Organoclastic Sulfate Reduction Research Articles

Authigenic carbonate and native sulfur formation in Messinian (upper Miocene) marine sediments: Sedimentological, petrographical and geochemical constraints

Carbonate concretions accompanied by elemental sulfur were found in an early Messinian (Late Miocene) marine succession of NW Italy. The rocks were studied with an integrated approach including sedimentological, petrographical, stable isotope (carbon, oxygen, and multiple sulfur isotopes), and lipid biomarker analyses. Unlike other examples from Messinian strata of the Mediterranean area, the studied carbonate and sulfur concretions did not derive from the diagenetic replacement of sulfate minerals. Three lithofacies were distinguished: a) laminated lithofacies representing aphotic carbonate stromatolites enclosing fossils of filamentous sulfide-oxidizing bacteria; b) brecciated lithofacies deriving from the brecciation of carbonate stromatolites by mud injections; c) sulfur-bearing lithofacies deriving from the precipitation of thin laminae of elemental sulfur at or close to the sediment-water interface. The carbon and oxygen stable isotope composition of authigenic carbonate minerals and lipid biomarkers indicate that the initial formation of the laminated lithofacies was favored by organoclastic sulfate reduction in the shallow subsurface close to the sediment-water interface, producing sulfide that sustained dense microbial mats of sulfide-oxidizing bacteria at the seafloor. Calcification of the mats and consequent formation of stromatolites were possibly favored by nitrate-driven sulfide oxidation at the seafloor. The subsequent brecciation of the stromatolites was apparently the consequence of sulfate-driven anaerobic oxidation of methane (SD-AOM) in an underlying sulfate-methane transition zone (SMTZ). Focused fluid flow from below, possibly resulting from destabilization of gas hydrates, was not only responsible for the brecciation of the stromatolites, but also for the delivery of bicarbonate ions and the consequent precipitation of additional, 13C-depleted calcite (δ13C values as low as −52‰). Along with bicarbonate, also hydrogen sulfide was produced by SD-AOM at the SMTZ and was transported upwards. The oxidation of hydrogen sulfide at or close to the seafloor promoted the formation of elemental sulfur characterized by δ34S values and Δ33S values close to coeval seawater sulfate.

Geochemical and mineralogical features as indicators of sulfate-methane transition zones in shallow gas-bearing offshore sediments from Zhoushan

Subsurface shallow gas, primarily composed of biogenic methane (>95%), is highly-enriched in global offshore sediments. The redox conditions of methane-rich pore fluid play a crucial role in shaping the geochemical signatures associated with the anaerobic oxidation of methane (AOM) and vertical displacement of sulfate-methane transition zones (SMTZs) within deep sedimentary records. However, long-period, and continuous records of AOM and SMTZs in shallow gas-bearing offshore sediments are sparse. Here, we employed a comprehensive analyses of iron sulfide, elemental, and stable isotopies on a 63-m drilled sediment core (JC-1) from offshore Zhoushan. Four different layers U1–U4 were identified in 11.5–24 mbsf, 24−42 mbsf, 42−51 mbsf, and 51−63 mbsf, respectively, as revealed by the lithofacies and sedimentary structures. By comparing the pyrite contents, total sulfur to total organic carbon ratios, and δ34S-chromium-reducible sulfur values, the commonly seen organoclastic sulfate reduction occurred in U1 and U2, whereas significant AOM activities were found in U1 and U4. Further, the peaks of total sulfur to total organic carbon ratios, sulfur contents, and multiple positive δ34S-chromium-reducible sulfur values indicated the presence of AOM in SMTZs at 18.3, 52, and 59 mbsf. These intervals were featured by a sub-oxic or anoxic condition with strong methane seepages, evident from the scarcity of metals and the enrichment of Mo/Al and U/Al ratios. The presence of multiple SMTZs was consistent with the pore-water data of the adjacent YS4 and YS7 cores. In light of these findings, it is prudent to exercise caution when utilizing geochemical indicators, such as trace element proxies and the δ34S values of sulfide minerals, to comprehend the progression of fluctuating depositional settings in reaction to sea-level fluctuations and shallow gas reservoirs. This study provides a new perspective to better understand the evolution of unsteady depositional environments in response to sea-level changes and shallow gas reservoirs.

