Chemistry 2013, 298, 867-875.
[8] Steeb, J. L.; Graczyk, D. G.; Tsai, Y.; Mertz, C. J.; Essling, A. M.; Sullivan, V.
S.; Carney, K. P.; Finck, M. R.; Giglio, J. J.; Chamberlain, D. B. Journal of
Analytical Atomic Spectrometry 2013, 28, 1493-1507.
[9] Strelow, F. W. E. Analytical Chemistry 1960, 32, 1185-1188.
[10] Strelow, F. W. E.; Rethemey. R; Bothma, C. J. C. Analytical Chemistry 1965,
37, 106-111.
[11] Huffman, E. H.; Iddings, G. M.; Lilly, R. C. Journal of the American Chemical
Society 1951, 73, 4474-4475.
[12] Bunney, L. R.; Ballou, N. E.; Pascual, J.; Foti, S. Analytical Chemistry 1959,
31, 324-326.
[13] Faris, J. P. Analytical Chemistry 1960, 32, 520-522.
[14] Pourmand, A.; Dauphas, N. Talanta 2010, 81, 741-753.
[15] Lallanilla, M. Live Science Retrieved March 24, 2014 from <
http://www.livescience.com/44318-chernobyl-trees-barely-
decomposed.html>.
[16] Institut de Radioprotection et de Santé Nucléaire Retrieved August 22,
2014 from <
http://environnement.irsn.fr/document/site_1/fckfiles/File/dossiers/tchernobyl/
tchernobyl_16.pdf>.
[17] Environmental Protection Agency Retrieved August 22, 2014 from <
http://www.epa.gov/radiation/radionuclides/strontium.html>
[18] Environmental Protection Agency Retrieved August 31, 2014 from <
http://epa.gov/radiation/radionuclides/iodine.html>.
[19] United Nations Scientific Committee on the Effects of Atomic Radiation
Retrieved August 31, 2014 from <
http://www.unscear.org/unscear/en/chernobyl.html>.
[20] Nielsen, E.; Greve, K.; Ladefoged, O. The Danish Environmental Protection
Agency 2013, 40 p.
83
[21] Glasstone, S.; Dolan, P. J.; United States Department of Defense and the
Energy Research and Development Administration 1977, 3rd edition, 605 p.
[22] International Atomic Energy Agency. Retrieved August 21, 2014 from <
http://www.iaea.org/OurWork/ST/NE/NEFW/News/2012/repository/RTGs-
Removed-Successfully-from-the-Baltic-Sea.html>.
[23] International Atomic Energy Agency. Retrieved August 22, 2014 from <
http://www.iaea.org/Publications/Magazines/Bulletin/Bull481/htmls/rtg_accid
ents.html>.
[24] BBC Retrieved August 22, 2014 from <
https://www.youtube.com/watch?v=opTHVe8fzlg>.
[25] Wallenius, M.; Mayer, K.; Ray, I. Forensic Science International 2006, 156,
55-62.
[26] Boulyga, S. F. International Journal of Mass Spectrometry 2011, 307, 200-
210.
[27] Becker, J. S.; Dietze, H.-J. Spectrochimica Acta Part B: Atomic
Spectroscopy 1998, 53, 1475-1506.
[28] Hou, X.; Roos, P. Analytica Chimica Acta 2008, 608, 105-139.
[29] Shimadzu. Retrieved August 31, 2014 from <
http://www.shimadzu.com/an/lcms/support/intro/lib/lctalk/61/61intro.html>.
[30] Patnaik, P. McGraw-Hill Handbooks 2004, 2nd edition, 1280 p.
[31] Vonderheide, A. P.; Zoriy, M. V.; Izmer, A. V.; Pickhardt, C.; Caruso, J. A.;
Ostapczuk, P.; Hille, R.; Becker, J. S. Journal of Analytical Atomic
Spectrometry 2004, 19, 675-680.
[32] Favre, G.; Brennetot, R.; Chartier, F.; Vitorge, P. International Journal of
Mass Spectrometry 2007, 265, 15-22.
[33] Thomas, R. CRC Press 2008, 2nd edition, 376 p.
[34] Dean, J. R. Wiley 2005, 1st edition, 208 p.
[35] Epov, V. N.; Taylor, V.; Lariviere, D.; Evans, R. D.; Cornett, R. J. Journal of
Radioanalytical and Nuclear Chemistry 2003, 258, 473-482.
[36] Isnard, H.; Aubert, M.; Blanchet, P.; Brennetot, R.; Chartier, F.; Geertsen, V.;
Manuguerra, F. Spectrochimica Acta Part B 2006, 61, 150-156.
[37] Feuerstein, J.; Boulyga, S. F.; Galler, P.; Stingeder, G.; Prohaska, T. Journal
of Environmental Radioactivity 2008, 99, 1764-1769.
[38] Amr, M. A.; Abdel-Lateef, A. M. International Journal of Mass Spectrometry
2011, 299, 184-190.
