Sulfate-driven Anaerobic Oxidation Of Methane Research Articles

The Impact of Sulfate-Driven Anaerobic Oxidation of Methane on the Carbon Isotopic Composition in Marine Sediments: A Case Study from Two Sites in the Shenhu Area, Northern South China Sea

Abstract Authigenic carbonate in seep environments, as a direct byproduct of sulfate-driven anaerobic oxidation of methane (SD-AOM), is usually absent within the sediment column because of the requirement of a strict formation condition. In this case, the lack of a reliable carbon signal may impede the identification of SD-AOM and methane leakage. Here, carbon and oxygen isotopes, elemental compositions, AMS 14C dates in sediments, and porewater geochemistry were investigated from two sites (A27 and SH1) of the Shenhu area, northern South China Sea (SCS), to discuss how SD-AOM affects the carbon isotope in methane-affected marine sediments. Porewater results at both sites indicate the occurrence of methane diffusion from the sulfate-methane transition zone (SMTZ) below. The carbon isotopes of bulk-sediment carbonate and foraminifera show no distinctly negative excursion, reflecting that these signals are invalid in response to SD-AOM in the investigated sites. Then, a mass balance model is adopted to evaluate the δ13C value of authigenic carbonate (δ13CAC). Consequently, three intervals (A2 and A3 from site A27 and S2 from site SH1) are identified, featuring negative δ13CAC values, high TS/TOC ratios, and enhanced contents of authigenic carbonate, which are most likely influenced by SD-AOM. Considering the current SMTZ located at deeper layers, intervals A2 and S2 represent the locations of paleo-SMTZ, while interval A3 is thought to be influenced by the current methane diffusion. Interestingly, the δ13C values of total organic matter (δ13CTOC) show positive excursions within the paleo-SMTZs, which can be explained herein by the diagenetic modification. In the course of SD-AOM at the SMTZ, high rate of (methylotrophic) methanogenesis preferentially consumes lighter carbon atoms in organic matter, with the remainder being gradually more positive. Our results indicate that the exploration of a reliable methane-carbon response in systems lacking seep carbonates plays an important role in constraining SD-AOM and methane release.

Diagenetic barite-calcite-pyrite nodules in the Silurian Longmaxi Formation of the Yangtze Block, South China: A plausible record of sulfate-methane transition zone movements in ancient marine sediments

The sulfate-methane transition zone (SMTZ) serves as an important geochemical transition especially during early diagenesis. Organoclastic sulfate reduction (OSR), sulfate-driven anaerobic oxidation of methane (SD-AOM), fermentation, and methanogenesis, the dominant diagenetic processes near the SMTZ, play key roles in marine sulfur and carbon cycling. However, the paleo-SMTZ has rarely been identified in the geologic record because of equivocal evidence. The presence of barite-calcite-pyrite assemblages (abundant nodules and pyritic laminae) concentrated over a 1-m thick interval of the Silurian Longmaxi Formation, Yangtze Block, South China, provide a unique opportunity to investigate possible vertical movements of the paleo-SMTZ in ancient sediments. The inferred paleo-SMTZ comprises nodules made up of barite (BaSO4), calcium carbonate (CaCO3), and pyrite (FeS2), and pyritic laminae. Strong 34S enrichment of barite (50 to 62.1‰ VCDT) and modestly 13C-depleted calcite (−11.4‰ to −5.3 VPDB) of the nodules associated with positive δ34S values of pyritic laminae (4 to 6.2‰ VCDT) suggest precipitation of these minerals sourced by mixed carbon and sulfur sources close to and/or within the paleo-SMTZ. Nodules from center to edge display mineral zonation that may reflect the effects of depth fluctuations of the paleo-SMTZ. Initial (stage 1) barite mineralization in nodule centers appears to have occurred within the base of the sulfate reduction zone (SRZ). By the time if stage 2 mineralization, the stratigraphic locus of precipitation had migrated closer to highly alkaline SMTZ resulting in barite dissolution and calcium carbonate precipitation. Higher proportions of calcium carbonate exhibiting some enrichment of 12C associated with cubic pyrite crystals in nodule centers are consistent with the occurrence of SD-AOM within the SMTZ. Stage 3 acicular barite mineralization along nodule edges likely took place near at the base of SRZ immediately above the SMTZ, whereas the replacement of barite by calcite during stage 4 mineralization occurred again within the SMTZ. Vertical movement of paleo-SMTZs suggested by the occurrences of barite-calcite-pyrite assemblages in the Longmaxi Formation across Yangtze Block, are likely the consequence of the complex interplay of varying sedimentation rate, organic matter quality, methane flux, and perhaps seawater sulfate concentration.

