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Understanding the controls on the sulfur isotope compositions of syndepositional pyrite (δ34S py) during early diagenesis is critical for environmental reconstructions, especially for the reconstruction of the marine sulfur cycle. Commonly, δ34S py values increase with depth in marine sediments; this phenomenon has been extensively studied, fostering the reconstruction of both global and regional depositional environments. However, more recently a decrease of δ34S py values with depth has been increasingly observed, but the corresponding controls on sulfur stable isotopes remain poorly constrained. This study investigated a gravity core collected from the northern continental slope of the South China Sea. Morphology, content, and δ34S values of pyrite, concentration and sulfur isotopic composition of porewater sulfate (δ34S SO4), carbon, nitrogen, and sulfur contents, and grain sizes of terrigenous sediments were analyzed and AMS14C dating of planktonic foraminifera was conducted. The δ34S py values were found to decrease with depth from −16.8‰ to −42.8‰, indicating low sulfur isotope fractionation (<38‰) during microbial sulfate reduction in the uppermost sediments and a larger fractionation (>64‰) at greater depth. Significant contributions of relatively 34S-enriched pyrite formed at shallow depth leads to overall δ34S py variations >26‰, whereby low δ34S py values coincide with higher sedimentation rates and higher organic matter supply. This study highlights the potential significance for relatively 34S-enriched, shallow-depth pyrite for δ34S py records, which may affect the reconstruction of depositional conditions and the global sulfur cycle. • Relatively 34S-enriched pyrite formed at shallow depth results from low sulfur isotope fractionation during MSR (<38‰). • Higher sedimentation rate and high organic matter supply led to lower δ34S py values. • Relatively 34S-enriched pyrite formed in uppermost sediments causes overall δ34S py variation >26‰. • δ34S py values provide new insight into the global sulfur cycle and past depositional processes. [ABSTRACT FROM AUTHOR]

Chemosymbiotic bivalves harboring endosymbiotic, chemotrophic bacteria have been investigated from a variety of hydrocarbon seeps worldwide. It has been shown that carbon, nitrogen, and sulfur isotopic compositions of the animal soft body parts are excellent indicators for evaluating energy transfer and food sources for the respective deep-sea habitats. However, recognition of chemosymbiosis has proven to be difficult for bivalves that dwelled at ancient seeps due to the lack of soft tissue. Here, we investigated δ 13 C, δ 15 N, and δ 34 S signatures of the tissue (mantle) and the shell organic matrix (SOM) of the same specimens of three bathymodiolin mussel species with different chemotrophic symbionts (methanotrophs in Bathymodiolus platifrons and B. childressi and thiotrophs in B. aduloides ) and one vesicomyid clam ( Calyptogena sp.) from a variety of hydrocarbon seeps from the South China Sea and the Gulf of Mexico. The data obtained demonstrate that all seep bivalves regardless of species or locations reveal overall small differences in δ 13 C (≤+4‰), δ 15 N (≤+1‰), and δ 34 S (≤+5‰) values between SOM and mantle (∆ SOM-mantle ) of the specimens. Relatively larger ∆ SOM-mantle for δ 13 C values (as high as +10‰) in B. platifrons and larger ∆ SOM-mantle for δ 34 S values (up to 16‰) in B. aduloides and Calyptogena sp. might be due to different symbionts in their gills. Since SOM can be extracted from fossil bivalve shells, the proxy can be used as a fingerprint of chemosynthesis-based food chains, although its utility will depend on the quality of preservation of the shell organic matter. Despite this uncertainty, the new proxy has great potential to reconstruct energy flow through different types of chemosynthesis-based ecosystems. [ABSTRACT FROM AUTHOR]

Sulfate-driven anaerobic oxidation of methane (SD-AOM) and organoclastic sulfate reduction (OSR) are the two processes that consume sulfate in methane-rich marine sediments. Determining the relative contribution of each process to overall sulfate reduction is critical to assess the global carbon and sulfur cycle in marine settings. The analysis of sulfur and oxygen isotope compositions of porewater sulfate (δ18O SO4 and δ34S SO4) provides crucial insight into sulfate reduction pathways and the dynamics of the sedimentary sulfur cycle. The δ18O SO4 /δ34S SO4 ratio is governed by net sulfate reduction rates and has been widely used to distinguish SD-AOM from OSR. Furthermore, δ18O SO4 /δ34S SO4 slopes are believed to vary with changing methane flux. To enhance the applicability of δ18O SO4 vs. δ34S SO4 plots for the tracing of SD-AOM activity and methane flux, we investigate sulfate sulfur and oxygen isotopes of porewaters from three piston cores collected from the Haima seeps of the South China Sea. Reaction-transport modeling previously indicated that sulfate consumption was dominated by SD-AOM under changing methane fluxes (1126 mmol m−2 yr−1 to 26 mmol m−2 yr−1). Our new data demonstrate an increase of the initial δ18O SO4 /δ34S SO4 slope when methane flux decreases. An initial slope of 0.43 corresponds to a methane flux of 194 mmol m−2 yr−1, the lowest currently known methane flux producing a small δ18O SO4 /δ34S SO4 slope diagnostic for SD-AOM in sediments close to the seafloor. When methane flux decreases to 26 mmol m−2 yr−1, a small slope (0.48) is only observed in deeper sediment layers. Our results also reveal an increase of δ18O SO4 /δ34S SO4 slopes with decreasing SD-AOM rates. We estimate that net sulfate reduction rates can be as low as 10−9 mol cm−3 yr−1 to produce slopes smaller than 0.5 in SD-AOM-dominated settings. In OSR-dominated settings, δ18O SO4 /δ34S SO4 slopes tend to be significantly higher than 0.5, while net sulfate reduction rates tend to be lower than 10−5 mol cm−3 yr−1. This study reveals that quantification of methane flux is required to utilize the full potential of δ18O SO4 vs. δ34S SO4 plots in the endeavor of tracing SD-AOM activity and the dynamics of the sulfur cycle in methane-rich environments. [ABSTRACT FROM AUTHOR]