Characterization of the benthic biogeochemical dynamics after flood events in the Rhône River prodelta: a data–model approach

Abstract. At the land–sea interface, the benthic carbon cycle is strongly influenced by the export of terrigenous particulate material across the river–ocean continuum. Episodic flood events delivering massive sedimentary materials can occur, but their short-term impact on carbon cycling is poorly understood. In this paper, we use a coupled data–model approach to estimate the temporal variations in sediment–water fluxes, biogeochemical pathways and their reaction rates during these abrupt phenomena. We studied one episodic depositional event in the vicinity of the Rhône River mouth (NW Mediterranean Sea) during the fall–winter of 2021/22. The distributions of dissolved inorganic carbon (DIC), sulfate (SO42-) and methane (CH4) were measured in sediment porewaters collected every 2 weeks before and after the deposition of a 25 cm sediment layer during the main winter flood event. Significant changes in the distribution of DIC, SO42- and CH4 concentrations were observed in the sediment porewaters. The use of an early diagenetic model (FESDIA) to calculate biogeochemical reaction rates and fluxes revealed that this type of flood event can increase the total organic carbon mineralization rate in the sediment by 75 % a few days after deposition. In this period, sulfate reduction is the main process contributing to the increase in total mineralization relative to non-flood deposition. The model predicts a short-term decrease in the DIC flux out of the sediment from 100 to 55 mmolm-2d-1 after the deposition of the new sediment layer with a longer-term increase by 4 %, therefore implying an initial internal storage of DIC in the newly deposited layer and a slow release over relaxation of the system. Furthermore, examination of the stoichiometric ratios of DIC and SO42- as well as model output over this 5-month window shows a decoupling between the two modes of sulfate reduction following the deposition – organoclastic sulfate reduction (OSR) intensified in the newly deposited layer below the sediment surface, whereas anaerobic oxidation of methane (AOM) intensified at depth below the former buried surface. The bifurcation depth of sulfate reduction pathways, i.e., the sulfate–methane transition zone (SMTZ), is shifted deeper by 25 cm in the sediment column following the flood deposition. Our findings highlight the significance of short-term transient biogeochemical processes at the seafloor and provide new insights into the benthic carbon cycle in the coastal ocean.

Near seafloor methane flux in the world's largest human-induced dead zone is regulated by sediment accumulation rate

The vast oxygen-depleted area of the central Baltic Sea is the largest human-induced dead zone in the world with 70,000 km2 or approximately three times the second largest one in the Gulf of Mexico. Methane occurs in high concentrations in bottom waters (3200 nM) and sediments (30 mM), and its dynamics is better constrained for the water column, but still poorly understood on sediments. Here we show that sediment accumulation rate plays a major role in regulating the quantity of organic matter and its residence time in the sulphate reduction and methanogenesis zones and, therefore, affects methane generation, consumption, and diffusive flux in sediments near the seafloor (< 1 m). High fluxes found in high sediment accumulation rate areas and competition for substrate (organoclastic sulphate reduction vs. anaerobic oxidation of methane with sulphate), compromise the ability of the thin microbial filter to consume and prevent methane diffusion through the seafloor.

Assessing biogeochemical controls on porewater dissolved inorganic carbon cycling in the gas hydrate-bearing sediments of the Makran accretionary wedge, Northeastern Arabian Sea off Pakistan

Quantitatively assessing the porewater dissolved inorganic carbon (DIC) cycling in methane-enriched marine sediments is crucial to understanding the contributions of different carbon sources to the global marine carbon pool. In this study, Makran accretionary wedge was divided into Zone 1 (high methane flux area) and Zone 2 (background area). Porewater geochemical compositions (Cl–, SO42–, NH4+, Mg2+, Ca2+, Ba2+, DIC and δ13C-DIC) and a reaction-transport model were used to determine the DIC source and calculate the DIC flux through carbonate precipitation and releasing into overlying seawater in sediments. Zone 1 is characterized by the shallower depth of sulfate-methane transition (SMT), where most of porewater sulfate was consumed by anaerobic oxidation of methane (AOM). In contrast, a relatively low flux of methane diffusion in Zone 2 results in a deeper SMT depth and shallow sulfate is predominantly consumed by organoclastic sulfate reduction (OSR). Based on the porewater geochemical profiles and δ13C mass balance, the proportions of porewater DIC originating from methane were calculated as 51% in Zone 1 and nearly 0% in Zone 2. An increase of porewater DIC concentration leads to authigenic carbonate precipitation. Solid total inorganic carbon (TIC), X-ray diffractometry (XRD) and scanning electron microscopy (SEM) analysis display that carbonate content increases with depth and aragonite appears at or below the depths of SMT. Meanwhile, the flux of DIC released from sediments calculated by the reaction-transport model is 51.3 ~ 90.4 mmol/m2·yr in Zone 1, which is significantly higher than that in Zone 2 (22.4 mmol/m2·yr). This study demonstrates that AOM serves as the dominant biogeochemical process regulating the porewater DIC cycle, which has an important impact on the authigenic carbonate burial and the seawater carbonate chemistry.

