Stable Isotopes: principles,

integration and applications

Stabl e i sotope
Long-l i ved radi oi sotope
Short-l i ved radi oi sotope
16
P27 15
Si26 Si25 14
Al25 Al24 Al23 13
Mg24 Mg23 Mg22 Mg21 Mg20 12
Na23 Na22 Na21 Na20 Na19 11
Ne22 Ne21 Ne20 Ne19 Ne18 Ne17 10
F21 F20 F19 F18 F17 F16 9
O20 O19 O18 O17 O16 O15 O14 O13 8
N19 N18 N17 N16 N15 N14 N13 N12 N11 7
C18 C17 C16 C15 C14 C13 C12 C11 C10 C9 C8 6
B17 B15 B14 B13 B12 B11 B10 B9 B8 5
Be14 Be12 Be11 Be10 Be9 Be8 Be7 Be6 4
Li11 Li9 Li8 Li 7 Li 6 Li5 3
He8 He6 He5 He4 He3 2
Isotopes
T D H 1
12 11 10 9 8 7 6 5 4 3 2 1 0
Neutron Number (N)
S40 S39 S38 S37 S36 S35 S34 S33 S32 S31 S30 S29
P39 P38 P37 P36 P35 P34 P33 P32 P31 P30 P29 P28 P27
Si36 Si35 Si34 Si33 Si32 Si31 Si 30 Si 29 Si 28 Si27 Si26
Al34 Al33 Al32 Al31 Al30 Al29 Al28 Al 27 Al26 Al25
Mg32 Mg31 Mg30 Mg29 Mg28 Mg27 Mg26 Mg25 Mg24
Na33 Na32 Na31 Na30 Na29 Na28 Na27 Na26 Na25 Na24 Na23
Ne27 Ne26 Ne25 Ne24 Ne23 Ne22
F25 F24 F23 F22 F21
O24 O23 O22 O21 O20
N21 N20 N19
C19 C18
B17
24 23 22 21 20 19 18 17 16 15 14 13 12
Neutron Number (N)
Neutron Number (N) http://www2.bnl.gov/CoN/
P
r
o
t
o
n

N
u
m
b
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(
Z
)

Isobars
Isotopes
Isotones
Brief history
By year 1800 ~39 elements were known
John Dalton all matter is made of atoms led to
hypothesis that equal volume of gas contain equal
numbers of particles (Avogadro, 1811), or that atomic
weights are multiples of the mass of H (Prout, 1815).
1870 Mendeleev related chemical properties with
atomic weights producing the periodic table.
Rayleigh and Ramsay discover Ar in 1894 and He in
1895, by using the periodic table predictions.
By 1900, periodic table complete up to U. However,
atomic weights of some elements did not increase
with atomic # and Prouts hypothesis was disproved.
TW Richard (1900) first measure different atomic
weights in Pb.
Brief history
1895-1897 discovery of X-rays, cathode rays
(electrons) and Becquerel (1896) discovered the
spontaneous emission of radiation by U.
In 1914, Frederick Soddy, reworked Daltons
hypothesis of atoms by stating that the place of
an element in the periodic table can accommodate
more than one atom. He called these atoms
isotopes which means same place.

Isotopes = Nuclides of a single element that have
different atomic weights
Brief history
JJ Thomson used a modified cathode ray tube (first
mass spectrometer) to measure the charge-to-mass
ratio q/m (q/z) of gas particles (electrons). By 1913
identified the first isotopic masses of Neon (20 and 22).








JJ Thomsons cathode ray tube, 1897
In 1919 Astons mass spectrograph allowed to detect
212 of the 287 naturally occurring isotopes. Nobel
prize 1922.