Impacts of sulfate-driven anaerobic oxidation of methane on the morphology, sulfur isotope, and trace element content of authigenic pyrite in marine sediments of the northern South China Sea

The presence of sulfate-driven anaerobic oxidation of methane (SD-AOM) generally influences the precipitation of authigenic pyrite in seepage areas. However, the relatively weak comprehensive studies on the morphological and geochemical characteristics of pyrite limit the understanding of its formation and application to diagenetic processes. Here, we analyzed the pyrite texture, abundance, sulfur isotopic composition, degree of pyritization, and the trace element (TE) content of pyrite from two sites (A27 and SH1) in a seepage area of the South China Sea, so as to better constrain the impacts of SD-AOM on pyrite formation. Pore-water results revealed that present-day methane seepages occurred at both sites. Under normal sedimentary environments, pyrite resulting from organiclastic sulfate reduction (OSR) showed low abundances with negative δ34S. In contrast, high contents of 34S-enriched pyrite aggregates, long pyrite tubes and large framboid sizes typified by radial overgrowths were documented at the lower part of both core sediments, suggesting the significant impacts of SD-AOM. At the proposed sulfate-methane transition zone (SMTZ), pyrite is a mixing product of OSR and SD-AOM, but the latter enhances the morphologic and isotopic anomalies of pyrite. Besides, SD-AOM increased the degree of pyritization and accelerated the pyrite-iron accumulation in sediments. With pyritization proceeding, Mo, Ni, Mn, and Cr were gradually incorporated into the pyrite phase, presenting a relatively high affinity of these TEs for pyrite in the studied locations. However, the contents of TE in pyrite were positively correlated with its concentrations in the current ocean, from which we can get that TE in diagenetic pyrite was basically influenced by seawater chemistry. The comprehensive results reflect that the authigenic pyrite can act as an excellent geological archive of modern and ancient oceans. In particular, pyrite formed in seepage-impacted sediments allows identifying the methane seepage and characterizing the biogeochemical cycling of carbon, sulfur, and TEs.

Contribution of deep-sourced carbon from hydrocarbon seeps to sedimentary organic carbon: Evidence from radiocarbon and stable isotope geochemistry

Sulfate-driven anaerobic oxidation of methane (AOM) limits the release of methane from marine sediments and promotes the formation of carbonates close to the seafloor in seepage areas along continental margins. It has been established that hydrocarbon seeps are a source of methane, dissolved inorganic carbon, and dissolved organic carbon to marine environments. However, questions remain about the contribution of deep-sourced carbon from hydrocarbon seeps to the sedimentary organic carbon pool. In this study, we analyzed carbon quantity, radiocarbon content (as percent modern carbon, pMC), stable carbon isotopic compositions (as δ13C) of organic matter enclosed within seep carbonates from the Gulf of Mexico and the South China Sea to assess if sediment organic matter may be used as a proxy for methane seepage intensity. The δ13C values of organic matter (δ13Corg) exhibited a large range from −81.4‰ to −23.9‰. Radiocarbon contents of the carbonate-bound organic matter in seep carbonates ranged from 6% to 28% pMC, suggesting organic matter of the carbonates is a mixture of marine particulate organic matter (δ13C = −22‰ VPDB and 90% modern carbon) and biomass resulting from methane oxidation (assumed to have 0% modern carbon). Assuming constant productivity in the marine photic zone, it is proposed that seepage intensity and duration are the most important factors controlling the contribution of methane-derived carbon to the sedimentary column. This study reinforces the potential for using δ13C values of organic carbon to discern methane-rich environments in ancient sedimentary environments where authigenic carbonate is not present and to constrain the record of AOM through Earth history.

