Isotope Geochemistry I

Applications of Stable Isotopes

.


5-2-2014

Examples of applications
To establish an isotopic profile for a material, the ratios of the
stable isotopes of a number of elements such us 2H/1H,
13C/12C, 15N/14N and 18O/16O can be measured. The isotopic
abundances of these elements were fixed when Earth was
formed and, on a global scale, have not changed since. Subtle
variations in the isotopic composition may be introduced during
biological, chemical and physical processes.
The technique:
Isotope Ratio Mass Spectrometry (IRMS) is used to measure
the relative abundance of isotopes in different materials

Examples of applications
Geosciences
Geochemistry and geology
- Extent and temperature of post-burial alteration of
rocks
- Provenancing of clasts
- Identifying the source of water smples

Palaeoclimatology
Paleoecology

Examples of applications
Biological sciences
Ecology
-

Photosynthetic pathways
Food webs
Ecohydrology
Nutrient cycling

Human provenancing
Metabolic studies
Sports medecine
Toxicology
- Distinguishing endogenous vs exogenous bio-chemicals

Examples of applications
Forensic sciences
Environmental forensics and monitoring
- Identifying the source of poluutants (eg. Oil spills)
- Monitoring atmospheric gases to distiguish
between natural anthropogenic sources
- Climate studies
- Water cycle research

Food authenticity and traceability

- Identifying adulteration of foods with cheaper foodstuffs

Isotopes
Isotopes have different ## of neutrons,
and thus a different mass
Affect on reactions in small, but real, and
provides another measurement of
reactions affected by similar
physicochemical parameters!
Also a critical tracer the isotopes can be
used to track molecules in a reaction!

Fractionation
A reaction or process which selects for
one of the stable isotopes of a particular
element
If the process selects for the heavier
isotope, the reaction product is heavy, the
reactant remaining is light

Fractionation Factor, a
R is the ratio of heavy to light isotopes
a, or fractionation factor, is the ratio between
reactant and product

Rreactan ts
a
R products

Why a ratio???
Differences between 2 isotopes of one
element is VERY small to measure them
individually with enough precision is difficult
to impossible for most isotope systems
By comparing a sample ratio to a standard
ratio, the difference between these two can
be determined much more precisely!!

Isotope Standards
VSMOW Vienna Standard Mean Ocean
Water bunch of ocean water kept in
Austria O and H standard
PDB Pee Dee Belemnite fossil of a
belemnite from the Pee Dee formation in
Canada C and O
CDT Canyon Diablo Troilite meteorite
fragment from meteor crater in Arizona,
contains FeS mineral Troilite S
AIR Atmospheric air - N

Measuring Isotopes
While different, isotopes of the same element
exist in certain fractions corresponding to
their natural abundance (adjusted by
Where Ra is the ratio of
fractionation) a Ra
heavy/light isotope and a is
ab
the fractionation factor
Rb
We measure isotopes as a ratio of the
isotope vs. a standard material (per mille )
Rsample Rstandard
103
O
Rstandard

18

10 ln a a b
3

a
b

a
b

 is delta, and is the isotope ratio of a particular

thing (molecule, mineral, gas) relative to a
standard times 1000. sometimes called del
Rsample Rstandard
103
O
Rstandard

18

is delta and is the difference between two

different isotope ratios in a reaction:
AB = A - B
Many isotopers are very sensitive about misuses of isotope terminology.
Harmon Craigs immortal limerick says it all:
There was was a young man from Cornell
Who pronounced every "delta" as "del"
But the spirit of Urey
Returned in a fury
And transferred that fellow to hell

Equilibrium Fractionation
For an exchange reaction:
C16O2 + H218O C18O2 + H216O
1
Write the equilibrium:
18
16
K

(C O2 ) 2 ( H

O)

1
2

(C 16O2 ) ( H 18 2O)

Where activity coefficients effectively cancel

out
For isotope reactions, K is always small,
usually 1.0xx (this K is 1.047 for example)

WHY IS K DIFFERENT FROM

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 1 2 h

k
m

F kx

Thus, the frequency of vibration depends

O
on the mass of the atoms, so the energy
H
H
of a molecule depends on its mass.

 The heavy isotope forms a lower energy

bond; it does not vibrate as violently.
Therefore, it forms a stronger bond in
the compound.
The Rule of Bigeleisen (1965) - The
heavy isotope goes preferentially into
the compound with the strongest bonds.

Temperature effects on
fractionation
The fractionation factors, a, are affected
by T (recall that this affects EA) and
defined empirically:
6
A

10
103 ln a ba
B
2
T

Then,

Where A and B are constants

determined for particular reactions
and T is temp. in Kelvins

10 ln a a b
3

a
b

a
b

As T increases, decreases at high T

goes to zero

FRACTIONATION DURING
PHYSICAL PROCESSES
Mass differences also give rise to
fractionation during physical processes
(diffusion, evaporation, freezing, etc.).
Fractionation during physical process is a
result of differences in the velocities of
isotopic molecules of the same compound.
Consider molecules in a gas. All molecules
have the same average kinetic energy, which
is a function of temperature.

