ASSIGNMENT 1: Oxygen and hydrogen isotope compositions in clay minerals

Ankan Bhattacharyya (PG-1), Presidency University, Kolkata, India

The isotope ratios of the oxygen and hydrogen forming part of the crystalline structure of clay
minerals depend on several factors:
a) The isotopic composition of the various waters that have encountered the clay mineral
during or after its formation.
b) The temperature of the environment at any time during which the clay mineral was
subject to isotope exchange1.
c) The water/rock ratio and the fractionation factors.
d) Whether the mineral has reached isotopic equilibrium with its environment1.
As per Craig (1961), most meteoritic waters have isotopic compositions lying near a straight
line described by the equation D = 8.0 O + 10 %o, known as the meteoric water line
(MWL). Since the O18/O16 and D/H ratios of meteoric water are related and the isotopic
composition of clay minerals depends on the isotopic composition of water, there should also
exist a relationship between the oxygen and hydrogen isotopic compositions of clay minerals
(Savin and Epstein, 1969).

Fig1.- Schematic representation of the isotope composition of H and O in clay minerals

formed from meteoritic water.

The same slope suggests that the clay minerals have undergone isotopic exchange
with a variety of meteoric waters under conditions such that the fractionation factors Oclay-
water and  clay-water are constant i.e., isotopic equilibrium at a constant temperature.
H

The isotopic compositions of the clays will lie along a line with the equation
D = A O + B
 here,
A = 8.0 * ( Hclay-water / Oclay-water) = 8.0 and,
B = 8000 * ( Hclay-water / Oclay-water) – 6990 Hclay-water – 1000
[Taken from Savin and Epstein, 1969]
Thus, the slope of the line is determined by the ratios of the ’s, and its intercept is determined
by the absolute values of the ’s. The sub-parallel lines of kaolinite and montmorillonite is due
to the isotopic exchange with meteoric water under conditions of relatively constant
fractionation factors and their δ18O values are systematically shifted to the right relative to the
meteoric water line, while D shifted by about 30‰ which suggests an out of equilibrium with
present-day waters. The offset is related to their respective fractionation factors.
Equations: a.) Kaolinite line: D = 7.5 18O – 220 b) Montmorillonite line: D = 7.3 18O - 260
In the clay-water system, the isotopic fractionation of hydrogen is lower than unity as
there is a depletion of the heavy isotope D (deuterium) in the mineral phase w.r.t meteoritic
water. The opposite takes place in the case of oxygen, the mineral phase is enriched in the
heavy isotope.
The mass difference of H2O16-H2O18 which is about 11% is higher compared to HDO-H2O16
(~5 to 5.5 %). Therefore, the mass-dependent fractionation of H2O16-H2O18 (oxygen) is more
prominent compared to that of HDO16-H2O16 (hydrogen). During rock-water interaction, (the
meteoric water has higher O values) the O18 fractionates from the meteoric water into the
mineral structure (O in tetrahedral and OH of clay minerals), as the heavier isotope prefers
mineral (higher bond strength) phase thereby getting enriched in clay minerals. On the other
hand, there will be less fractionation of D into the mineral structure and hence there is a
depletion of D in the mineral phase compared to that of meteoric water.
Montmorillonite line is more towards the right than that of kaolinite, this can be explained by
their structural differences.
1. Kaolinite has a T(tetrahedral layer)-O(Octahedral layer) structure where the adjacent
layers are held together by hydrogen bonding between the basal oxygens of the
tetrahedral sheet and the hydroxyls of the exterior plane of the adjacent octahedral
sheet.
2. Montmorillonite has a T-O-T structure with more O ions compared to that of kaolinite
and the T-O-T sheets are held together with water molecules in association with
interlayer cations.
 Fig2.- Crystal structure of Kaolinite, Illite and Montmorillonite (After Budhu,2010). Kaolinite
has 5 O sites and 4 OH sites whereas Montmorillonite has 10 O sites and 2 OH sites.

The interlayer water and the higher number of O sites of montmorillonite isotopically exchange
almost completely with meteoric water in a few hours and thus the 18O will be higher
compared to that of Kaolinite. Once clays are formed, they do not re-equilibrate unless heated
to T > 100oC (H) or T > 300oC (O).
In all the above cases, we are considering a case of isotopic equilibrium. However,
oxygen/hydrogen will not necessarily exchange at the same rate in all the sites and will not
have identical isotopic properties thereby complicating the derivation of equilibrium
fractionation factors from an incomplete exchange.
Sheppard and Gilg (1996) concluded that convincing evidence for complete O- and/or H-
isotope exchange without recrystallization is usually lacking, unless the clay has been subjected
to either higher temperatures of ~350oC or an unusual set of geological circumstances.
The modern soil composition correlates with that of kaolinite which is plotted sub-parallel to
that of the meteoric water line. This indicates that the isotopic composition of soil is preserved
without any diagenetic modification in the geological record.
In Fig 1., the warm areas have higher 18O compared to the cold areas. The warm areas signify
lower latitudes where the rate of evaporation is higher, because of which more O18 fractionates
into the condensate. As the condensate travels toward the polar regions, it becomes heavier and
due to gravity, precipitation occurs. The amount of precipitation will be higher in lower to mid-
latitudes resulting in enrichment of O18 (being a heavier isotope, it will be in the precipitate).
Whereas the precipitation is very less in the higher latitudes (cold polar regions) and therefore
less 18O values compared to lower-mid latitudes.

References:
1. Savin S.M and Epstein S. (1970) The oxygen and hydrogen isotope geochemistry of
clay minerals. Geochim. Cosmochim. Acta, 1970, Vol. 34.
2. Delgado A and Reyes E. (1996) Oxygen and hydrogen isotope compositions in clay
minerals: A potential single-mineral geothermometer. Geochim. Cosmochim. Acta,
Vol 60.
3. Sheppard S.M.F and Gilg H.A. (1996) Stable isotope geochemistry of clay minerals
4. Isotope Geochemistry by William White.