Sulfate distribution and sulfate reduction in global marine sediments

The quantification of anaerobic oxidation of organic matter in the global seabed is to a large extent based on transport-reaction modeling of pore water ions involved in the mineralization processes. As the predominant of these processes, sulfate reduction can be modeled from the depth distribution of sulfate and other relevant solutes. An active organoclastic sulfate reduction is typically characterized by sulfate profiles with a concave-down shape. We use here a comprehensive database to show that half of all competent sulfate profiles have an opposite, concave-up shape, which may appear inconsistent with this concept. We also show that there is a strong discrepancy between sulfate profiles obtained by gravity coring and by IODP coring, with generally much higher sulfate flux and shallower sulfate penetration depth in the gravity cores (the term IODP here covers the international ocean drilling programs, DSDP, ODP and IODP). The discrepancy is correlated with a selectivity for coring sites in the published studies, by which gravity coring is focused towards the ocean margins and continental shelf and towards high surface water productivity and high sedimentation rate. In contrast, IODP coring is more frequently done in low sedimentation regions and is largely absent from the continental shelf. As a result, estimates of sulfate reduction in the global seabed may be biased by a selection of only IODP core data for the modeling. Furthermore, the modeling of pore water profiles shows net rates of sulfate reduction, while 35S-radiotracer experiments show the higher gross rates of the process. Estimates from 35S-radiotracer measurements suggest that dissimilatory sulfate reduction oxidizes 77 Tmol yr−1 of organic carbon globally, which is 3- to 4-fold higher than recent data based on modeling of IODP data. The potential biases by global estimates of sulfate reduction in marine sediments are discussed.

Discerning the sulfur geochemical features of turbidites and methane-rich sediments from the South China sea

Upward diffusion of dissolved methane and associated anaerobic oxidation of methane (AOM) coupled with microbial sulfate reduction (MSR) are widespread in normal hemipelagic sediments of continental margins. The occurrence of authigenic sulfur enrichment in such sediments is usually regarded as an indicator of AOM; however, extensive MSR and authigenic iron sulfide generation also occur in turbidites. Therefore, research attention should be directed toward determining the geochemical features of authigenic sulfur mineralization in methane-rich background sediments and turbidites. Here we report the sedimentology and geochemical composition of sediments from four piston cores (CL30, CL44, CL47, and CL3A) containing turbidite layers from methane-rich areas of the South China Sea. The turbidite layers were deposited at 17–15 kyr BP or earlier during the last glacial period and were located above the present sulfate–methane transition zone (SMTZ). The median grain size, proportion of sand-sized grains, and Si, Ti, K, and Zr contents show marked elevation in the turbidite layers compared with the background sediments, indicating the input of large amounts of terrigenous detrital matter with coarser grains. High total sulfur (TS) contents and low δ34SAIS values (AIS: acid-insoluble sulfur) (−35.2‰ to −26.1‰) are observed within turbidite layers relative to the background hemipelagic sediments in core CL44. These results suggest that intensive sulfidization occurred as a result of enhanced organoclastic sulfate reduction rates in turbidite horizons, which were probably caused by the resultant decrease in downward oxygen flux and waning bioturbation after rapid deposition of turbidites. In comparison, TS contents are higher and δ34SAIS values are positive (0.2‰–46.8‰) within the SMTZ on account of the rapid consumption of sulfate and build-up of isotopically heavier hydrogen sulfide pools via intensive AOM. Moreover, authigenic barium (Ba) enrichments commonly occur in the depth interval immediately above the SMTZ rather than within turbidite layers; therefore, they serve as a useful indicator of the position of the SMTZ. This study presents distinct differences in the geochemical compositions of turbidity deposits and methane-rich background sediments and highlights that a multi-proxy approach including sedimentological and geochemical analyses should be used to constrain the types of MSR in deep-sea sediments, given the common occurrence of turbidites and subsurface methane release in marginal deep-sea areas. It is also suggested that if applied with caution, S–C–Ba geochemical patterns can be used to identify palaeo-SMTZs and palaeo methane-rich zones in turbidite-containing strata.

