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Stable isotopes
Many elements of low atomic weight have two or more
stable isotopes, e.g.:
Hydrogen - H, D, T
Carbon - 12C, 13C
Nitrogen - 14N, 15N
Oxygen - 16O, 17O, 18O
Sulfur - 32S, 33S, 34S, 35S
The different masses cause isotopes to behave differently
in physical and chemical processes. For example, 2H218O is
much heavier than 1H216O and will be left behind during
evaporation.
Stable isotopes
Stable Isotope geochemistry is concerned with variations of the isotopic compositions
of elements arising from physicochemical processes (vs. nuclear processes).
Fractionation refers to the change in an isotope ratio that arises as a result of a
chemical or physical process.
Occurs during:
- isotopic exchange reactions in which the isotopes are
redistributed among different molecules containing that element
- unidirectional or incomplete reactions
- physical processes like evaporation/condensation,
melting/crystallization, adsorption/desorption, diffusion
Characteristics of a useful stable isotope system:
1.
large relative mass difference between stable isotopes (m/m)
2.
abundance of rare isotope is high (0.1-1%)
3.
element forms variety of compounds in natural system
Examples: 2H/1H, 7Li/6Li, 11B/10B, 13C/12C, 15N/14N, 18O/16O, 26Mg/24Mg, 30Si/28Si,
34 32
S/ S, 37Cl/36Cl, 40Ar/36Ar, 44Ca/40Ca, 56Fe/54Fe
- note convention of putting the heavy isotope above the light isotope
Isotope fractionation
The degree of fractionation depends on the relative
weights of the isotopes.
Commonly fractionated: H, C, N, O, S
Somewhat fractionated: Si, Fe, Cl
Fractionation impossible (monoisotopic): Be, F, Na, Al, P
C
K
C
18
16
H
O H
O2
16
2
18
O
O
Why is K 1.0?
Because 18O forms a stronger covalent bond with C than does 16O.
The vibrational energy of a molecule is given by the equations:
Evibrational
k
m
Js
k (Boltzmanns constant) = 1.38 x 10-23 J/K
m = mass
-34
Ekinetic
mv
vH
mL
In the case of 12C16O and 13C16O we have:
vL
28.99827
1.0177
vH
27.994915
Ra
Rb
a
b
where RA, RB are the isotope ratios in two phases (e.g., carbonate
and water, or water vapor and water)
For example, consider: H2O(l) H2O(v) at 25C
Rl
l
v (O )
Rv
18
O
18
O
O l
1.0092
16
O v
16
10
ba a
b 103
10
1000 ln ba
B
2
T
Experimentally determined
equilibrium oxygen isotope
fractionation factors as a
function of temperature.
Experimentally
determined equilibrium
carbon isotope
fractionation factors as a
function of temperature.
varies inversely with T
A useful approximation
Natural logarithms of small numbers like 1.00X have
the property that
1000 ln 1.00X X
as long as X 9.
This approximation holds for ba for C, N, O and S
isotopes in many systems. This leads to the
following:
103 ba 1 103 ln ba a b ab
so
6
A
10
103 ln ba ab
B
2
T
13
13
Canyon Diablo
meteorite from
Meteor Crater,
Arizona (CDT).
12
10
C sample 13C
13
12
C standard
18
C standard
12
H sample D H standard
H standard
103
O sample 18O
16
18
O standard
16
O standard
16
103
103
Map of North
America
showing
contours of the
approximate
average D
values of
meteoric surface
waters.
ti
a
L
gh
i
H
e
d
tu
Closed
basins
Evaporation
(slope ~5)
Rayleigh distillation
Isotopic fractionation that occurs during condensation
in a moist air mass can be described by Rayleigh
distillation. The equation governing this process is:
Rv R f
o
v
Rl
Rv
18O increasingly
negative with continued
precipitation
Effect of Rayleigh
distillation on the
18O value of water
vapor remaining in
the air mass and of
meteoric precipitation
falling from it at a
constant temperature
of 25C.
Complications:
1) Re-evaporation
2) Temperature
dependency of
Metamorphic
warm
H2O (300-600C)
Primary
magmatic
H2O
cool
Modern soils
An example
Consider a hydrothermal vein in which quartz, calcite and
chlorite were deposited together. The minerals were
analyzed for their O-isotopes which resulted in:
18Oquartz = 5.1 ; 18Ocalcite = 3.8 ; 18Ochlorite = -1.5 .
Assuming these three minerals were all in equilibrium
with one another, calculate the temperature of formation.
First, we need the fractionation factors for these minerals:
6
3
.