Depositional control on carbon and sulfur preservation onshore and offshore the Oujiang Estuary: Implications for the C/S ratio as a salinity indicator

Carbon and sulfur preserved in estuary and shelf sediments play a critical role in controlling sediment diagenesis related to the global biogeochemical cycle. Their ratio (C/S = 2.8) in mud sediments has been widely used to distinguish freshwater from marine environments; however, this ratio can be influenced by depositional evolution, physical reworking, and other sedimentological parameters. We present a new C/S ratio data set from surface sediments of five rivers (Aojiang, Feiyunjiang, Jiaojiang, Oujiang, and Qiantangjiang Rivers), as well as core sediments offshore of the Oujiang Estuary (core EC2005, 60 m), to discuss how the evolution of the depositional environment influenced carbon and sulfur preservation since the last deglaciation. To this aim, we measured the contents of total organic carbon (TOC), total sulfur (TS), and carbonate in the collected samples. Our results demonstrate that a C/S ratio of 2.8 can effectively separate freshwater environments (river sediments and core sediments deposited before 13.1 ka), suggesting the initial impact of sulfate-enriched seawater on carbon and sulfur perseveration at ~13.1 ka. However, the TS content is independent of the TOC content after 13.1 ka, implying that pyrite sulfur is derived not only from organoclastic sulfate reduction (OSR) but also from sulfate-driven anaerobic oxidation of methane (AOM) under anoxic diagenetic conditions. In the shallowest core section (shallower than 5 m; < 1.5 ka), the C/S ratios gradually increase from 1 to 2.8, which corresponds to an interval with sulfide reoxidation under suboxic conditions caused by strong physical reworking. When the sediment is buried to a certain depth (deeper than 5 m; > 1.5 ka), a high sedimentation rate is conducive to an AOM reaction, resulting in the generation of a large amount of pyrite and finally causing the minimum value of the C/S ratio to be approximately 1. However, during the transitional period of 13.1–11.0 ka, sediments deposited in the tidal environment show overlap with those deposited in the marine shelf environment, and C/S ratios decrease from >10 to ~1. In addition, we propose that C/S and C/N ratios could be combined to reveal the depositional evolution from terrestrial to marine environments, which is sensitive to sea level and climatic changes. Therefore, our new findings suggest that the sedimentation process can modulate the diagenetic path of mud sediments (e.g., OSR versus AOM), and geochemical indicators of environmental evolution should be carefully used in combination with sedimentological parameters in shallow depositional environments.

Carbon-sulfur signals of methane versus crude oil diagenetic decomposition and U-Th age relationships for authigenic carbonates from asphalt seeps, southern Gulf of Mexico

Offshore hydrocarbon accumulations in the Gulf of Mexico (GoM) are often accompanied by natural seepage of oil and gas from subsurface reservoirs into shallow sediments and the water column. This study investigated the temporal patterns and carbon-sulfur (C-S) coupling associated with authigenic carbonate samples recovered from surface sediments of a crude oil seepage site in southern GoM (Chapopote asphalt volcano, Bay of Campeche) using radioactive U-Th dates, and stable C, O, and S isotopes. The results were compared with data from multiple seep sites in the northern GoM where methane seepage is dominant along with non-methane hydrocarbons (ethane , propane, crude oil, etc.). U-Th age-dating of Chapopote seep carbonate samples yielded ages of 13.5 ka to 4.6 ka before present (BP), suggesting that Chapopote asphalt seepage has been ongoing for thousands of years. The results are also consistent with previous studies from the northern GoM that hypothesize that seeps along the GoM continental slope were active during the last deglaciation. δ13CCaCO3 and δ18OCaCO3 values from authigenic carbonates at Chapopote indicated a mixed contribution of methane and non-methane hydrocarbons to the dissolved inorganic carbon (DIC) pool, consistent with previous results. Comparison of δ13CCaCO3 vs. δ34SCRS (CRS = chromium reducible sulfur) from carbonate samples showed noticeable differences at the Chapopote seep site (average δ13CCaCO3 -25‰ VDPB, δ34SCRS -27‰ VCDT) relative to the methane seep-dominated samples from the northern GoM (average δ13CCaCO3 < -40‰ VDPB, δ34SCRS >0‰ VCDT). Our results point toward distinguishable differences in the paired δ13CDIC and δ34Ssulfide signatures produced via the diagenetic processes of sulfate-driven anaerobic oxidation of methane versus non-methane hydrocarbons. These results potentially provide an important proxy for identification of such diagenetic processes within the sedimentary records.