Dual sources and consumption of methane in shallow sediments of southern SCS: Insight from porewater composition and numerical modeling

Methane seepages have significant impacts on marine environments and ecosystems. Deep understanding of that is critical for the resources exploration and the climate change. Numerous methane seepages have been reported worldwide, and mostly investigated on the slope and margin, with less attention paid to the basin. Here presents the determination of three sediment cores (H59, H79, and H55Y) retrieved in the Beikang Basin in the southern of the South China Sea (SCS), an important hydrocarbons and gas hydrates potential domain.A preliminary evaluation of the methane-related geochemical processes was obtained based on the compositions of porewater, and a reactive transport model was further developed to quantitively investigate the corresponding processes. The model results matched well the measurements. Both porewater compositions and model results indicated that anaerobic oxidation of methane dominantly consumed the sulfate at sites H55Y and H59, while sulfate was mainly consumed by organoclastic sulfate reduction at site H79. The shallow depths of SMI (3.8–7.8 mbsf), benthic methane fluxes (0.5–1.5 mmol m−2 yr−1) and high AOM rates (37–103 mmol m−2 yr−1) indicated the methane seepages at H55Y and H59. Model and sensitivity tests revealed further that the consumed methane was mainly supplied by external source, which ascended from deep reservoir, while in-situ methanogenesis contributed only a negligible fraction. The deduced δ13C of the external methane of H55Y demonstrated it was also microbial origin, which was probably contributed by the biogenic source rocks and/or dissociation of gas hydrates.The comprehensive regional research of the source and consumption of methane determined different seepage scenarios in the basin of southern SCS and enhanced our understanding of methane cycling in the marine basins.

Two modes of gypsum replacement by carbonate and native sulfur in the Lorca Basin, SE Spain

Organoclastic sulfate reduction and bacterial sulfide oxidation have been suggested to explain the formation of authigenic carbonate and native sulfur replacing gypsum in the Lorca Basin, Spain. To gain more insight into the nature of this replacement, two types of sulfur-bearing carbonate (laminated and brecciated) from the late Miocene Lorca Basin were studied. Petrographic observations revealed that a sulfur-bearing laminated carbonate consists of clay-rich and dolomite-rich laminae with carbonate and native sulfur pseudomorphs after gypsum. Positive δ18Ocarbonate values in the laminae (δ18O = 2.6‰) and lipid biomarkers of halophilic archaea (e.g., extended archaeol) suggest formation under hypersaline conditions. Bacterial sulfate reduction, evidenced by biomarkers such as iso-C15, iso-C16, and iso-C17 fatty acids, produced hydrogen sulfide inducing the abiotic formation of organic sulfur compounds. Gypsum in the laminated carbonate likely dissolved due to undersaturation as evidenced by a low content of carbonate-associated sulfate (3,668 ppm) and 34S-enriched native sulfur (δ34S = 22.4‰), reflecting sulfate limitation. Such 34S-enrichment implies limited fluid flow, which probably restricted the supply of molecular oxygen required for native sulfur formation through oxidation of hydrogen sulfide. Alternatively, sulfate-reducing bacteria may have mediated native sulfur formation directly as a stress response to environmental conditions. The formation of sulfur-bearing calcite in brecciated carbonates is due to post-depositional alteration. Negative δ18O values of the calcite (δ18O = −1.5‰) and a tenfold decrease in carbonate-associated sulfate content (752 ppm) suggest gypsum dissolution and subsequent calcite precipitation from meteoric water. Relatively 34S-depleted native sulfur (δ34S = 13.1‰) leaves it ambiguous whether meteoric water influx could have supplied sufficient molecular oxygen for oxidation of hydrogen sulfide. In case of the brecciated carbonate, methanogenesis, anaerobic oxidation of methane, and bacterial sulfate reduction apparently mediated the formation of secondary minerals as indicated by 13C-depleted lipid biomarkers representative for the respective metabolisms. This study reveals that the conditions and timing of gypsum replacement are variable–taking place 1) during or shortly after gypsum deposition or 2) significantly after sedimentation–and suggests that methanogens in addition to anaerobic methanotrophic archaea and sulfate-reducing bacteria may be involved in the mineral-forming processes in the sedimentary subsurface.

Sulfate-driven anaerobic oxidation of methane inferred from trace-element chemistry and nickel isotopes of pyrite

