Ocean Circulation, Nutrient Cycling, and the S-isotope Composition of Earth Paleozoic Marine Systems

Linda C. KahDepartment of Earth & Planetary Sciences

University of Tennessee

Evolution of the marine sulfur cycle and its linkage to oceanic carbon cycling is a critical link in understanding depositional environments and time-temperature pathways experienced during hydrocarbon maturation. Many of these depositional and diagenetic models, however, are based on assumptions of marine sulfate concentrations similar to that of today, despite growing evidence that marine sulfate concentrations may have been much lower than present for much of Earth history. For instance, lower sulfate concentrations in the Early Paleozoic would have been influenced by even small changes in marine oxygenation and redox cycling, potentially driven by changing oceanic circulation patterns. Redox cycling, in turn would result in substantially more variable isotopic compositions, and may even contribute, ultimately, to organic carbon availability.

This project has produced high-resolution isotopic records of both oxidized and reduced forms of carbon (carbonate and organic matter) and sulfur (carbonate-associated sulfate and pyrite) from gas-producing Cambrian and Ordovician rocks of the Argentine Precordillera. Rapid isotopic variation in carbonate-associated sulfate (6‰ over 10-20 meters) suggests that variation results from short-term redox cycling rather than wholesale changes in the size of the marine sulfate reservoir. In this model, rapid shift in the S-isotope composition of seawater was driven by relative changes in the extent of bacterial sulfate reduction and sulfide oxidation with a fluctuating marine redox boundary, and perhaps enhanced by nutrient-driven changes in organic carbon transport to the deep ocean. Currently, we are involved in high-resolution radiometric dating of strata to determine the time-scale of observed fluctuations in oceanic chemistry.