Deciphering the sulfur and oxygen isotope patterns of sulfate-driven anaerobic oxidation of methane

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 (δ18OSO4 and δ34SSO4) provides crucial insight into sulfate reduction pathways and the dynamics of the sedimentary sulfur cycle. The δ18OSO4/δ34SSO4 ratio is governed by net sulfate reduction rates and has been widely used to distinguish SD-AOM from OSR. Furthermore, δ18OSO4/δ34SSO4 slopes are believed to vary with changing methane flux. To enhance the applicability of δ18OSO4 vs. δ34SSO4 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 δ18OSO4/δ34SSO4 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 δ18OSO4/δ34SSO4 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 δ18OSO4/δ34SSO4 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, δ18OSO4/δ34SSO4 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 δ18OSO4 vs. δ34SSO4 plots in the endeavor of tracing SD-AOM activity and the dynamics of the sulfur cycle in methane-rich environments.

Molybdenum isotope composition of seep carbonates – Constraints on sediment biogeochemistry in seepage environments

Methane seepage causes significant changes in the local diagenetic environment and impacts the marine sedimentary cycles of sulfur, carbon, and molybdenum (Mo), which are intimately linked to each other. Molybdenum isotopic compositions were determined for authigenic carbonate nodules and bulk sediments of a 230-m long sediment core collected at a methane seep site in the South China Sea. Authigenic carbonate nodules occur at different sediment depths and display low δ13C values around −50‰ revealing that carbon predominantly derived from biogenic methane. Moreover, seep carbonate nodules are substantially enriched in Mo (Al-normalized enrichment factors MoEF between 27 and 70), and display nearly constant δ98Mo values around an average of +1.9‰ (relative to NIST3134 = +0.25‰), close to the Mo isotopic composition of modern seawater (+2.3‰). Linear positive correlations between δ98Mo values and pyrite sulfur contents and Mo contents were identified for seep carbonate samples. This implies that Mo scavenging into pyrite is likely controlled by hydrogen sulfide availability derived from sulfate-driven anaerobic oxidation of methane (SD-AOM). The essentially constant and high δ98Mo values suggest that Mo species were nearly quantitatively incorporated into the authigenic carbonates under highly sulfidic conditions, probably at times when the sulfate-methane transition zones (SMTZ) was situated at shallow sediment depth at times of high seepage activity. In contrast, bulk sediments that exhibit typical marine δ13C values close to 0‰ (versus VPDB), hence devoid of methane-derived seep carbonates, are characterized by low Mo contents (MoEF = ~0.9). Their lower δ98Mo values mostly ranging from +0.2 to +0.8‰, in accord with low Mo contents, likely reflect input of detrital Mo. Bulk sediments bearing seep carbonate nodules display variable δ13C values lower than −5‰ and are characterized by a wide range in Mo contents (MoEF from 1.5 to 45.3) and δ98Mo values (+0.7 to +3.0‰). The high δ98Mo values of some sediment samples, relative to the seep carbonate signature, might indicate an additional accumulation of a 98Mo enriched pool of molybdenum during later SD-AOM at a deeper SMTZ postdating initial seep carbonate formation; such 98Mo enrichment was probably caused by preceding preferential removal of lighter Mo isotopes from pore fluids. Our results indicate that Mo isotope systematics of seep deposits can provide constraints on the dynamics of the biogeochemical cycling of carbon, sulfur, and trace elements in methane seep environments. A potential for authigenic carbonates to archive the Mo isotopic composition of seawater is indicated, but will have to be assessed in future studies.

