Stable Isotope Geochemistry

Based on the principle of fractionation. Certain elements (light ones) separate

(fractionate) appreciably under normal geologic conditions.
Only works for the lighter elements (At mass <40). Occurs because mass difference
results in substantial differences in the vibrational energy. The heavier isotopes vibrate
more slowly while the lighter isotopes vibrate more rapidly. Hence, the bonds to the
lighter isotopes are weaker and more easily broken.
Elements used:
1) 1H, 2H
2) 12C, 13C
3) 16O, 18O
4) 32S, 34S
Processes Responsible for Fractionation
1. Physical Processes
o Evaporation - most important. Concentrates the lighter isotope of the pair
in the gas phase and heavier in the liquid/solid. Evaporation of seawater
enriches the atmosphere in 1H and 16O.
o Diffusion - lighter isotopes will diffuse more rapidly causing fractionation.
Not an important mechanism.
2. Organic Processes
o Bacterial reduction - sulfate reducing bacteria preferentially break the
weaker bonds enriching the sulfide phase in 32S relative to the 34S
enrichment of the remaining sulfate.
3. Inorganic Processes
o Temperature - at elevated temperature atoms are vibrating more rapidly
and hence the lighter isotopes which form the weaker bonds are less likely
to be incorporated in the crystallizing mineral. Thus, the early-formed
minerals will be enriched in the heavier isotope relative to those formed
later at a lower temperature. Studies of ore deposits have shown that the
sequence pyrite--> sphalerite-->chalcopyrite-->galena show a progressive
enrichment in the light isotope of sulfur.
Isotopic values are reported in the following manner:

heavy = (heavy/light)sample - (heavy/light)standard /(heavy/light)standard X 1000

Examples of Specific Isotopes

O and H - used in conjunction they have been very useful in the determination of the
source of the water in many types of ore deposits.
Studies by Taylor (circa 1970) show that surface water generally shows an enrichment in
O and H near the coastline (decreasing toward the center of the continent) and toward the
equator.

First rainfall from storms off the ocean will be enriched in the heavier 18 isotope.
Hence the high 18O and 2H near the coast. Progressively lighter rainfalls inland
due to the initial loss of the heavier isotopes.
Enrichment toward the equator a function of evaporation rate. Highest in the
tropics and lowest at the poles.

Figure shows the isotopic composition of various waters.

1. Meteoric water plots as a line which is latitude dependent as discussed above.

2. Seawater plots as a single point due to the general homogeneity of ocean water.
3. Magmatic water plots as relatively small box. Determined by analyzing the water
in hydrous silicates.
4. Metamorphic water plots as a larger box the result of analyzing hydrous minerals
which are a mixture from igneous and sedimentary protoliths.
The Oxygen Isotope Shift
Studies by Taylor of geothermal waters which many feel closely approximate the water
responsible for ore deposits have shown what is termed the "oxygen isotope shift"
(Figure). That is geothermal waters show and enrichment in 18O relative to meteoric
waters from nearby streams, whereas 2H shows no similar trend. This is interpreted as the
result of a new isotopic equilibrium established when "hot" geothermal waters contact
oxygen-bearing silicate minerals. Since little H is present in the rocks there is no similar
H isotope shift. This is a powerful argument to support those geologists who feel that

most hydrothermal waters are of meteoric origin and not evolved from magmas. In the
latter case, the geothermal waters should plot on the magmatic rectangle.

Figure shows the oxygen isotopic ratios of some ore deposits. Note they plot all over the
diagram. This indicates there must be a significant meteoric water component.

Sulfur - important because sulfur is the dominant anion in many ore deposits and sulfur
isotopes can often tell us the source of the sulfur.

34S -5 to -60. Deposit is of organic origin and due to bacterial reduction. Wild
fluctuations of values between various layers coincides with extinctions.
34S -5 to +5. Sulfur of primary magmatic origin. Because the standard is sulfur
from the Canyon Diablo meteorite.
34S +5 to +50. Sulfur of inorganic origin and probably the result of inorganic
reduction of sulfate. Values closer to zero may be due strictly to temperature
fractionation.

Table shows some typical sulfur isotope values for various ore deposits.