It was 1932 when Chadwick discover the missing puzzle
piece: neutrons. Isotope existence was explained.
Brief history
FW Astons photograph
plate, 1919. Elements
with same mass will hit
the same spot
Stabl e i sotope
Long-l i ved radi oi sotope
Short-l i ved radi oi sotope
16
P27 15
Si26 Si25 14
Al25 Al24 Al23 13
Mg24 Mg23 Mg22 Mg21 Mg20 12
Na23 Na22 Na21 Na20 Na19 11
Ne22 Ne21 Ne20 Ne19 Ne18 Ne17 10
F21 F20 F19 F18 F17 F16 9
O20 O19 O18 O17 O16 O15 O14 O13 8
N19 N18 N17 N16 N15 N14 N13 N12 N11 7
C18 C17 C16 C15 C14 C13 C12 C11 C10 C9 C8 6
B17 B15 B14 B13 B12 B11 B10 B9 B8 5
Be14 Be12 Be11 Be10 Be9 Be8 Be7 Be6 4
Li11 Li9 Li8 Li 7 Li 6 Li5 3
He8 He6 He5 He4 He3 2
Isotopes
T D H 1
12 11 10 9 8 7 6 5 4 3 2 1 0
Neutron Number (N)
S40 S39 S38 S37 S36 S35 S34 S33 S32 S31 S30 S29
P39 P38 P37 P36 P35 P34 P33 P32 P31 P30 P29 P28 P27
Si36 Si35 Si34 Si33 Si32 Si31 Si 30 Si 29 Si 28 Si27 Si26
Al34 Al33 Al32 Al31 Al30 Al29 Al28 Al 27 Al26 Al25
Mg32 Mg31 Mg30 Mg29 Mg28 Mg27 Mg26 Mg25 Mg24
Na33 Na32 Na31 Na30 Na29 Na28 Na27 Na26 Na25 Na24 Na23
Ne27 Ne26 Ne25 Ne24 Ne23 Ne22
F25 F24 F23 F22 F21
O24 O23 O22 O21 O20
N21 N20 N19
C19 C18
B17
24 23 22 21 20 19 18 17 16 15 14 13 12
Neutron Number (N)
Neutron Number (N) http://www2.bnl.gov/CoN/
P
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o
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N
u
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(
Z
)

Isobars
Isotopes
Isotones
Around 1920, professor of physics A. J. Dempster of
the University of Chicago developed a magnetic
deflection instrument with direction focusing--a format
later adopted commercially and still in use today.
Dempster also developed the first electron impact
source, which ionizes volatilized molecules with a beam
of electrons from a hot wire filament. Electron impact
ion sources are still very widely used in modern mass
spectrometers. Many MS applications have derived
from this design.
The new model for the atom, and the neutron discovery
led H.C. Urey to the discovery of Deuterium (and a job
at U of Chicago), and to Ureys measurements of isotope
effects and isotope fractionation.
The discovery came when Urey
and Murphy measured that the
mass of Hydrogen was about
0.02% heavier than 1 (earth
abundance of
2
H is 0.015%).
A.O. Nier developed the first high
precision mass spectrometer
for stable isotopes.
Brief history
1940s Nier type MS
Nucleosynthetic process Elements created

Big bang
1
H,
4
He,
2
H,
3
H (Li, B?)

Main sequence stars:

Hydrogen burning
4
He

Helium burning
12
C,
4
He,
24
Mg,
16
O,
20
Ne

Carbon burning
24
Mg,
23
Na,
20
Ne

CNO cycle
4
He

x-process (spallation)
& supernova (?) Li, Be, B

o-process
24
Mg,
28
Si,
32
S,
36
Ar,
40
Ca

e-process
56
Fe & other transition

s-process up to mass 209

r-process up to mass 254
Nucleosynthesis Schematic
Nucleosynthesis during the Big Bang
- initially, protons (
1
H) and neutrons
combine to form
4
He,
2
H (D), and
3
He
via exothermic fusion reactions.

- some uncertainty about whether
some B, Be, and Li were created at
this stage

- H & He comprise 99% of
mass of universe


Nucleosynthesis during small star evolution
- star must form from gravitational
accretion of primordial H and He

- temperature ~ 10
7
after formation

- H-burning creates
4
He from
1
H,
longest stage of star (10
7
- 10
10
y)

- He-burning begins with formation
of Red Giant (T=10
8
)

4
He +
4
He -->
8
Be

8
Be +
4
He -->
12
C

12
C +
4
He -->
16
O and so on to
24
Mg

- core contracts as He consumed,
o-process begins (T=10
9
)

20
Ne -->
16
O +
4
He

20
Ne +
4
He -->
24
Mg and so on to
40
Ca
For small star, such as our Sun
Terrestrial Abundances of Stable Isotopes of
Main Interest in Ecological Studies