In marine sediments, formation of pyrite (FeS2) is promoted by both organoclastic sulfate reduction (OSR) and sulfate-driven anaerobic oxidation of methane (SD-AOM), and these two microbial pathways might yield differing patterns of sulfur and nickel isotopic fractionation and trace-element enrichment. To better understand these pathways, we analyzed the geochemistry of authigenic pyrite aggregates from the Upper Quaternary of the western Andaman Sea (International Ocean Discovery Program, Expedition 353, Site U1447A). 34S-enriched pyrites (to ∼+41‰) in Unit Ib are interpreted as products of SD-AOM, and their enrichments in Co and Ni and low δ60Ni values (−0.63‰ to −0.09‰) may represent diagnostic signatures of a reverse-methanogenesis microbial pathway. In contrast, 34S-depleted pyrites (∼–46‰ to –38‰) in both Units I and II are consistent with sulfide formation through early diagenetic remineralization of organic matter, and their relative enrichments in Cu and V and heavier δ60Ni values (to +0.41‰) may be diagnostic of this alternative microbial pathway. This study reports for the first time a fractionation of Ni isotopes linked to preferential uptake of isotopically light Ni by the enzyme Mcr (M reductase enzyme) in reverse methanogenesis and demonstrates that OSR- and SD-AOM-associated pyrites are potentially distinguishable on the basis of their δ60Ni compositions. Such geochemical signatures may prove useful in determining processes of pyrite formation in paleo-depositional systems and in identifying ancient methane emission events.

The effects of organic matter and anaerobic oxidation of methane on the microbial sulfate reduction in cold seeps

Cold seep sediments are dominated by intensive microbial sulfate reduction coupled to anaerobic oxidation of methane. However, the contribution proportion between this process and the role of organic matter has remained enigmatic. Here, pore water data combined with PROFILE model, fluxes of sulfate and methane concentration calculated from Fick's first law, and δ34SSO4 and δ18OSO4 of pore water sulfate were studied to reconstruct co-occurring microbial organoclastic sulfate reduction and anaerobic oxidation of methane coupled with sulfate reduction in methane seep sediments collected from South China Sea. The sulfate concentration profiles of C9 and C14 in Qiongdongnan Basin generally show quasilinear depletion with depth. Reaction-transport modeling provided close fits to concentration data. δ18OSO4 and δ34SSO4 increase fastest with sediment depth above 400 cmbsf and slowest below that depth. The values of methane flux are always lower than those of total sulfate reduction of sulfate diffusive flux at GC-10, GC-9, GC-11 and HD319 sites in Taixinan Basin. Besides, positions of sulfate methane transition zone in all study sites are approximately ~400 to 800 centimeters below seafloor. These results showed that microbial sulfate reduction in sediments is mainly controlled by intense anaerobic oxidation of methane, but there is a certain relationship with organic matter metabolism process. This emphasizes that traditional redox order of bacterial respiration is highly simplified, where, in sediments such as these seeps, all of these microbial sulfate reduction processes can occur together with complex couplings between them.

Diagenetic Geochemistry of Iron, Sulfur, and Molybdenum in Sediments of the Middle Okinawa Trough Impacted by Hydrothermal Plumes and/or Cold Seeps

AbstractIron (Fe), sulfur (S), and molybdenum (Mo) geochemistry in marine sediments impacted by hydrothermal plumes and/or cold seeps is complex and has not been systematically documented. Here we characterize Fe, S, and Mo diagenesis in sediments between the Minami‐Ensei Knoll hydrothermal field and a cold‐seep site of the middle Okinawa Trough. Results show that distances away from the hydrothermal field and the steep trough slope may significantly affect the transport of hydrothermal Fe. The transformation of hydrothermal reactive Fe to poorly reactive or unreactive Fe‐bearing phyllosilicates decreased the relative fractions of highly reactive Fe (FeHR) in total Fe (FeHR/FeT). Despite this, the standing stocks of Fe oxides in the methane‐free sediments have not been dampened, indicating no net impacts of hydrothermal Fe inputs on the size of Fe oxides. In the methane‐free sediments, low ratios of total reduced inorganic sulfide (TRIS) to total organic carbon (TOC) (TRIS/TOC), highly 34S‐depleted pyrite, and low Mo contents suggest that organoclastic sulfate reduction is at low rates and plays a limited role in carbon cycle. In the cold‐seep sediments, however, intense sulfate reduction coupled to anaerobic methane oxidation significantly elevate TRIS/TOC ratios, Mo enrichment, and isotope compositions of Mo and pyrite‐S. This pathway is expected to be important in carbon cycle in the basin due to the wide occurrence of cold seeps. Our results highlight the important controls of the local extreme depositional/diagenetic conditions on sedimentary S and Mo records, with implications for the reconstruction of paleoredox states of the past earth's surface.

