Description: Elemental sulfur is commonly regarded as the product of oxidative sulfur cycling in the sediment. However, reports on the occurrence of elemental sulfur in seepage areas are few and thus its origin and mechanisms controlling its distribution are insufficiently understood. Here, we analyzed the multiple sulfur isotopic compositions for elemental sulfur and pyrite from an iron-dominated gas hydrate-bearing sedimentary environment of the South China Sea to unravel the impact of sulfate-driven anaerobic oxidation of methane (SO4-AOM) on the formation of elemental sulfur. The multiple sulfur isotopes reveal variable ranges for both elemental sulfur and pyrite (δ34S: between −15.7 and +23.3‰ for elemental sulfur and between −35.3 and +34.4‰ for pyrite; Δ33S: between −0.08 and +0.06‰ for elemental sulfur and between −0.03 and +0.15‰ for pyrite). The enrichment of 34S in pyrite throughout the sediment core suggests pronounced SO4-AOM in paleo-sulfate-methane transition zones (SMTZ). In addition, the occurrence of seep carbonates with very negative δ13C values (as low as −57‰, V-PDB) coincides with the inferred paleo-SMTZs and agrees with formerly locally pronounced SO4-AOM. Interestingly, the multiple sulfur isotopic composition of elemental sulfur reveals a different pattern from that of pyrite derived from organoclastic sulfate reduction (i.e., with low δ34S and high Δ33S values for the latter). In comparison to coexisting pyrite, most of the elemental sulfur reveals higher δ34S values (as much as +28.9‰), which is best explained by an enrichment of 34S in the residual pool of dissolved sulfide generated by SO4-AOM. As an intermediate sulfur phase, elemental sulfur can form via sulfide oxidation coupled to iron reduction, but it can only persist in the absence of free sulfide. Therefore, the occurrence of 34S enriched elemental sulfur is likely to represent an oxidative product after hydrogen sulfide had vanished due to vertical displacement of the SMTZ. Our observations suggest that elemental sulfur may serve as a useful recorder for reconstructing the dynamics of sulfur cycling in modern and possibly ancient seepage areas.

Description: Depth profiles of the stable sulfur isotopic composition of dissolved sulfate in near-surface sediments were measured at five stations of the deep Arabian Sea between 1918 and 4426 m water depth (WAST, WAST-Top, CAST, SAST, NAST), sampled in April 1997. The results clearly indicate that net microbial sulfate reduction took place in the sediments at stations WAST and NAST below about 12 cm depth. Sulfate reduction at WAST was more pronounced compared to station NAST, most likely due to higher organic carbon content in turbiditic sediments. No net sulfate reduction took place within the upper 10 cm of the surface sediments at all stations, and no significant isotopic indication for sulfate reduction was found down to 30 cm bsf at station SAST. Results are in accordance with accumulation of reduced isotopically light sulfur species below about 6 cm bsf at station WAST. It is concluded that the sulfur isotopic composition of remaining sulfate is more sensitive to net sulfate reduction than the [SO4]/[Cl] ratio. The sulfur isotopic composition of a vertical profile for dissolved sulfate through the water column at station WAST was essentially constant (250–4047 m: Full-size image (〈1 K)‰ vs. V-CDT n=8). A similar constancy (20–4565 m water depth Full-size image (〈1 K)‰ vs. V-CDT n=15) was found for the station BIOTRANS in the northeastern Atlantic (47°11′ 19°33W), indicating that the oxygen minimum zone in the Arabian Sea has no influence on the sulfur isotopic composition of dissolved sulfate.

Description: Interstitial water samples from seven ODP sites (Leg 181, Sites 1119–1125) of the southwestern Pacific Ocean have been analyzed for the stable sulfur isotopic composition of dissolved sulfate along with major and minor ions. Sulfate from the interstitial fluids (δ34S values between +20.7 and +60‰ vs. the SO2-based Vienna–Canyon Diablo troilite standard) was enriched in 34S with respect to modern sea water (δ34S≈+20.6‰) indicating that microbial sulfate reduction takes place to different extents at all investigated sites. Microbial sulfate reduction (MSR) was found at all sites, the intensity depending on the availability of organic matter which is controlled by paleo-sedimentation conditions (sedimentation rate, presence of turbidites) and productivity. Microbial net sulfate reduction was additionally confirmed by modeling interstitial water sulfate profiles. Areal net sulfate reduction rates up to 14 mmol m−2 yr−1 have been calculated which were positively related to sedimentation rates. Total reduced inorganic sulfur (TRIS; essentially pyrite) as a product of microbial sulfate reduction was isotopically characterized in squeeze cake samples and gave δ34S values between −51 and +9‰ indicating pyrite formation both close to the sediment–water interface and later diagenetic contributions.