STABLE ISOTOPES

Hand-out Table 2-13

Isotope fractionation

1/2C16 O2 H2 18 O 1/2C18 O2 H 2 16 O
18 1/2 16
(C O2 ) (H 2 O)
K 16 1/2 18
At equilibrium
(C O2 ) (H 2 O)
Isotope Fractionation: isotope exchange reactions and
mass-dependent differences in the rates of certain chemical
reactions and physical/biological processes which results in
changes in the relative abundances of isotopes
What does K tell us about fractionation?
If no fractionation then K = 1.00

1/2C16 O2 H2 18 O 1/2C18 O2 H 2 16 O
18 1/2 16
(C O2 ) (H 2 O)
K 16 1/2 18
(C O2 ) (H 2 O)
For this reaction at 25oC K = 1.0412

One isotope is favored over the other

Why doesnt K = 1?

18O forms stronger bonds with C than 16O does at 25oC

Energy and fractionation

Hand out figure 2-13

Its a quantum thing.

h = Planks constant
E = 1/2 hn
n = frequency of vibration
E = 1/2 hn
When a heavy isotope replaces alight isotope the Energy decreases
because the mass of the molecule increases

The vibrational frequency decreases so the heavy isotope forms

a stronger bond the molecule is more stable
 Heavy isotope goes preferentially to the chemical compound in
which the element is bound most strongly Bigeleisien, 1965

Another cause of fractionation is related to mass differences

2 16 1 16
H2 O Heavy water is 11.1% greater in mass than H2 O

This difference can affect the rates if physical and chemical

processes like diffusion, evaporation and dissociation

Hand-out Table 2-14

Fractionation Factor

Ra Ra = heavy/light ration in molecule or phase a

b
a Rb = heavy/light ratio in molecule or phase b
Rb
In class example:
fraction factor for oxygen isotopes in water

R1

1
v 1.0092 fractionat ion factor of O isotopes in water
Rv
18
R 1 O 16 in liquid
O
18
R v O 16 in vapor
O
Text table 17.1 p. 302

Avg. terrestrial O ratio is 18O/16O = 0.200/99.762=0.0020

Avg. terrestrial D/H ratio is 0.00015

Example systems
d18O
D/H
d13C
Small differences in measured ratios requires values to be in per mil
o/ difference of isotope ratio of sample to standard
oo

Rsample Rstd 3 o
d O
18
x10 / oo R= heavy/light
Rstd
Standard for O and H is SMOW (standard mean ocean water)

Standard for C is PDB (Peedee belemnite)

d18O SMOW = 1.03086 o/oo
d18OPDB= +30.86 o/oo

Standard for N is N2 of atmosphere

Standard for S is triolite (FeS) from Canyon Diablo Meteorite
+d = heavy isotope enriched
-d = heavy isotope depleted

Rstd (d a 10 )10 d a 10
3 3 3
3
a

10 Rstd (d b 10 ) d b 10
b 3 3
In class example:
Hand-out figure 12.22

Assume no isotopic fractionation during pyrite oxidation in a

periodically wet tailings pile, that oxidation is 20% by Fe3+ and
80% by O2 and that d18O = -10.9 per mil in H2O and +23.0 per
mil in O2. Compute d18O for the sulfate.
1) need an equation that relates the oxidation of pyrite to sulfate

4 FeS2 15O2 14 H 2O 4 Fe(OH )3 8SO42 16 H

2) because were dealing with oxidation separate the reaction into

half reactions
2 2
FeS2 O2 H 2O Fe 2SO 2 H
7
2 4

FeS2 14 Fe3 H 2O 15Fe2 2SO42 16 H

3)
d OSO oxidation by Fe and O 2
18
2
4

percent oxidation by Fe and O2 (given)

20% by Fe3+=0.2
80% by O2 = 0.8

per mil 18O values given

d 18OH O 10.9 per mil

2

d OO 23 per mil
18
2
4) calculate d18Osulfate using stoichiometry

d 18Osulfate 0.2(10.9) 0.8(10.9) 0.8(0.875(23) 12.8 per mil

ferric iron Stoichiometry

btn. Fe3+ and FeS2
and O2 and FeS2

Stoichiometry
(1-0.125)
Would you expect isotopic fractionation by T. ferroxidans to
change the isotope ratio values of the sulfate?

Yup, isotope fractionation should enrich the sulfate in 16O which

would reduce the d18O of the sulfate

How would this change the relationship between the isotopic

composition of the sulfate relative to the water?
compute the difference between DSO42- and water

12.8 o/oo - (-10.9 o /oo) = 23.7 o/oo

Fractionation would lower the DSO42- - H2O

See handout Figure 12.22

Isotopic thermometer equations

6
Ax10
10 ln d a d b D
3 a
b 2
B a
b
T
A and B are constants
T in Kelvin

Text figure 17.1 p. 307

dD and dO have a strong T dependent fractionation

In class example:
Given that a fluid inclusion filled with water in calcite that formed
in a cave has a measured value of dD = -17.5 per mil and that
d18O of calcite is +10.0 per mil (SMOW). What was the temperature
of deposition of the calcite in oC assuming that the water was
of meteoric origin and isotopic equilibrium existed between
calcite and water at the time of deposition.

The meteoric water line dD = 8d18O+10

1) meteoric water

dDw=-175 o/oo dDw 10

d O
18

175 10
d O
18
23.125 / oo
o

d Oc 10
18 3
= 1.00390
d 18
c

d Ow 10
w 3
 6
A10 A=2.78
10 ln d 2 B
3 c
w
T B=2.89

2.78 106
2
10 ln w 2.89
3 c

2.78 106 2.78 106

T 277.01K 3.86 o
C
10 ln w 2.89
3 c
36.2280
Homework:
Faure Chapter 16 #5-7
Faure Chapter 17 #14