Using multi-proxy approach to constrain temporal variations of methane flux in methane-rich sediments of the southern South China Sea

Methane seeps are widespread on the seafloor in continental margins. However, the responses of methane flux and diagenetic processes at cold seeps to drastic environmental changes in the geological history are still poorly understood. Here, we report the geochemical composition of porewaters and sediments in a sediment core (CL3A) collected from methane-rich sediments in the southern South China Sea, in order to assess the variations in upward methane flux since the last glacial period. A sediment horizon at depths of ca. 510–660 cm below seafloor just above the current sulfate-methane transition zone (SMTZ) is identified, which shows geochemical anomalies including high total inorganic carbon (TIC) and total sulfur (TS) contents, extremely negative δ13CTIC values and positive sulfur isotopic ratios of acid insoluble sulfur (δ34Sacid-insoluble). We propose that the diagenetic records of sulfate-driven anaerobic oxidation of methane within a paleo-SMTZ were recorded by the accumulation of authigenic carbonate and iron sulfide within this zone. Such geochemical pattern implies a fixation of the SMTZ at a certain depth for a prolonged time, which is estimated as ~13,000 years. The stagnation of the SMTZ is probably attributed to a large decline in sedimentation rate during the transition of last glacial/interglacial period, which is supported by the 14C ages throughout the core. Moreover, a non-steady-state modelling for the concave-up depth profiles of porewater species suggests that a recent enhancement in upward methane flux has lasted for at least 550 years. In summary, this study suggests that the fixation of SMTZ during the glacial/interglacial transitions in dynamic sedimentation regimes can lead to the accumulation of large amount of authigenic carbonate and iron sulfide in continental margins and should be considered in global carbon and sulfur biogeochemical cycles.

The Carbon-Sulfur Link in the Remineralization of Organic Carbon in Surface Sediments

Here we present the carbon isotopic composition of dissolved inorganic carbon (DIC) and the sulfur isotopic composition of sulfate, along with changes in sulfate concentrations, of the pore fluid collected from a series of sediment cores located along a depth transect on the Iberian Margin. We use these data to explore the coupling of microbial sulfate reduction (MSR) to organic carbon oxidation in the uppermost (up to nine meters) sediment. We argue that the combined use of the carbon and sulfur isotopic composition, of DIC and sulfate respectively, in sedimentary pore fluids, viewed through a δ13CDIC vs. δ34SSO4 cross plot, reveals significant insight into the nature of carbon-sulfur coupling in marine sedimentary pore fluids on continental margins. Our data show systemic changes in the carbon and sulfur isotopic composition of DIC and sulfate (respectively) where, at all sites, the carbon isotopic composition of the DIC decreases before the sulfur isotopic composition of sulfate increases. We compare our results to global data and show that this behavior persists over a range of sediment types, locations and water depths. We use a reactive-transport model to show how changes in the amount of DIC in seawater, the carbon isotopic composition of organic matter, the amount of organic carbon oxidation by early diagenetic reactions, and the presence and source of methane influence the carbon and sulfur isotopic composition of sedimentary pore fluids and the shape of the δ13CDIC vs. δ34SSO4 cross plot. The δ13C of the DIC released during sulfate reduction and sulfate-driven anaerobic oxidation of methane is a major control on the minimum δ13CDIC value in the δ13CDIC vs. δ34SSO4 cross plot, with the δ13C of the organic carbon being important during both MSR and combined sulfate reduction, sulfate-driven AOM and methanogenesis.