[39] Sakama, M.; Nagano, Y.; Saze, T.; Higaki, S.; Kitade, T.; Izawa, N.; Shikino,
O.; Nakayama, S. Applied Radiation and Isotopes 2013, 81, 201-207.
[40] Eiden, G. C.; Barinaga, C. J.; Koppenaal, D. Rapid Communications in Mass
Spectrometry 1997, 11, 37-42.
[41] Pennsylvania State University Environmental Health & Safety. Retrieved
August 22, 2014 from < http://www.ehs.psu.edu/radprot/LSC_Theory2.pdf>.
[42] L'Annunziata, M. F. Academic Press 2012, 3rd edition, 1418 p.
[43] IUPAC. Retrieved August 22, 2014 from <
http://goldbook.iupac.org/D01817.html>.
[44] Littlewood, A.B. Elsevier 2013, 560 p.
[45] Naushad, M. Khan, M. R. CRC Press 2014, 480 p.
[46] Weston, A. Brown, P. R. Academic Press 1997, 280 p.
84
[47] Bayne, S.; Carlin, M. CRC Press LLC 2010, 272 p.
[48] GE Healthcare. Retrieved September 1, 2014 from < https://www.uni-
ulm.de/uploads/media/Ion_exchange_chromatography_and_Chromatofocusi
ng_02.pdf>.
[49] Helfferich, F. G. McGraw-Hill 1962, 624 p.
[50] Triskem. Retrieved August 22, 2014 from < http://www.triskem-
international.com/full_extraction_chromatographie.asp>.
[51] Braun, T.; Ghersini, G. Elsevier Science 1975, 2, 584 p.
[52] Lamb, J. D.; Nordmeyer, F. R.; Drake, P. A.; Elder, M. P.; Miles, R. W.; Lash,
R. P. Journal of Radioanalytical and Nuclear Chemistry 1989, 134, 317-331.
[53] Kraus, K. A.; Nelson, F. Annual Review of Nuclear Science 1957, 7, 31-46.
[54] Tompkins, E. R.; Khym, J. X.; Chon, W. E. Journal of the American Chemical
Society 1947, 69, 2769-2777.
[55] Saito, N. Pure and Applied Chemistry 1984, 56, 523-539.
[56] Lee, M. H.; Ahn, H. J.; Park, J. H.; Park, Y. J.; Song, K. Applied Radiation
and Isotopes 2011, 69, 295-298.
[57] Harrison, J. J.; Zawadzki, A.; Chisari, R.; Wong, H. K. Journal of
Environmental Radioactivity 2011, 102, 896-900.
[58] Maxwell, S. L. Journal of Radioanalytical and Nuclear Chemistry 2006, 267,
537-543.
[59] Wang, J.-J.; Chen, I.-J.; Chiu, J.-H. Applied Radiation and Isotopes 2004,
61, 299-304.
[60] Roane, J. E.; DeVol, T. A.; Leyba, J. D.; Fjeld, R. A. Journal of
Environmental Radioactivity 2003, 66, 227-245.
[61] Mellado, J.; Llaurado, M.; Rauret, G. Analytica Chimica Acta 2001, 443, 81-
90.
[62] La Rosa, J. J.; Burnett, W.; Lee, S. H.; Levy, S. H.; Gastaud, J.; Povinec, P.
P. Journal of Radioanalytical and Nuclear Chemistry 2001, 248, 765-770.
[63] Maxwell, S. L.; Culligan, B. K. Journal of Radioanalytical and Nuclear
Chemistry 2009, 279, 901-907.
[64] Kim, C. K.; Al-Hamwi, A.; Torvenyi, A.; Kis-Benedek, G.; Sansone, U.
Applied Radiation and Isotopes 2009, 67, 786-793.
[65] Horwitz, E. P.; Dietz, M. L.; Chiarizia, R. Journal of Radioanalytical and
Nuclear Chemistry 1992, 161, 575-583.
[66] Eichrom. Retrieved August 22, 2014 from <
http://www.eichrom.com/products/info/dga_resin.aspx>.
[67] Packer, A.-P.; Lariviere, D.; Li, C.; Chen, M.; Fawcett, A.; Nielsen, K.;
Mattson, K.; Chatt, A.; Scriver, C.; Erhardt, L. S. Analytica Chimica Acta
2007, 588, 166-172.
[68] Kozuka, S.; Yokote, Y.; Abe, K.; Hayashi, M.; Matsunaga, H. Fresenius
Journal of Analytical Chemistry 1995, 351, 801-802.
[69] Lahiri, S. New Delhi: Norosa Publishing House 2008, 186 p.
[70] Strelow, F. W. E. Analytical Chemistry 1959, 31, 1974-1977.
[71] Strelow, F. W. E. Analytical Chemistry 1959, 31, 1201-1203.
[72] Neue, U. D. Wiley-VCH 1997, 416 p.
85
86
Annexe 1
87