Reinterpreting the Early Cretaceous Sulfur Isotope Records: Implications for the Evolution of Seawater Chemistry

The geologic record of the Cretaceous is punctuated by several periods of high organic carbon burial interpreted to represent global Ocean Anoxic Events (OAEs). In addition to the short-term (<1-Myr) changes in carbon (C) cycling associated with OAEs, evidence from a number of geochemical proxies has been interpreted to represent large-scale changes in ocean chemistry during the period. Specifically, the sulfur (S) isotope composition of early Cretaceous seawater sulfate as recorded in marine barite exhibits an ~5 permil shift in d34Ssulfate that persists for ~15Myr before returning to pre-excursion values. Superimposed upon this long-term shift in S-isotopes is OAE1a, the second major anoxic event recognized in the Cretaceous. Two hypotheses have been proposed to explain this S isotope perturbation: (1) massive evaporite deposition associated with rifting during the opening of the South Atlantic and a corresponding decrease in pyrite burial rates and (2) increased inputs of volcanic-derived S due to extensive LIP-volcanism. While there is geologic evidence for both evaporite deposition and enhanced hydrothermal activity, the relative influence of these potential driving factors remains largely unconstrained. Variation in the strontium (Sr) isotope composition of marine carbonates provides a tool for distinguishing between these influences. We examine the S isotope composition of carbonate-associated sulfate (CAS) spanning the Barremian through Aptian from Resolution Guyot (ODP Site 866) and compare the S isotope record to time equivalent records of carbon and strontium isotopes. Correlative changes in the C, S, and Sr cycles are observed: an ~5 permil shift in d34Ssulfate, which begins at the onset of OAE1a and continues after the positive d13Ccarb excursion, is accompanied by a contemporaneous, parallel shift in 87Sr/86Sr to unradiogenic values. The tight coupling observed between S and Sr throughout the interval is highly suggestive of a common driving mechanism and suggests that changes in the S-cycle were dominantly driven by increases in volcanism and hydrothermal activity. Constraints on S-cycle fluxes and implications for seawater chemistry will be discussed in the context of coupled S-Sr geochemical models.