The crucial role of deep-sourced methane in maintaining the subseafloor sulfate budget

Methane (CH4) is a powerful greenhouse gas and its largest reservoir on Earth is held in marine sediments. CH4 in marine sediments is mainly stored in gas-hydrate reservoirs and deep sedimentary strata along continental margins, where large amounts of deep-sourced CH4 ascend to different degrees toward the seafloor. However, the amount of deep-sourced CH4 and its role in subseafloor carbon and sulfur cycling remains poorly constrained. We analyzed sulfate (SO42−) profiles of 157 sites along with previous published 85 sites to determine the regional distribution and amount of SO42− reduction for an area of 1.23 × 105 km2 of the northern South China Sea. Then we compared these obtained results with estimates based on sedimentation rates from the same area. Significantly higher regional SO42− flux estimates based on SO42− profiles (4.26 × 10−3 Tmol a−1), compared to lower estimates based on sedimentation rates (1.23 × 10−3 Tmol a−1), reflect abundant ascending deep-sourced CH4. The difference of the regional SO42− flux estimates (3.03 × 10−3 Tmol a−1) represents the amount of SO42− reduced by CH4 through the anaerobic oxidation of CH4 (AOM). Deep-sourced CH4 contributes 71% to total SO42− consumption in the study area, largely exceeding SO42− consumption by organoclastic sulfate reduction. Our findings substantiate that deep-sourced CH4 governs subseafloor carbon and sulfur cycling to a previously underrated extent, fueling extensive chemosynthesis-based ecosystems along continental slope and rise.

Porewater geochemistry indicates methane seepage in the Okinawa Trough and its implications for the carbon cycle of the subtropical West Pacific

The Kuroshio Current, originating from the West Pacific Warm Pool and flowing through the Okinawa Trough, connects the equator and the subtropical West Pacific and plays an important role in the carbon cycle in the West Pacific Ocean. Previous studies have focused on the effects of surface export productivity and bottom redox conditions on the carbon cycle in the late Quaternary. Recent studies have demonstrated that methane seepages are very common in the Okinawa Trough, however, their significance for the carbon cycle remains not well understood. Here, methane seepages and sulfate-driven anaerobic oxidation of methane (SD-AOM) are constrained by the geochemical characteristics of porewater at site CSHC-4 (Length: 1555 cm) derived from the water depth of 934 m on the western continental slope of the Okinawa Trough. Using the △(DIC+ Ca2++ Mg2+)/△SO42− ratio, it is suggested that the sulfate reduction in the upper part of site CSHC-4 is dominated by organoclastic sulfate reduction (OSR), while that between 655 and 1055 cm is gradually dominated by SD-AOM with deepening depth. However, with the depletion of sulfate, the methanogenesis process predominates at the bottom of site CSHC-4. The depth of the sulfate-methane interface (SMI) and the methane diffusive flux of site CSHC-4 is calculated to be ∼1156 cm and ∼ 63 mmol m−2 yr−1, respectively. Near the SMI, the changes in concentrations of Ca2+, Mg2+, Sr2+ and ratios of Mg/Ca and Sr/Ca in the porewater indicate the possibility of the precipitation of authigenic high-Mg calcite in the sediments. In contrast, the increase in the concentration of Ba2+ in porewater below the SMI may imply the dissolution of barite (BaSO4). In addition, redox-sensitive elements in porewater exhibit various geochemical behaviours due to changes in redox conditions caused by SD-AOM. The above SD-AOM processes will affect the reconstruction of surface productivity and redox conditions of bottom water in the Okinawa Trough since the late Quaternary based on biogenic elements (e.g., Ca and Ba) and redox-sensitive elements (e.g., U and Cr), which requires careful evaluation. Therefore, our new findings illustrate the modern methane seepage in the Okinawa Trough and provide a reference for calculating the ancient carbon cycle in the subtropical West Pacific.

Multiple sulfur isotope systematics of pyrite for tracing sulfate-driven anaerobic oxidation of methane

Sulfate-driven anaerobic oxidation of methane (SD-AOM) is ubiquitous in marine sedimentary environments, governing the global methane budget and the redox evolution of Earth's surface. Tracing SD-AOM and organoclastic sulfate reduction (OSR) from the pyrite archive is key to the reconstruction of SD-AOM activity and paleoenvironmental interpretation. However, discriminating the origins of pyrite – basically SD-AOM and OSR – is commonly challenging due to frequent overlap of δ34Spy values. Multiple sulfur isotopes of pyrite are expected to be an effective tool to distinguish between OSR and SD-AOM, yet variable uncertainties and unknowns remain. Here we investigated the δ34S and Δ33S values of pore-water sulfate and authigenic pyrite from a piston core taken on the continental slope of the South China Sea. A positive Δ33S - δ34S correlation of pore-water sulfate is observed in the upper OSR-dominated zone, resulting in Δ33S and δ34S values of sulfate diffusing into the sulfate-methane transition zone (SMTZ) >0.1‰ and >30‰ larger than the corresponding values of seawater sulfate. A negative Δ33S - δ34S trajectory of pore-water sulfate and pyrite is observed for the SMTZ, agreeing with low sulfur isotope fractionation characteristic for SD-AOM and a diagnostic large Δ33S - δ34S field of SD-AOM-derived pyrite. These findings elucidate that the multiple sulfur isotope systematics of pyrite in methane-bearing sediment depends on (1) mass transport effects of dissolved sulfate and sulfide, (2) the relative contribution of OSR and SD-AOM to the pore-water sulfide and pyrite pools, and (3) the sulfur isotope fractionation during microbial sulfate reduction. Our study highlights the importance of mass transport dynamics on the isotopic composition of pyrite, a factor that needs to be considered in any attempt to reconstruct the origin of early diagenetic pyrite and the paleoenvironmental setting with multiple sulfur isotopes.