Element Isotope Abundance Reference Ter. Range
(%) Std in
Hydrogen
1
H 99.985 V-SMOW D= -450 to +50

2
H 0.015
Carbon
12
C 98.89 PDB
13
C= -120 to +10

13
C 1.11
Nitrogen
14
N 99.63 AIR
15
N= -20 to +30

15
N 0.37
Oxygen
16
O 99.759 V-SMOW
18
O= -50 to +40

17
O 0.037 or PDB

18
O 0.204
Sulfur
32
S 95.00 CDT
34
S= -65 to +90

33
S 0.76

34
S 4.22

36
S 0.014

V-SMOW: standard mean ocean water, Atomic Energy Commission, Vienna (
2
H/
1
H=0.00015595;
18
O/
16
O=0.0020052); PDB: Pee Dee Belemnite in NC (
13
C/
12
C =0.0112372); AIR:Atmospheric Nitrogen
(
15
N/
14
N=0.0036765); CDT: Canyon Diablo Troilite (
34
S/
32
S=0.0450451). Oxygen isotopes PDB
(carbonates) or V-SMOW (water and silicates).

Nucleosynthesis during small star evolution (cont)
For small star, such as our Sun
- odd # masses created by proton bombardment

- slow neutron addition (s-process) during
late Red Dwarf:

13
C +
4
He -->
16
O + n
21
Ne +
4
He -->
24
Mg + n
follows Z/N stability up to mass 209



Heavy element formation - the s and r processes
Neutron # (N)
Relative composition of heavy elements in sun very similar to primordial
crust (the carbonaceous chondrite), so we assume that solar system
was well-mixed prior to differentiation.
The abundance of the elements - our solar system
Stabl e i sotope
Long-l i ved radi oi sotope
Short-l i ved radi oi sotope
16
P27 15
Si26 Si25 14
Al25 Al24 Al23 13
Mg24 Mg23 Mg22 Mg21 Mg20 12
Na23 Na22 Na21 Na20 Na19 11
Ne22 Ne21 Ne20 Ne19 Ne18 Ne17 10
F21 F20 F19 F18 F17 F16 9
O20 O19 O18 O17 O16 O15 O14 O13 8
N19 N18 N17 N16 N15 N14 N13 N12 N11 7
C18 C17 C16 C15 C14 C13 C12 C11 C10 C9 C8 6
B17 B15 B14 B13 B12 B11 B10 B9 B8 5
Be14 Be12 Be11 Be10 Be9 Be8 Be7 Be6 4
Li11 Li9 Li8 Li 7 Li 6 Li5 3
He8 He6 He5 He4 He3 2
Isotopes
T D H 1
12 11 10 9 8 7 6 5 4 3 2 1 0
Neutron Number (N)
S40 S39 S38 S37 S36 S35 S34 S33 S32 S31 S30 S29
P39 P38 P37 P36 P35 P34 P33 P32 P31 P30 P29 P28 P27
Si36 Si35 Si34 Si33 Si32 Si31 Si 30 Si 29 Si 28 Si27 Si26
Al34 Al33 Al32 Al31 Al30 Al29 Al28 Al 27 Al26 Al25
Mg32 Mg31 Mg30 Mg29 Mg28 Mg27 Mg26 Mg25 Mg24
Na33 Na32 Na31 Na30 Na29 Na28 Na27 Na26 Na25 Na24 Na23
Ne27 Ne26 Ne25 Ne24 Ne23 Ne22
F25 F24 F23 F22 F21
O24 O23 O22 O21 O20
N21 N20 N19
C19 C18
B17
24 23 22 21 20 19 18 17 16 15 14 13 12
Neutron Number (N)
Neutron Number (N) http://www2.bnl.gov/CoN/
P
r
o
t
o
n

N
u
m
b
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(
Z
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Isobars
Isotopes
Isotones
Terrestrial Abundances of Stable Isotopes of
Main Interest in Ecological Studies

Element Isotope Abundance Reference Ter. Range
(%) Std in
Hydrogen
1
H 99.985 V-SMOW D= -450 to +50