Deciphering the geochemical link between seep carbonates and enclosed pyrite: A case study from the northern South China sea

Sulfate-driven anaerobic oxidation of methane (SD-AOM) is an important microbial process at methane seeps, which consumes most of the methane migrating from sediments and can lead to the formation of seep carbonate and pyrite. Geochemical proxies archived in seep carbonates have been long used to uncover the nature of seepage. Recently, the sulfur isotopic composition of enclosed pyrite shows ideal prospects for targeting the seepage dynamics, but it remains challenging due to a possible decoupled precipitation of carbonate and pyrite. In order to decipher the geochemical link between seep carbonates and enclosed pyrite, multiple geochemical proxies of both carbonate (major elements, rare earth elements, δ13C) and pyrite (contents and δ34Spy) were analyzed from two seep sites of the northern South China Sea. Multiple carbonate phases were identified via X-ray diffraction and transmission electron microscopy, including microcrystalline aragonite and botryoidal aragonite from Haima seeps, and micritic high-magnesium calcite (HMC), weakly ordered dolomite and botryoidal aragonite from site TVG11. The δ13C values for carbonates from both sites exhibit very light carbon isotopic signatures (from −59.2 to −35.8‰), confirming that the carbon source is mainly derived from the oxidation of biogenic methane. For pyrite enclosed in carbonates, their contents and sulfur isotopic compositions (δ34Spy) reveal generally positive correlations with Mg/Ca ratios, where HMC and dolomite show higher pyrite contents and δ34Spy values, but microcrystalline aragonite and botryoidal aragonite display lower pyrite contents and negative δ34Spy values. This is consistent with our knowledge that HMC and dolomite tend to precipitate at a deeper sulfate-methane transition zone (SMTZ) where the replenishment of seawater sulfate is limited, whereas microcrystalline aragonite and botryoidal aragonite tend to form at shallow SMTZ with enhanced seawater sulfate supplement. Thus, the δ34S values of pore water sulfate greatly affect the resulting sulfur isotopic composition of pyrite, i.e., the higher δ34Spy values in HMC and dolomite are attributed to the 34S enrichment in pore water sulfate at deeper SMTZ. This is supported by SIMS results that pyrite entrapped in botryoidal aragonite displays lower δ34SSIMS values than those in HMC. Our results suggest that geochemical proxies archived in both carbonate and pyrite point to the similar sedimentary environments, suggesting an intrinsic link between these two archives in our study sites.

Behavior of Mg isotopes during precipitation of methane-derived carbonate: Evidence from tubular seep carbonates from the South China Sea

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.

The impact of diffusive transport of methane on pore-water and sediment geochemistry constrained by authigenic enrichments of carbon, sulfur, and trace elements: A case study from the Shenhu area of the South China Sea

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.

Environmental evolution of the East China Sea inner shelf and its constraints on pyrite sulfur contents and isotopes since the last deglaciation

To better understand the depositional constraints on the sulfate reduction process, we present a set of sulfur isotope data for hand-picked pyrites (δ34Spyr) from the coarse fraction (63–250 μm) of bulk sediments, coupled with the contents of carbonate, total organic carbon (TOC) and nitrogen (TN), as well as δ13C values of the TOC, from sediments of core EC2005 on the inner shelf of the East China Sea (ECS) since 16.4 ka. Our results show that core sediments were deposited in a terrestrial environment before 13.1 ka (stage I) when pyrite rarely occurred. During stages II (13.1–12.3 ka) and III (12.3–12.1 ka) seawater began to influence the core location, forming a tidal flat environment where abundant pyrites are well preserved. Then the inner shelf of the ECS was fully flooded, and two intervals with high (stage IV:12.1–6.0 ka; stage VI: 5.2–1.5 ka) and low sedimentation rate (stage V: 6.0–5.2; stage VII: 1.5 ka-present) are identified respectively. When compared with previous δ34S values of chromium-reducible sulfur (δ34SCRS) derived from the bulk sediments, δ34Spyr values are usually higher, indicating the macroscopic pyrites form in the later stages of sedimentary diagenesis when ongoing sulfate reduction has distilled porewater sulfate to a high degree. Considering the wide occurrence of biogenic shallow gas (dominated by CH4) in these sediments, sulfate-driven anaerobic oxidation of methane (SO4-AOM) and organoclastic sulfate reduction (OSR) are expected to be two competitive pathways for sulfate reduction. We propose that the changes in sedimentation rate controls the pace of migration of the sulfate methane transition zone (SMTZ). When sedimentation rate is low, the SMTZ may be fixed in a certain depth (e.g., sediments deposited in stage III and V), where H2S is produced by SO4-AOM. In contrast, when sedimentation rate is very high (> 1 cm/yr), the SMTZ would be deep, and H2S is mostly produced by OSR. Further, our results imply that sulfur diagenesis in recent (since 1.5 ka) ECS mud sediments might be influenced by physical reworking (e.g., typhoon) and/or biological activity (bioturbation), resulting in partial reoxidation of pyrite crystals in fluid mud. Our findings therefore demonstrate that pyrite sulfur isotope compositions (bulk δ34SCRS & hand-picked δ34Spyr) are sensitive to local environmental evolution and the combined use of these two indicators can provide new insights into pathway of sulfate reduction in unsteady environments.

