Description: The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates (SRR). Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT). Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydr)oxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS). Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron monosulfide phases meters below the SMT demonstrates that in sulfide-limited systems metastable sulfur constituents are not readily converted to pyrite but can be buried to deeper sediment depths. Our data show that in non-steady state systems, redox zones do not occur in sequence but can reappear or proceed in inverse sequence throughout the sediment column, causing similar mineral alteration processes to occur at the same time at different sediment depths.

Description: The Cretaceous period (similar to 145-65 m.y. ago) was characterized by intervals of enhanced organic carbon burial associated with increased primary production under greenhouse conditions. The global consequences of these perturbations, oceanic anoxic events (OAEs), lasted up to 1 m.y., but short-term nutrient and climatic controls on widespread anoxia are poorly understood. Here, we present a high-resolution reconstruction of oceanic redox and nutrient cycling as recorded in subtropical shelf sediments from Tarfaya, Morocco, spanning the initiation of OAE2. Iron-sulfur systematics and biomarker evidence demonstrate previously undescribed redox cyclicity on orbital time scales, from sulfidic to anoxic ferruginous (Fe-rich) water-column conditions. Bulk geochemical data and sulfur isotope modeling suggest that ferruginous conditions were not a consequence of nutrient or sulfate limitation, despite overall low sulfate concentrations in the proto-North Atlantic. Instead, fluctuations in the weathering influxes of sulfur and reactive iron, linked to a dynamic hydrological cycle, likely drove the redox cyclicity. Despite the potential for elevated phosphorus burial in association with Fe oxides under ferruginous conditions on the Tarfaya shelf, porewater sulfide generation drove extensive phosphorus recycling back to the water column, thus maintaining widespread open-ocean anoxia.

Description: The occurrence of microbially induced smectite-to-illite (S-I) reaction has challenged both the notions of solely inorganic chemical control for this reaction and the conventional concept of a semiquantitative illite geothermometer for the reconstruction of the thermal and tectonic histories of sedimentary basins. Here, we present evidence for a naturally occurring microbially induced S-I transition, via biotic reduction of phyllosilicate structural Fe(III), in mudstones buried at the Nankai Trough, offshore Japan (International Ocean Discovery Program Site C0023). Biotic S-I reaction is a consequence of a bacterial survival and growth strategy at diagenetic temperatures up to 80 °C within the Nankai Trough mudstones. These results have considerable implications for petroleum exploration, modification of fault behavior, and the understanding of microbial communities in the deep biosphere.