Page 264: Biomarker Indicators of Oxicity

and Anoxia
Determining the environmental conditions of deposition of a source rock, and perhaps most
especially the degree of oxygenation (which strongly influences organic matter preservation),
is of fundamental importance in source rock quality prediction within a basin. In oils,
molecular parameters that indicate the reducing/oxidising (redox) conditions of the source
rock can be important in constraining the potential source(s) of an oil.

264.1 Pristane/Phytane Ratio

The most widely used (and mis-used) biomarker parameter for the assessment of redox
conditions during sediment accumulation is the pristane/phytane ratio. The idea that the ratio
of these two acyclic isoprenoid alkanes is influenced by the degree of oxygenation was first
voiced by Brooks et al. (1969), but developed and popularised by Didyk et al. (1978). These
latter authors proposed that pristane/phytane ratios of >1 indicated oxic conditions of
sedimentation (at the sediment/water interface), whilst values of <1 reflected anoxic
conditions. Subsequently, these values have often been applied by authors without due
consideration to the complexities that impact on this ratio. Indeed, it is worth quoting from
the concluding remarks of Didyk et al. (1978): "We wish to emphasise that we do not regard
the Pr/Ph ratio as a single, definitive indicator of the sedimentation conditions of
palaeoenvironments. Indeed, it is likely to become less definitive as additional data are
acquired, since the number of processes and conditions which bear on this ratio is
considerable."
Fig. 264.1: Simplified diagenetic scheme for the conversion of phytol to pristane and phytane
(after Didyk et al., 1978).

The underlying rationale behind the application of pristane/phytane ratio as an indicator of

oxicity is that both compounds are derived from phytol (mainly derived from the side chain
of chlorophylls), with oxidation tending to promote a decarboxylation reaction (to form the
C19 isoprenoid skeleton), and reduction tending to form phytane in preference. ten Haven et
al. (1987) highlighted the many other influences that impact on the pristane/phytane ratio, the
most important being (1) additional biological inputs of precursors of either pristane or
phytane, and (2) the tendency for the ratio to increase with maturity (a feature that had been
recognised by both Brooks et al., 1969 and Didyk et al., 1978). As a result, the ratio should be
used with caution and in association with other indicators of redox conditions. Peters et al.
(2005) recommend that the pristane/phytane ratio is not used in immature samples, and that
even within the oil window, values between 0.8 and 3 are equivocal. High Pr/Ph values (>3)
are common in samples with abundant terrestrial organic matter deposited under oxic
conditions, whilst very low values (<0.8) are common in hypersaline environments, where
anoxic conditions typically prevail.

264.2 Homohopane Index

The Homohopane Index (C35/[C31-35] αβ-hopanes; Peters & Moldowan, 1991) is often applied
as an indicator of redox conditions in marine sediments. Higher values (> ca. 0.1) are
associated with anoxic marine conditions, and are often notable in having the C35 hopanes
more abundant than the C34 homologues (Peters & Moldowan, 1993; Bishop & Farrimond,
1995; Peters et al., 2005).

Homohopane Index = C35αβ(S+R) / (ΣC31-C35αβS+R)

Fig. 264.2: An m/z 191 mass chromatogram showing the distribution of hopanes for a sample
 with a high Homohopane Index (~0.35).

The enrichment in C35 homohopanes under anoxic marine conditions is due to the preferential
preservation of the intact biologically-derived C35 bacteriohopane skeleton via various
sulphurisation reactions (e.g. inter- and intra-molecular sulphur incorporation; Sinninghe
Damsté et al., 1995) under conditions where reduced sulphur species (e.g. H2S and
polysulphides) are abundant. Sediments deposited under anoxic conditions in saline lakes
may also fulfil this criterion. The C35 hopanes may be released from the S-bound
macromolecules during burial and maturation, due to the weakness of carbon-sulphur (and
particularly sulphur-sulphur) bonds. Under oxidising conditions, the tendency is for the side
chain to be cleaved by oxidative reactions, leading to a dominance of shorter hopanes
(Sinninghe Damsté et al., 1995). The relative enrichment of C35 homohopanes can be shown
for suites of samples using carbon number abundance plots (Peters & Moldowan, 1991) or a
C31-C33-C35 ternary plot (Bishop & Farrimond, 1995). It is important to note that any
prominence of C35 hopanes is likely to decrease at higher maturity levels, due to preferential
generation of shorter-chain hopanes (Peters & Moldowan, 1991), and that biodegradation can
modify the Homohopane Index due to the preferential removal of certain carbon number
hopanes (e.g. Requejo & Halpern, 1989; McCaffrey et al., 1996). Nevertheless, oils generated
from sulphur-rich source rocks (anoxic marine or anoxic saline lake) typically display
elevated C35 hopanes (Huang & Pearson, 1999).