Phosphorus Species in Deep-Sea Carbonate Deposits: Implications for Phosphorus Cycling in Cold Seep Environments

Phosphorus (P) is an important nutrient for biological communities in cold seeps. However, our knowledge on the source, species, and cycling of P in cold seep environments is limited. In this study, the concentration, species, and micro to nanometer scale distribution of P in seep carbonates were examined at three deep-sea cold seeps in the South China Sea and East China Sea. The Ca-P accounts for the largest proportion of P—followed by detrital-P, Fe-P, organic-P, and exchangeable-P. The distribution patterns of Ca-P, detrital-P, and organic-P in the seep carbonates differ from one another, as shown by elemental mapping with NanoSIMS and scanning electron microscopy. The covariation of P with Ca and C reveals that Ca-P co-precipitates with Ca-carbonate, which is linked to the process of sulfate-driven anaerobic oxidation of methane. Organic-P is also observed within biofilm-like organic carbon aggregates, revealing the microbial enrichment of P by fluids in the process of anaerobic oxidation of methane. P with a granulated morphology was identified as detrital-P derived from deep sediments. Most importantly, it is evident that Ca-P is positively correlated to the Fe content in all the seep carbonates. This indicates the likelihood that the dissolved P in cold-seep fluids is released primarily from Fe oxides through Fe-driven anaerobic oxidation of methane in deep sediments. These processes associated with different species of P may have significant implications for P geochemical cycling and anaerobic oxidation of methane impelled by Fe and sulfate reduction in cold seep environments.

Zone of metal-driven anaerobic oxidation of methane is an important sink for phosphorus in the Taixinan Basin, South China Sea

Phosphorus (P) is an important nutrient and has an important impact on global primary productivity. Presently, the dynamics of the P cycle in low sulfate, anoxic settings are largely unknown. In this study, the adsorption–desorption behavior of Fe-bound P, organic-P, loosely-bund P, detrital apatite P, and refractory P was described in the sulfate and methane transition zone (SMTZ) at site 973–4 in the cold-seep area of the Taixinan Basin, South China Sea. Results showed that the Fe-bound P and organic-P were influenced by sulfate-driven anaerobic oxidation of methane (SD-AOM) and metal-driven anaerobic oxidation of methane (MD-AOM), and subsequently, the Fe-bound P and organic-P were released as HPO42− into the pore water. Meanwhile, significant increases were detected in authigenic carbonate fluorapatite (PCFA) and vivianite within the MD-AOM zone, which indicate that this zone is an important P-sink area. The MD-AOM plays an important role in the formation of PCFA and vivianite because MD-AOM provide the necessary HPO42− and Fe2+ for the formation of these minerals. Our findings have major implications for understanding the P cycle in low sulfate, anoxic settings and are important for understanding the influence of MD-AOM on the phosphate cycle.