Ekinetic

mv

Using isotopes to get information on

physical and chemical processes
Fractionation is due to some reaction,
different isotopes can have different
fractionation for the same reaction, and
different reactions have different
fractionations, as well as being different at
different temperatures and pressures
Use this to understand physical-chemical
processes, mass transfer, temperature
changes, and other things

Equilibrium Fractionation II

For a mass-dependent reaction:

Ca2+ + C18O32- CaC18O3
Ca2+ + C16O32- CaC16O3
Measure 18O in calcite (18Occ) and water
(18Osw)
Assumes 18O/16O between H2O and CO32- at
some equilibrium
T C = 16.998 - 4.52 (18Occ - 18Osw) + 0.028 (18Occ-18Osw)2

Empirical Relationship between Temp. &

Oxygen Isotope Ratios in Carbonates
At lower temperatures, calcite
crystallization tends to incorporate a
relatively larger proportion of 18O
because the energy level (vibration)
of ions containing this heavier isotope
decreases by a greater amount than ions
containing 16O.
As temperatures drop, the energy level
of 18O declines progressively by an
amount that this disproportionately
greater than that of the lighter 16O.

ISOTOPE FRACTIONATION IN THE

HYDROSPHERE
Evaporation of surface water in equatorial regions
causes formation of air masses with H2O vapor
depleted in 18O and D compared to seawater.
This moist air is forced into more northerly, cooler air
in the northern hemisphere, where water
condenses, and this condensate is enriched in 18O
and D compared to the remaining vapor.
The relationship between the isotopic composition of
liquid and vapor is:

Ol a Ov 10 10
18

l
v

18

Assuming that 18Ov = -13.1 and avl(O) =

1.0092 at 25C, then

Ol 1.0092 13.1 10 10 4.0 0 00

18

and assuming Dv = -94.8 and avl(H) = 1.074

at 25C, then
Dl 1.074 94.8 103 103 27.8 0 00
These equations give the isotopic composition
of the first bit of precipitation. As 18O and D
are removed from the vapor, the remaining
vapor becomes more and more depleted.
Thus, 18O and D values become increasingly
negative with increasing geographic latititude
(and altitude.

Map of North
America
showing
contours of the
approximate
average D
values of
meteoric surface
waters.

Because both H and O occur together in water, 18O and D

are highly correlated, yielding the meteoric water line
(MWL):
D 818O + 10

Deviation from MWL

Any additional fractionation process which
affects O and D differently, or one to the
exclusion of the other will skew a water
away from the MWL plot
These effects include:
Elevation effects - (D -8/1000m, -4/C)
Temperature (a different!)
Evapotranspiration and steam loss
Water/rock interaction (little H in most rocks)

Iron Isotopes
Earths Oceans 3 Ga had no
oxygen and lots of Fe2+,
cyanobacteria evolved,
produced O2 which oxidized
the iron to form BIFs in time
the Fe2+ was more depleted
and the oceans were stratified,
then later become oxic as they
are today

This interpretation is largely based on iron

isotopes in iron oxides and sulfide minerals
deposited at those times (Rouxel et al., 2005)

Experiments
Fe2+ and
FeSmackinawite at
equilibrium,
separate physically
(filter) and measure
each component:

From Butler et al., 2005 EPSL 236 430-442

Fe isotope exchange with a particle

Particles coarsen via
Ostwald ripening or
topotactic alignment
how fast can isotopes
exchange with Fe in a
xstal actively getting
bigger?
At certain size internal
Fe2+ does not
exchange

Fe2+
Fe2+

Fe2+
2+

Fe2+Fe

Fe2+
Fe2+

Fe2+

Fe2+

Fe2+
Fe2+

Guilbaud et al., 2010 EPSL 300 174-183

What can we get from using

multiple isotopes?
Many isotope systems have more than 2
stable isotopes 56Fe, 57Fe, 58Fe; 32S, 33S,
34S, 36S
Looking at multiple isotopes can provide
new insight on multiple processes,
especially useful for complicated reaction
pathways, also helps get at equilibrium v.
kinetic processes, and mass-dependent v.
independent processes

 Tracing S-isotopic fractionation from

different communities of organisms
(Sulfate-reducers, sulfur
disproportionation, phototrophic S oxid.)

From Zerckle et al., 2009 GCA 73, 291-306

S isotopes and microbes

The fractionation of H2S formed from
bacterial sulfate reduction (BSR) is affected
by several processes:
Recycling and physical differentiation yields
excessively depleted H2S
Open systems H2S loss removes 34S
Limited sulfate governed by Rayleigh process,
enriching 34S
Different organisms and different organic
substrates yield very different experimental 34S

Ends up as a poor indicator of BSR vs. TSR

Mass-independent fractionation
Mass effects for 3 stable isotopes
(such as 18O, 17O, and 16O) should
have a mass-dependent relationship
between each for any process
Deviation from this is massindependent and thought to be
indicative of a nuclear process
(radiogenic, nucleosynthetic,
spallation) as opposed to a physicochemical process
Found mainly associated with
atmospheric chemistry, effect can be
preserved as many geochemical
reactions in water and rock are massdependent

S-isotopic evidence of Archaen

atmosphere
Farquar et al., 2001; Mojzsis et al., 2003
found MIF signal in S isotopes (32S, 33S,
34S) preserved in archaen pyrites
precipitated before 2.45 Ga
Interpreted to be signal from the photolysis
of SO2 in that atmosphere the reaction
occurs at 190-220nm light, indicating low
O2 and O3 (which very effficiently absorb
that wavelength)

Volatilization
calcite + quartz = wollastonite + carbon dioxide
CaCO3 + SiO2 = CaSiO3
+
CO2
As the CO2 is produced, it is likely to be expelled

 Other volatilization reaction examples