Description: Authigenic carbonates and pyrite associated with sulfate-driven anaerobic oxidation of methane (AOM) at methane seeps provide archives to explore the biogeochemical processes involved and seepage dynamics over time. The wide range and extremely high δ34S values of pyrite (δ34Spy) have been used to trace the AOM-related processes. However, the detailed mechanism for this phenomenon is not well understood. We propose that the characteristics of δ34Spy were mainly controlled by the competition between sulfate reduction and sulfate supply, as well as the redox condition. To test this hypothesis, we investigated Sr/Ca and Mg/Ca ratios, trace element compositions, pyrite contents and sulfur isotopic compositions in seep carbonates from Site F and Haima in the northern South China Sea. Calcite and aragonite contents were distinguished through the Sr/Ca and Mg/Ca ratios. The data show that aragonites are always associated with relatively low δ34Spy values compared to calcites. The Mo contents show a good correlation with pyrite contents in calcites and aragonites, and the slope in aragonites is larger than that in calcites. This relationship indicates that the aragonite precipitated in a relatively open system with higher Mo availability. Thus, we conclude that sulfides with low δ34S values formed at high supply of sulfate under the relatively open system with respect to diffusive replenishment of sulfate, where the carbonate precipitation occurred close to the seafloor due to a strong methane flux. Under vigorous methane flux simultaneously, the high potential of less anoxic conditions, which could limit the additional pyrite accumulation and/or favor the microbial disproportionation, could also be the cause of the low δ34Spy, as supported by samples from the Haima sites. Evidence for this assumption is based on the occurrence of bivalve shells and less enrichment in As and Sb. Conversely, the positive δ34Spy values result from near to complete exhaustion of dissolve sulfate via AOM within a deeper sulfate-methane transition zone, where Mo is less available. The combination of a detailed elemental study of authigenic carbonates with sulfur isotopic composition of sulfide minerals in carbonates is a promising tool for reconstructing the dynamics of seep intensities at modern and, potentially, geological seep sites.

Description: Highlights • Elemental and radiocarbon analysis of southern Mariana Trench (SMT) sediments since 30 ka. • Shift to more reducing (suboxic) deep waters during the Last Glacial Maximum (LGM). • Blooms of giant diatom Ethmodiscus rex formed laminated diatom mats (LDMs) during LGM. •Redox changes were due to increased primary productivity induced by enhanced Asian dust inputs. • Biogenic and authigenic apatite are the main carriers of rare earth elements (REEs) in SMT sediments. Abstract: The modern southern Mariana Trench is characterized by oligotrophic surface waters, resulting in low primary productivity and well-oxygenated bottom waters. This study investigates changes in the redox conditions of bottom waters in the southern Mariana Trench during the Last Glacial Maximum (LGM) and their potential causes. We measured major, trace, and rare earth elements (REE) in three gravity cores (GC03, GC04, and GC05) and one box core (BC11) retrieved from the southern Challenger Deep at water depths from 5289 to 7118 m. The upper sediment layers of both GC05 and BC11 are dominated by valve fragments of the giant diatom Ethmodiscus rex, forming laminated diatom mats (LDMs). 14C-AMS dates of bulk organic matter show that the LDMs accumulated between 18.4 and 21.8 kyr B.P., corresponding to the LGM. Modest enrichments of U and Mo along with weak or absent Ce anomalies in the LDM point to suboxic conditions during the LGM. In contrast, non-LDM samples exhibit little to no enrichment of redox-sensitive elements as well as negative Ce anomalies, indicating deposition under oxic bottom-water conditions. The Ce anomalies are considered valid proxies for bottom-water redox conditions because REE signatures were acquired in the early diagenetic environment, as indicated by strong P-REE correlations and middle-REE enrichment associated with early diagenetic cycling of Fe-Mn oxyhydroxides in the sediment column followed by capture of the REE signal by biogenic and/or authigenic apatite. We postulate that the more reducing bottom-water conditions during the LGM were linked to increased primary productivity induced by enhanced Asian dust input. As shown in earlier studies, the increased primary productivity associated with Ethmodiscus rex blooms in the eastern Philippine Sea played a significant role in capturing atmospheric CO2 during the LGM. Consequently, the magnitude of atmospheric CO2 sequestration by giant diatom blooms during the LGM may have been greater than previously envisaged.