Dissolved Inorganic Carbon Pump in Methane-Charged Shallow Marine Sediments: State of the Art and New Model Perspectives

Methane transport from subsurface reservoirs to shallow marine sediment is characterized by unique biogeochemical interactions significant for ocean chemistry. Sulfate-Methane Transition Zone (SMTZ) is an important diagenetic front in the sediment column that quantitatively consumes the diffusive methane fluxes from deep methanogenic sources toward shallow marine sediments via sulfate-driven anaerobic oxidation of methane (AOM). Recent global compilation from diffusion-controlled marine settings suggests methane from below and sulfate from above fluxing into the SMTZ at an estimated rate of 3.8 Tmol yr-1 and 5.3 Tmol yr-1 respectively, and wider estimate for methane flux ranges from 1—19 Tmol yr-1. AOM converts the methane carbon to dissolved inorganic carbon (DIC) at the SMTZ. Organoclastic sulfate reduction (OSR) and deep-DIC fluxes from methanogenic zones contribute additional DIC to the shallow sediments. Here, we provide a quantification of 8.7 Tmol yr-1 DIC entering the methane-charged shallow sediments due to AOM, OSR, and the deep-DIC flux (range 6.4–10.2 Tmol yr-1). Of this total DIC pool, an estimated 6.5 Tmol yr-1 flows toward the water column (range: 3.2–9.2 Tmol yr-1), and 1.7 Tmol yr-1 enters the authigenic carbonate phases (range: 0.6–3.6 Tmol yr-1). This summary highlights that carbonate authigenesis in settings dominated by diffusive methane fluxes is a significant component of marine carbon burial, comparable to ~15% of carbonate accumulation on continental shelves and in the abyssal ocean, respectively. Further, the DIC outflux through the SMTZ is comparable to ~20% of global riverine DIC flux to oceans. This DIC outflux will contribute alkalinity or CO2 in different proportions to the water column, depending on the rates of authigenic carbonate precipitation and sulfide oxidation and will significantly impact ocean chemistry and potentially atmospheric CO2. Settings with substantial carbonate precipitation and sulfide oxidation at present are contributing CO2 and thus to ocean acidification. Our synthesis emphasizes the importance of SMTZ as not only a methane sink but also an important diagenetic front for global DIC cycling. We further underscore the need to incorporate a DIC pump in methane-charged shallow marine sediments to models for coastal and geologic carbon cycling.

Triple sulfur isotope relationships during sulfate-driven anaerobic oxidation of methane

Sulfate-driven anaerobic oxidation of methane (SD-AOM) plays a critical role in regulating the global methane budget. Determination of the diagnostic triple isotope exponent θ33 (≡ln33⁡α/ln34⁡α) for SD-AOM can help to identify and quantify microbial sulfate reduction via SD-AOM in the environment. The history of Earth's surface redox conditions can also be examined through the measurement of triple sulfur isotope compositions in sedimentary rocks. Due to difficulties in both culturing anaerobic methanotrophs and sampling pore-water sulfate in SD-AOM-dominated environments, however, the θ33 values for the processes of SD-AOM have not been constrained. We propose that a set of modern cold-seep associated barite samples with low Δδ18O/Δδ34S values bear a record of residual pore-water sulfate during SD-AOM, and therefore the triple sulfur isotope composition of these barites can be used to deduce θ33 values. We applied a 1-D diagenetic reaction–transport model to fit Δ33S and δ′34S results from modern cold seep barites collected from five sites in the Gulf of Mexico. Based on revealed negative correlations (R2=0.77) between Δ33S and δ′34S values we calculated an upper-limit θ33 value of 0.5100 to 0.5112 (±0.0005) given a 1000ln34⁡α value of −30‰ to −10‰. This θ33 value is distinctively lower than that of organoclastic sulfate reduction (OSR) in marine environments where the diagnostic isotope fractionation (1000ln34⁡α) is typically more negative than that of SD-AOM. In addition, cold seep barite data display a negative Δ33S–δ′34S correlation whereas pore-water sulfates of all OSR-dominated settings show a positive one. Therefore, the diagnostic triple-sulfur isotope exponent and associated negative Δ33S–δ′34S correlation may allow for the identification of SD-AOM in sedimentary records.

Multiple sulfur isotopic evidence for the origin of elemental sulfur in an iron-dominated gas hydrate-bearing sedimentary environment

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.

Environmental controls on sulfur isotopic compositions of sulfide minerals in seep carbonates from the South China Sea

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.