264.3 Diahopane/C29Ts
The ratio of the rearranged hopanes 17α(H)-diahopane/C29Ts has been proposed to be
sensitive to redox conditions, with higher values being found in oils from shales deposited
under more oxidising conditions (Peters & Moldowan, 1993). However, this ratio has not
been widely applied (Sachsenhofer et al., 1995), and may increase with maturity, particularly
in the late oil window (Peters & Moldowan, 1993), so precise values cannot be given to
define redox conditions.

References:
Bishop, A.N. & Farrimond, P. (1995). A new method of comparing extended hopane
distributions. In: Organic Geochemistry vol. 23 pp. 987-990.
Brooks, J.D., Gould, K. & Smith, J.W. (1969). Isoprenoid hydrocarbons in coal and
petroleum. In: Nature vol. 222 pp. 257-259.
Didyk, B.M., Simoneit, B.R.T., Brassell, S.C. & Eglinton, G. (1978). Organic geochemical
indicators of paleoenvironmental conditions of sedimentation. In: Nature vol. 272 pp. 216-
222.
Huang, H. & Pearson, M.J. (1999). Source rock palaeoenvironments and controls on the
distribution of dibenzothiophenes in lacustrine crude oils, Bohai Bay Basin, Eastern China.
In: Organic Geochemistry vol. 30 pp. 1455-1470.
McCaffrey, M.A., Legarre, H.A. & Johnson, S.J. (1996). Using biomarkers to improve heavy
oil reservoir management: an example from the Cymric field, Kern County, California. In:
American Association of Petroleum Geologists Bulletin vol. 80 pp. 898-913.
Peters, K.E. & Moldowan, J.M. (1991). Effects of source, thermal maturity, and
biodegradation on the distribution and isomerization of homohopanes in petroleum. In:
Organic Geochemistry vol. 17 pp. 47-61.
Peters, K.E. & Moldowan, J.M. (1993). The biomarker guide., Prentice-Hall Inc. p. 363
ISBN: 0-13-086752-7.
Peters, K.E., Walters, C.C. & Moldowan, J.M. (2005). The biomarker guide., Cambridge
University Press p. 1155 ISBN: 0 521 83763 4.
Requejo, A.G. & Halpern, H. I. (1989). An unusual hopane biodegradation sequence in tar
sands from the Pt Arena (Monterey) Formation. In: Nature vol. 342 pp. 670-673.
Sachsenhofer, R.F., Curry, D.J., Horsfield, B., Rantitsch, G. & Wilkes, H. (1995).
Characterization of organic matter in late Cretaceous black shales of the Eastern Alps
(Kainach Gosau Group, Austria). In: Organic Geochemistry vol. 23 pp. 915-931.
Sinninghe Damsté, J.S., Van Duin, A.C.T., Hollander, D., Kohnen, M.E.L. & De Leeuw,
J.W. (1995). Early diagenesis of bacteriohopanepolyol derivatives: Formation of fossil
homohopanoids. In: Geochimica et Cosmochimica Acta vol. 59 pp. 5141-5155.
ten Haven, H.L., de Leeuw, J.W., Rullkotter, J. & Sinninghe-Damsté, J. (1987). Restricted
utility of the pristane/phytane ratio as a palaeoenvironmental indicator. In: Nature vol. 330
pp. 641-643.