Sulfur Isotope Composition of Pyrite and Organic Matter from the
Monterey Formation: Implications for δ34S as a Paleoenvironmental Proxy
Abstract
The isotopic composition of organic sulfur (δ34Sorg) is a potential
recorder of past biogeochemical conditions that has, thus far, received
relatively little attention in comparison to the pyrite sulfur isotope
record (δ34Spyr). This study presents continuous organic and pyrite δ34S
records from three basins of the organic-rich Miocene Monterey
Formation, deposited over a similar time interval of c.14.5-6 Ma but
under varying depositional conditions. In the San Joaquin basin, δ34Sorg
and δ34Spyr average 0‰ and -4‰ respectively and maintain a relatively
constant pyrite-organic sulfur isotopic offset of c. 5‰. The Santa Maria
Basin exhibits δ34Sorg values that are >10‰ higher than in
coeval San Joaquin basin intervals, with average δ34Sorg of c. 24‰ in
the upper siliceous member the highest yet reported for marine organic
sulfur and roughly 2-3‰ higher than Miocene seawater sulfate. δ34Spyr is
consistently c. 12‰ depleted in comparison to organic sulfur in the
lower phosphatic member of the Santa Maria Basin, but an abrupt
enrichment in both δ34Spyr and δ34Sorg coincident with a sharp
lithostratigraphic transition at c. 11 Ma reduces this offset to
<4‰ for much of the upper siliceous shales. The Santa Barbara
Basin shows a sulfur isotope record intermediate between the San Joaquin
and Santa Maria Basins, with average δ34Spyr and δ34Sorg of 3‰ and 12‰
respectively, and relatively consistent c. 10‰ pyrite-organic isotope
offset. Records for all three basins demonstrate a close correlation
between coeval δ34Spyr and δ34Sorg values which we attribute to
derivation from an equivalent, or at least similar, source of
sedimentary or water column sulfide. However, marked offset in the
isotopic composition of coexisting pyrite and organic sulfur, of
variable magnitude within and between basins, implies some contrast in
the diagenetic processes underlying sulfur incorporation into the two
phases. We argue that the prominent δ34Spyr and δ34Sorg isotopic
differences between broadly coeval basin sections are largely the result
of differences in sedimentation regime and the associated balance of
iron and sulfide supply during diagenesis. A likely factor of additional
importance to this iron-sulfide balance is basin-specific sedimentary
and water column redox. These findings illustrate the importance of
determining independent constraints on the nature of a sedimentary
system before conclusions are made relating the sulfur isotope
composition of sedimentary species to paleoenvironmental conditions.
Additionally, we suggest that records of δ34Spyr have a strong
dependence on interaction with organic sulfur during formation, and thus
that existing δ34Spyr records are more effectively interpreted in
combination with δ34Sorg records.