2
H 0.015
Carbon
12
C 98.89 PDB
13
C= -120 to +10

13
C 1.11
Nitrogen
14
N 99.63 AIR
15
N= -20 to +30

15
N 0.37
Oxygen
16
O 99.759 V-SMOW
18
O= -50 to +40

17
O 0.037 or PDB

18
O 0.204
Sulfur
32
S 95.00 CDT
34
S= -65 to +90

33
S 0.76

34
S 4.22

36
S 0.014

V-SMOW: standard mean ocean water, Atomic Energy Commission, Vienna (
2
H/
1
H=0.00015595;
18
O/
16
O=0.0020052); PDB: Pee Dee Belemnite in NC (
13
C/
12
C =0.0112372); AIR:Atmospheric Nitrogen
(
15
N/
14
N=0.0036765); CDT: Canyon Diablo Troilite (
34
S/
32
S=0.0450451). Oxygen isotopes PDB
(carbonates) or V-SMOW (water and silicates).

Delta () notations are referred to
arbitrary standards
Atom %:
Delta () notation vs. N standard (N
2
air):
where,
Ion Source and Mass Separation
Isotope Mass Spectrometry
Sample
introduction
Ionization
Minimize collisions, interferences
Separate
masses
Count ions
Collect results
Nier-type
mass spec
Basic equations of mass spectrometry
2
1
2
mv zV =
2
/ F mv R =
F Bzv =
2
/ mv R Bzv =
2 2
/ / 2 m z B R V =
Ions kinetic E function of accelerating voltage (V) and charge (z).
Centrifugal force
Applied magnetic field
balance as ion goes through flight tube
Fundamental equation of mass spectrometry
Combine equations to obtain:
Change mass-to-charge (m/z) ratio by
changing V or changing B.

NOTE: if B, V, z constant, then:


r m
Ion generation and focusing
Ionization occurs in the source
Electron Ionization
Gas stream passes through beam of e
-
,
positive ions generated.

Thorium, tungsten or Rhenium filaments
Thermal Ionization
Plasma: Gas stream passes through plasma
maintained by RF current and Ar.
Themal: Filament heated to ~1500C
Mass Analyzers - the quadrupole vs. magnetic sector
Quadrupole:
Changes DC and RF
voltages to isolate
a given m/z ion.
PRO: cheap, fast, easy
Magnetic Sector:
Changes B and V to focus
a given m/z into detector.
PRO: turn in geometry means
less dark noise,
higher precision,
Examples of mass spec data output
You can scan in B or V to sweep masses
across a single detector.
OR
You can put different masses into
multiple cups without changing B or V.
Ex: B
Isotope ion Ratio Mass Spectrometers
Continuous Flow Dual Inlet
Sample Introduction Systems (aka front ends)
1) Gas source (lighter elements)
dual inlet - sample purified and measured with standard gas at identical conditions
precisions ~ 0.005%
continous flow - sample volatized and purified (by EA or GC) and injected into
mass spec in He carrier gas, standards measured before and after,
precisions ~ 0.005-0.01%

2) Solid source (heavier elements)
TIMS - sample loaded onto Re filament, heated to ~1500C, precisions ~0.001%
laser ablation - sample surface sealed under vacuum, then sputtered with laser
precisions ~0.01%?

3) Inductively coupled plasma (all elements, Li to U)
ICPMS - sample converted to liquid form,
converted to fine aerosol in nebulizer,
injected into ~5000K plasma torch
Popular combinations
Gas source
1) Dual inlet isotope ratio mass spec (at UIC, VG-SIRA II; Lynch-Steiglitz and Cobb)
- O, C, H ratio analyses

2) Elemental analyzer IRMS (Costech-Delta+XL)
- N, C, S ratio analyses

3) Gas chromatograph IRMS (at UIC, Delta XP; New 4D-GC-MS: Pegasus 4D-LECO)
- compound-specific ratio analyses

Solid source
1) Thermal Ionization mass spec (multi-collector) (coming to UIC)
- heavy metals, organics

ICP
1) ICP quadrupole mass spec
- trace metal analysis

2) Single collector magnetic sector ICPMS
- higher-precision trace metal
analysis

3) Multi-collector ICPMS
- U/Th dating, TIMS
replacement
Micromass IsoProbe - MC-ICPMS
3) Dark Noise - detector will register signal even without an ion beam
- no vacuum is perfect
and
- no detector is perfect

- must measure prior to run, acceptable values = 3-10cpm


4) Detector gain - what is the relationship between the electronic signal recorded
by the detector and the number of ions that it has counted?
- usually close to 1 after factory testing
- changes as detector ages
- must quantify with standards

Cardinal rule of mass spectrometry:
Your measurements are only as good as your STANDARDS!

