Effects of climate change and methane-rich fluid activity on sedimentary sulfur geochemical records in the northern South China Sea since mid-Pleistocene

Abstract

Microbial sulfate reduction (MSR) and associated pyritic sulfide formation are important diagenetic processes in marine sediments. The sulfur isotopic composition of pyrite (δ³⁴S_pyr) is proven to be sensitive to changes in sedimentation rates and the content and reactivity of organic carbon, especially on the continental shelves and upper slopes (water depth < 350 m). However, the diagenetic responses of sulfur to variations in climatic and depositional conditions in the deep-sea sediments are still poorly understood. This study combines element contents and isotopes to characterize diagenetic interplays of sulfur, organic carbon, and methane in the continental slope sediments of the northern South China Sea since the mid-Pleistocene. Our data suggest that the total organic carbon (TOC) increased during glacial times, implying enhanced primary productivity due to increased nutrient supply by the East Asian Winter Monsoon, in addition to efficient transfer of organic carbon and better preservation of organic carbon due to reduced bottom water oxygen. Total sulfur and chromium reduction sulfur contents varied concomitantly with the TOC, suggesting an increased burial of organic carbon that enhanced the organoclastic sulfate reduction (OSR) and the formation of authigenic pyrite. The environmental changes did not induce a significant shift in δ³⁴S_pyr, due most likely to relatively low sedimentation rates and large fractionation in sulfur isotope through OSR during the glacial-interglacial cycles. Instead, it is hypothesized that the sulfate-driven anaerobic methane oxidation promoted the formation of a higher amount of authigenic pyrite. Consequently, it created a closed diagenetic system leading to positive excursions in δ³⁴S_pyr at the sulfate-methane transition zone. Our results suggest the vulnerability of pyrite formation and its sulfur isotopic composition to the changes in monsoon-driven primary productivity and the methane-rich fluid migrations in the continental margin sediments. This study complements the growing evidence for the local diagenetic controls on sedimentary sulfur geochemical records by highlighting the importance of early diagenesis in paleoenvironment reconstruction based on the content and sulfur isotopic composition of pyrite.