Organoclastic sulfate reduction in deep-buried sediments: Evidence from authigenic carbonates of the Gulf of Mexico

The fate of organic matter in deep-buried marine sediments determines the formation of hydrocarbon reservoirs, shapes the deep biosphere, and affects the global carbon cycle. Several geochemical processes such as silicate weathering, iron and manganese (hydr)oxide reduction, and sulfate reduction influence the remineralization of organic matter in buried sediments. However, little information on deep-seated organoclastic sulfate reduction is available and the involved geochemical processes are largely unknown. Here, authigenic carbonates recovered from Ship Shoal Block 296 (SS296) of the Gulf of Mexico, all dominated by low-magnesium calcite, were investigated to constrain organoclastic sulfate reduction in deep-buried sediments. The SS296 carbonates had been previously suggested to be of a deep origin and transported upward by salt diapirism. The presence of cone-in-cone textures in samples 3110R1 and 3110R2 as well as vitrinite reflectance values of 0.48% to 0.58% indicate carbonate formation at a relatively deep burial. Likewise, clumped isotope thermometry yielded formation temperatures from 45 °C to 53 °C for sample 3110R1, 60 °C for sample 3110R2, and 11 °C to 37 °C for sample 3110R3. In spite of formation at greater depth, the temperatures of samples 3110R1 and 3110R2 are still within the temperature range of microbial sulfate reduction, reflecting formation depths between 1 km and 2.7 km. The presence of framboidal pyrite and its relatively low δ34S values (−27.8‰ to +11.5‰) agree with the occurrence of microbial sulfate reduction during carbonate precipitation. The carbon isotopic composition of the carbonates (δ13C: −16.6‰ to −8.9‰) and enclosed organic matter (δ13Corg: −26.8‰ to −20.5‰) suggests that organic matter is the dominant carbon source of carbonate minerals. This study confirms that microbial sulfate reduction occurs in deep-buried sediments, driving the degradation of organic matter. Our findings suggest that organoclastic sulfate reduction might be common in deep-seated sedimentary environments, controlling the fate of organic matter in deep subsurface environments and affecting the global carbon cycle.

Quantitative assessment of dissolved inorganic carbon cycling in marine sediments from gas hydrate-bearing areas in the South China Sea

Quantitatively assessing dissolved inorganic carbon (DIC) cycling in methane-rich marine sediments is essential for understanding the contributions of different carbon sources to the global carbon cycle. Here, the data of δ13C-DIC, SO42−, DIC, Ca2+, Mg2+, PO43−, and a reactive transport model were used to analyze the DIC and methane source and calculate the DIC budget in the shallow sediments at two methane seep sites in the Xisha Trough (CL27A) and to the west of the Haima cold seeps in the Qiongdongnan Basin (CL44). Model results show that methane contributed to 92.75% and 79.95% of DIC sources through anaerobic oxidation of methane (AOM) versus only 7.25% and 12.90% by organic matter via organoclastic sulfate reduction (OSR) and methanogenesis at both sites. However, the methane sources vary between the two sites. External thermogenic methane that is decoupled from contemporaneous organic matter deposition drives the AOM at CL27A. A combination of upwardly diffusing external biogenic methane and internal methane derived from in situ methanogenesis drives the AOM at CL44. Internal methane flux from depth reveals the deep methanogenic zone influences the DIC cycling in the shallow sediments at CL44. It is accompanied by the upward diffusive DIC flux that can be identified by the δ13C-DIC data when modeling, which contributes to the remaining 7.15% of the DIC source. Neglecting this DIC source that is set as a fixed value at the lower boundary will misunderstand the DIC cycling in the shallow sediments. This study identified and highlighted the influence of external thermogenic methane and the methanogenic zone on the DIC cycling in marine sediments, and demonstrated assessing DIC cycling accurately in methane-rich marine sediments is important to estimate its contribution to oceanic carbon cycling.