The magnesium (Mg) isotopic composition of marine carbonate has been used as a proxy to constrain the geochemical composition of seawater and to trace the global Mg cycle. Sulfate-driven anaerobic oxidation of methane (SD-AOM) is a prominent process that facilitates the formation of marine authigenic carbonate. Yet the understanding of the impact of SD-AOM on the Mg isotope composition of authigenic carbonate under natural conditions is limited. Here we present the analysis of two tubular methane-seep carbonates from the South China Sea. The tubular carbonates reveal a trend of decreasing δ13C values and increasing carbonate contents from the periphery (i.e., the outer surface of the carbonate) to the inner portion (i.e., close to the inner surface of the carbonate pipes). The tubular carbonates are interpreted as former fluid conduits, indicating intense and lasting seepage that apparently increased with time. The observed variability in composition probably results from changes in the intensity of SD-AOM and correlating carbonate precipitation rates. Trends of enrichment of middle rare earth elements (MREEs), molybdenum (Mo), and uranium (U) from the periphery inward indicate more reducing formation conditions toward the inner surface of the former conduit. Along the same transects, δ26Mg values decrease from periphery to inner portion in one tubular carbonate (−2.63‰ to −3.24‰), while δ26Mg values are close to constant for the second tubular carbonate (−3.42‰ to −3.37‰); such patterns highlight the complexity of Mg isotope fractionation during seep carbonate formation. A positive correlation between δ26Mg and δ13C values and a negative correlation between δ26Mg and Mg/Ca molar ratios suggests that enhanced SD-AOM facilitates the incorporation of light Mg isotopes into the carbonate lattice. However, such assumption contradicts with the fact that higher carbonate precipitation rates reduce Mg isotope fractionation due to incomplete dehydration of Mg ions. It is hypothesized that hydrogen sulfide produced by SD-AOM may enlarge the extent of fractionation by weakening the hydration of Mg. If this interpretation is correct, the effect of sulfide on the fractionation of Mg isotopes can even offset or exceed the effect of precipitation rate. Our study indicates that SD-AOM has an effect on the Mg isotope fractionation during carbonate precipitation. Similar effects may have occurred in geological periods with more widespread carbonate authigenesis. A better understanding of the factors affecting the Mg isotopic fractionation during marine carbonate authigenesis is needed to efficiently use this archive of paleoenvironments and element cycling. [ABSTRACT FROM AUTHOR]

Marine sediments represent the largest reservoir of methane on Earth. Anaerobic oxidation of methane (AOM) mediated by anaerobic methanotrophic archaea (ANME) and associated sulfate-reducing bacteria is the main process controlling methane emission from marine sediments. Recent laboratory studies have revealed that ANME or AOM consortia can mediate nitrogen (N) fixation and ammonium assimilation. These processes are known to preferentially utilize 14N rather than the 15N isotope. However, geochemical fingerprints of microbial nitrogen uptake in marine sediments are lacking, limiting our understanding of its role in modern and ancient sedimentary environments. Here we report prominent negative excursions of bulk sediment δ15N values (up to −5‰) at sulfate-methane transitions (SMTs) where ANME show peak abundances in sediments at four sites of the Haima seeps of the South China Sea. Such δ15N excursions are restricted to SMTs, suggesting that 15N depletion results from ANME-mediated nitrogen uptake. We posit that this process is ubiquitous at the SMT – a reaction front in coastal and continental margin sediments worldwide – resulting in similar isotope patterns. Negative δ15N excursions are consequently a promising proxy to track AOM in the geological record and to better constrain carbon and nitrogen cycling in ancient sedimentary environments. [ABSTRACT FROM AUTHOR]

Sulfate-driven anaerobic oxidation of methane (SD-AOM) controls methane release from marine sediments to the ocean. A variety of authigenic precipitates within sediments has been widely used to identify past occurrences of SD-AOM. However, the lack of a systematic evaluation of the formation conditions of these precipitates sometimes impedes the recognition of SD-AOM in past environments characterized by diffusive transport of methane. Carbon, sulfur, and trace element geochemistry of pore-water and sediments was investigated at a site affected by upward methane diffusion in the Shenhu area of the South China Sea. Here, the sulfate-methane transition zone (SMTZ) is located ~7.6 m below the seafloor based on sulfate and methane concentrations. The slope of δ34S vs. δ18O values of sulfate is consistent with diffusive transport of methane. Concentration and isotope profiles of pore-water species point to diffusive rather than advective transport of solutes. Enhanced sulfate reduction inferred from δ34S values of sulfate agrees with the local occurrence of relatively abundant, 34S-enriched iron sulfide minerals. The time required to produce the observed authigenic iron sulfides around the SMTZ is estimated to be ~1.1 ka based on the amount of iron sulfide minerals and the present diffusive flux of sulfate. No enrichment of authigenic carbonate, barium (Ba), and molybdenum (Mo) was detected in the studied sediments. This observation is consistent with the calculation that the current fluxes of pore-water calcium, magnesium, Ba, and Mo are too low to allow for authigenic enrichments. The low fluxes are largely controlled by diffusion, which facilitates the formation of 34S-enriched iron sulfide minerals. The observed enrichment patterns – unlike those of sediments affected by advective seepage – are expected to be prevalent in modern and ancient continental-margin sediments, and may contribute to the identification of past methane-rich zones and overlying SD-AOM zones as sinks for methane in the geological record. [ABSTRACT FROM AUTHOR]