Standards (both concentration and isotopic) can be purchased from NIST
Hurdles in mass spectrometry (cont.)
Ex: NBS-19, O, C carbonate isotopic standard
Cardinal rule of mass spectrometry:
Your measurements are only as good as your STANDARDS!

Standards (both concentration and isotopic) can be purchased from NIST
Designing an analytical strategy for isotopic analysis
1. How much material do you have available for analysis?
- often set by external factors (no sample is unlimited)

2. What is the expected concentration of the isotopes of interest?

3. What is the error on the isotope ratio expected from counting statistics?

4. What are the other sources of error?
- blanks (know the sources of contamination and their isotopic signatures)

5. Is the expected/desired isotopic signal larger than the sum of all expected
errors?
yes? proceed
no? back to square one can you use more sample? limit blanks? etc

6. What instrument will deliver you the required precision?

7. What particular sources of error are associated with this analysis technique?
- poor yield from sample injection to detection (lowers N)
- mass fractionation, abundance sensitivity, etc

8. Is the expected/desired isotopic signal larger than the sum of all expected
errors?
A review of terms
accuracy: how close the measurement is to a true value

precision: how well we can measure something analytically

Good science: quote values that are accurate within the precision
Systematic error: cannot be assessed by repeated measurements (ex?)

Random error: can be assessed by repeated measurements (ex?)
Internal error: measure ratio repeatedly, assess scatter (aka precision)

External error: compare measurements of standards with internal
errors to truth (aka accuracy)
Reducing systematic errors:
1) minimize systematic errors, add them to random errors
2) make sure systematic errors are small compared to random errors (<10%)
3) measure unknowns relative to a standard so systematic errors cancel out
* Different applications require different approaches (2 & 3 most popular in mass spec work)
Systematic error
Examples:
detector gain (only counts a fraction of signal, usually close to 1)
uncorrected blank or memory
wrong mass discrimination law assumed
spike calibration not accurate
How do you hunt for
systematic errors?
Random error
Counting Statistics:
problem of counting subset of a large set (sometimes the subset will reflect the
large set, sometimes over-estimate, sometimes under-estimate)

theoretical limit: 68% chance of being within of measured values

so need 10,000 realizations to get 1% error (at 68% confidence, or 1o)
1/ n
Internal error:
derives from imperfect measurement (collector noise, electronic noise, etc)

measure ratio repeatedly and use scatter to assess uncertainty
External error:
the ability to reproduce standards over many runs (why might this change long-term?)
measure standard repeatedly, over a very long time
cite as 2 s.d. and mention how many standards based on
Ex.: External reproducibility was assessed with repeated measurements
of the NBS-19 carbonate standard, and is reported as 0.05 (2 s.d., N=550).
238U/235U ratios over typical multi-collector ICPMS run
1.40E+02
1.40E+02
1.40E+02
1.40E+02
1.40E+02
1.40E+02
0 50 100 150 200
Scan number
2
3
8
U
/
2
3
5
U
Example U isotope ratios in single run
Statistic
1) mean = 140.0833


2) standard deviation (1o) = 0.038
* variance = (o)
2

3) standard error (1o) = 0.0027


4) relative standard error (1o) = 1.93 x 10
-5
i
x
N
=

2
1
( )
1
i
x x
N
o =

. . s e
N
o
=
. .
. . .
s e
r s e

=
238U/235U ratio
F
r
e
q
u
e
n
c
y

M
E
A
N

-
1
o

+
1
o

-
2
o

+
2
o





0.9999994
0.9999366
0.9973002
0.9544997
0.6826895
CI range
The Gaussian, or normal distribution
2
1 1
exp
2
2
G
x
P

o
o t
(

| |
=
(
|
\ .
(

Probability density equation: