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Staying Focussed..

An introduction to stable
isotope mass spectroscopy
Stable Isotope analysis

Sample preparation
Chemically convert sample material (ie rocks, water, biological materials)
into gas
Quantitative

Measurement of isotope ratios


Mass spectroscopy
Laser cavity molecular spectroscopy

Normalization of results
Laboratory references
International standards
Stable Isotope mass specs are
gas-source
D/H H2
18O/16O CO2, CO, O2
C/12C
13 CO2, CO
15N/14N N2
34S/32S SO2, SO, SF6
Cl/35Cl
37 CH3Cl
Combust:
(C6H10O5)n + O2 CO2 + H20

(C6H10O5)n + C CO + H2

Reduce:
H20 + Zn H2 + ZnO

React:
SiO2 + BrF5 O2 + SiF2

O2 + C CO2

Equilibrate:
C16O2 + 2H218O C16O18O + 2H216O18O
Purification
Vacuum lines
Cryogenic (LN2) traps for
separation of gasses

Reaction vessels for chemical


reactions in vacuum

Usually used in conjunction


with off-line isotope analysis

Necessary for some analyses ie


silicate analyses
Gas Chromatography
Uses a GC column to separate gasses

He

TCD detectors

usually in a singe instrument as a


preparatory inlet to a mass spectrometer

Combustion/Reduction

Automation Mass
Spec
On-Line
Mass spectrometers
JJ Thomspon 1910 parabola
spectrograph
Discovered first stable isotopes (Ne mass 20-22)
Discovered the electron
Awarded nobel prize 1906

F.W.Aston mass spectrograph


Discovered 21Ne
212 out of 287 naturally occurring isotopes
Mass defect binding energies
Awarded nobel prize 1922
A Nier
First stable isotope abundance instrument
Electron-impact source
Dual detectors
Magnetic sector
Electronic rather than photographic ion counting
A lot has changed, a lot has
stayed the same
Inlet System:
DI or CF

Source of ions
M+ Pumping system
Diffusion or turbo
pumps
Analyser =
Magnetic sector

Detectors
-Faraday cups
-electronic ion
counting
Ion Source
Electron Impact source: M + e- M+ + 2e-

Electron energies ca. 100 eV


Electron emission 1mA or 6x1015 e-/s
Efficiency = 1 in 2400 molecules ionized

Problems:
-Linearity current const
measured ratios

-memory

-stability

-chemical inertness of hot filiament


Ionization efficiency - sensitivity
Electrons about 70 eV de
Broglie is about equal to Ca 70V
molecule bond lengths
About 1 in 1000 impacts give
ionization
Emission is about 1 mA
Cross section is low 10-7 mm2
About 1nA ion current from
1mA emission
Increased source pressure-
closed ion box
Potential across ion box too
high variable ion energies
too low ion-molecule
interactions.
fragmentation
Ion optics
About 50% efficient

Burn marks

Extraction

Half plate focussing

Fine-tuning

Generally

empirically tuned
Problem areas of source design
1. Deviations from linear behavior discrimination
ion-molecule interactions forming isobaric interferences
ie H3+
collimating magnetic field can lead to non-linear
response
changes in number of ions affects space charge of
ion-source therefore extraction conditions
careful source design
more important in CF instruments.
Problem areas of source design
2. Gas exchange
Minimize gas exchange in ion source
Pumping efficiency of source region
Avoidance of dead volumes
Chemical inertness of source materials
Filament chemical inertness and
conditioning
Problem areas in ion sources
3. High stability over time
electrostatic potentials need to be

stable to 200 ppm


insulating surface layers lead to

charging source cleaning


Analyser
Magnetic Sector

U=HT, B=Mag Field, z = # charge, e= charge, m=mass

m/z 44 (CO2) at 5KV = 13.5 cm, B=0.5T


Permanent/electromagnets
Magnetic field more uniform with electromagnets
Need two magnets for low mass
Image broadening by inhomogeneous ion energy
Large-radius high energy (10kV) less affected
E/U less in large radius instruments
Early instruments x-only focussing
All modern instruments X-Y (cross)focussing
Cross focussing
Stigmatic focussing
Ions enter and exit magnet at an
offset angle rather than 90
Fringing fields at the magnet
pole gap result in y-direction
focussing
Mat 250 1977
Permanent vs Electromagnets
From a theoretical veiwpoint both are identical
Limited mass selection with permanent magnets
5KV for N2 (typically designed at high end of HT range)
3.2 kV for CO2
2.2 kV for SO2 (v. low HT- lower resolution)
cannot scan lower than mass 28 without magnet change
HD separate magnet
Detectors
Faraday cups
Mechanically simple
Named after Micheal Farrady who first theorized ions about 1830

Error sources
-Secondary electrons
Circuit where charged ions are
-backscattering
the charge carriers in vacuum

Cup gains charge that can be


measured as current when
discharged

N/t = I/e
N/t= #of ions/sec, I= current,
e= elementary
charge(1.6x10-19 C)

1nA = 6x109 ions/sec


Electrometers
Measure charge or currrent (charge/sec)
Solid state transistors
Ohms law E=IR
1V = 10-9A x 109 ohms
Different resistors different currents - similar
voltages
Measured by ADC
High amplifications shielded
r m

Masses not evenly spaced so


cant get a collector array for
more than element

-compromise triple array or


moving collectors
Flat-topped peaks defining slit width
Inlets
McKinney (1950) introduced change-
over valve, thereby eliminating most
instrumental effects allowed measurement
of O2 and CO2 to 0.1 per mil
-Measured d13C to precisions of about 0.1
per mil
-Has essentially remained unchanged in
50 years
-smallest sample limited by
requirement to maintain viscous-
flow conditions
-Practical limit about 15-20 mbar
-Cold fingers for small volumes.
-Smallest sample size about 0.2
mol
- With a few exceptions, most
sample preparations are off-line
Continuous Flow or IR monitoring
inlet

GC techniques coupled to MS
No change over or dual inlet
Viscous flow in GC stream
Smaller sample sizes
Completely taken over most modern
analyses
Well suited for automated analyses

Things to be aware of:


o Linearity effects
o small measurement times
o absolute sensitivity
o isotope chromatography
o statistical limits on precision
o large He background (HD)
o Background corrections
Isotope Chromatography
Transport of gas through GC
not only separates chemical
species but also isotopic species
Cannot measure instantaneous
isotope ratios, but must
integrate entire peaks to count
ions
Makes correct background
subtraction, and peak
integration algorithms essential
HD measurement in He
Large mass 4 (He+) tails into m/z
3
Generally reduced by modern
instrument design
Differential pumping
Increased abundance sensitivity
by increased dispersion
Energy filters to homogenize
minimize U
Statistical Limits to precision
IRMS is basically measuring ion
currents
Ion currents have a standard deviation
as a result of shot noise
For low ion currents - poisson
distribuion
- = 1/N
Implications for CF-IRMS

-Typically small total ion numbers


are measured

For example typical 10nA CO2


peak
about 3x1011 ions for mass 44
-about 3x109 ions for mass 45

= 1/3x109 = 2x10-5 or about


0.02 per mil

Reference peak has similar


precisions so that minimum
statistical limit of is about 0.05
permil or so. Minimum.
Mass Resolution
Abundance Sensitivity
Basically, how much does one mass
peak overlap the other

About 10-5 on modern instruments for m/z=45


=0.001 per mil
Instrument Corrections 1. Leak correction (zero
enrichment)
Corrections to measured d values based - corrects for differences in the
on instrument properties two viscous leaks
- crimp is adjusted so that
Not as important on newer instruments as enrichment is zero
manufacturing and materials have
improved 2. Abundance sensitivity
- effect of one mass on the
Should be monitored to evaluate adjacent mass
instrument performance - principally controlled by
instrument design
- is different for each mass
- dependent on inlet pressure

3. Valve mixing
-mixing of reference and sample
gasses in the changeover valve
by cross seat leakage
- new changeovers minimize
this
Computation of values

Mass spectrometers measure abundance ratios or mass enrichments

Need to correct for isobaric interferences to get isotope ratios


Optical Methods
Two Competing technologies:
1. Wavelength-Scanned Cavity Ring Down Spectroscopy (WS-CRDS)
Picarro Inc
2. Off-axis integrated cavity output spectroscopy (OA-ICOS)
Los Gatos Research

HDO

H2O
Absorption spectrometry is a
direct measure of concentration

Very selective - C2H2 absorbs


light between 1510 - 1545 nm

Fast laser can be reproducibly


swept at > 100 Hz

For a 1 meter sample containing


100 torr of 1 ppm acetylene, I/I0
~ 10-5

Increase pathlength by (1-R)-1 ~


10,000 times, giving several
kilometers of effective path
Single-pass I/I0 ~ 10-5
Multipass I/I0 ~ 10-1 (a
considerable absorption)
Pros - cons
Pros
Cons
Do one thing really well eg Do one thing
H2O Difficult to calibrate
No compressed gasses Like IRMS instrumental
No moving parts effects
Cheap
Simple mechanically
Wikipedia A modern stable isotope ratio mass spectrometer