38
10
qtz
18
18
103 ln wqtz
3
.
40
Ow
w
qtz
2
T
6
2
.
78
10
cc
18
18
103 ln wcc
2
.
89
Ow
w
cc
2
T
6
1
.
56
10
chl
18
18
103 ln wchl
4
.
70
Ow
w
chl
2
T
6
6
3
.
38
10
2
.
78
10
qtz
cc
qtz
3.40
2.89
cc
w
w
2
2
T
T
0.6 106
18
18
0
0
.
51
5
.
1
3
.
8
1
.
3
Occ
00
qtz
2
T
T 575.75 K 302.6o C
qtz
chl
6
6
3
.
38
10
1
.
56
10
chl
qtz
3.40
4.7
w
w
2
2
T
T
1.82 106
18
18
0
1
.
30
5
.
1
1
.
5
)
6
.
6
Ochl
00
qtz
2
T
T 586.0 K 312.9o C
2.78 106
1.56 106
2.89
4 .7
2
2
T
T
1.22 106
18
18
0
1
.
81
3
.
8
1
.
5
)
5
.
3
Ochl
00
cc
2
T
T 591.2 K 318.1o C
6
A
10
103 ln ba ab
B
2
T
Oxygen fractionation
in rock-forming minerals
Sulfur isotopes
The stable sulfur isotopes are: 32S, 33S, 34S, 35S, but
the fractionation between 32S and 34S is the most
34
32
34
32
studied.
S
S
S
S standard
sample
34
3
S
34
32
S standard
10
Sulfate reduction
The reaction can be written:
CH4 + SO42- + 2H+ H2S(g) + CO2(g) + 2H2O(l)
For this reaction at 25C, Gr = -26.324 kcal mol-1
or log K = 19.3, so the reaction is highly favored
thermodynamically, but is slow in the absence of
bacteria.
The reaction is not at equilibrium and a large
kinetic isotope fractionation factor between sulfate
and sulfide occurs when bacteria are involved.
Sulfide/sulfate fractionation
The extent of fractionation of S-isotopes between
sulfate and sulfide depends on:
1) The rate of metabolism by bacteria.
2) Composition and abundance of food supply.
3) Size of sulfate reservoir.
4) Temperature.
5) The rate of removal of H2S.
Alternative scenarios
Closed system - the concentration of H2S may build up
until it poisons the bacteria, e.g., in the Black Sea. The
H2S is then strongly depleted in 34S.
Open system - the sulfate reservoir is virtually infinite,
and H2S is removed. Metabolized sulfide is depleted in
34S, but the isotope composition of sulfate remains
constant.
Open system, sulfate-limited - H2S is free to escape.
Rayleigh distillation occurs. The remaining sulfate and
each new batch of H2S become enriched in 34S.
Seawater
S isotopes as tracers
Metabolic H2S may react with metals and form
sulfides. These generally have 34S < 0, but this
may vary stratigraphically (and may even be > 0)
depending on the extent of Rayleigh distillation.
Thus, sedimentary and igneous sulfides tend to
exhibit different trends in their 34S values.
Sedimentary sulfides - 34S exhibits a wide range,
generally towards negative values.
Igneous sulfides - 34S values close to 0 .
Caveats!
We need to be careful in using S-isotopes as tracers
because:
1) 34S of some sedimentary sulfides can be near zero or
positive.
2) 34S of some magmatic sulfides could be negative if
the S originally came from sedimentary rocks that
were melted.
3) 34S values of igneous rocks can vary from zero
depending on pH and partial pressure of oxygen.
4) 34S of sulfides in igneous and metamorphic rocks can
be changed by isotope exchange during alteration.
Variation of isotope
composition of S and Sr in
Phanerozoic time. Note that
both 34S and the 87Sr/86Sr ratio
declined irregularly during the
Paleozoic Era from the
Cambrian to the Permian
periods. During the Mesozoic,
both parameters had low values
but began to rise during the
Cretaceous and continued to
rise in the Tertiary. The
observed variations in isotopic
compositions of S and Sr in the
oceans were caused by global
changes in the geochemical
cycles of these elements.
S-isotope geothermometry
We can use sulfur isotopic fractionation in sulfide and
sulfate minerals as a geothermometer if all minerals
precipitated at the same time in equilibrium with one
another.
For example, consider the fractionation between galena
and sphalerite:
5
7
.
2
10
sp
spgn 34 S sp 34 S gn 1000 ln gn
2
T
Then we calculate:
7.2 10
T
4.0
424 K 151 o C
Experimentally determined
equilibrium sulfur isotope
fractionation factors as a
function of temperature.