Methane seep in the Shenhu area of the South China sea using geochemical and mineralogical features

Extensive studies on methane seeps have facilitated the exploration of potential gas hydrates and have revealed biogeochemical processes on the seafloor. In this study, a short core, GG00, was collected from the Shenhu area, South China Sea. By combining various geochemical and mineralogical methods—including planktonic foraminiferal AMS14C dating, as well as their carbon and oxygen isotopes, chromium-reducible sulfur (CRS) content and δ34S values, and hand-picked pyrite and other minerals, we identified a methane seeps that has been stable since the end of the Last Glacial Period. Extremely negative values of δ34S for CRS (as low as −49.7‰) indicated that only organoclastic sulfate reduction and its coupled sulfur intermediate disproportionation were present in the shallow sediments (from 0 to 209 cmbsf). Conversely, the increasing TS and Mo content and the progressively more positive δ34S values (up to −34.76‰) of the CRS indicated enhanced sulfate reduction coupled with the anaerobic oxidation of methane (SR-AOM) in deeper sediments (between 209 and 370 cmbsf). In addition, a large number of hypautomorphic-euhedral elemental sulfur (ES) microcrystals was found at 237 cmbsf using scanning electron microscopy, and energy-dispersive X-ray spectroscopy identified the upper edge of the sulfate–methane transition zone (SMTZ), which was close to the position that was determined from other data (e.g., major and trace elements as well as CRS and its δ34S value). The construction of a stratigraphic framework based on planktonic foraminiferal AMS14C dating and carbon and oxygen isotopes, combined with the large number of framboid pyrites consisting of cubic microcrystals found further below the SMTZ, suggests that this SMTZ has been relatively stable since the end of the Last Glacial Period. In addition, discrepancies in the aggregation morphology of cubic pyrite at different intervals are indicative of variations in Fe and S supply and growth space. Therefore, this study demonstrates the significance of detailed geochemical and mineralogical signatures in revealing the correlation between methane seep and climate.

Effects of sulfate reduction processes on the trace element geochemistry of sedimentary pyrite in modern seep environments

Although it has been suggested that the trace element patterns of sedimentary pyrite can be affected by early diagenesis, detailed studies on modern marine environments addressing this hypothesis are scarce. Organoclastic sulfate reduction (OSR) and sulfate-driven anaerobic oxidation of methane (SD-AOM) are the dominant sulfate reduction processes in organic-rich and methane-rich marine sediments, and commonly result in the formation of authigenic pyrite. To better understand how OSR and SD-AOM affect the trace element geochemistry of pyrite, we applied laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) to analyze trace element contents of pyrite from two methane-seep sites (DH-CL11 and HS148) of the South China Sea. The trace element data are complemented by the measurement of iron isotope compositions of authigenic pyrite. This new data set, supplemented by published sulfur isotope data, improves our understanding of the diagenetic processes during early diagenetic pyrite formation. High δ56Fe and δ34S values of pyrite reflect the dominance of SD-AOM within sulfate-methane transition zones (SMTZs) at both sites (i.e., from 705 to 767 cm below seafloor at site DH-CL11 and from 490 to 690 cm below seafloor at site HS148), whereas pyrite from shallow depth characterized by low δ56Fe values points to early OSR processes. Within the SMTZs, pyrite exhibits highly variable but overall high manganese (Mn) contents (12 to 732 mg/kg at site DH-CL11; 12 to 1145 mg/kg at site HS148), compared to OSR-derived pyrite from shallow depth. Similar to this pattern, pyrite formed at the SMTZ shows higher lead (Pb), zinc (Zn), copper (Cu), and vanadium (V) contents than pyrite formed at shallower depths above the SMTZ. Enrichments of these metals in pyrite forming at the SMTZ are best explained by enhanced reductive dissolution of iron and manganese (oxyhydr)oxides under sulfidic conditions induced by SD-AOM, and subsequent trace element incorporation into pyrite. Arsenic (As), molybdenum (Mo), and antimony (Sb) distributions in pyrite vary between the two study sites. Pyrite from shallow depth of site HS148 has high contents of all three elements, indicating effective immobilization of dissolved As, Mo, and Sb during pronounced OSR. In contrast, apparently less intense OSR at shallow depth of site DH-CL11 allowed for more dissolved As, Mo, and Sb to diffuse downward to greater depth, resulting in the enrichments of these elements in pyrite formed at or close to the SMTZ. Positive correlations between As and cobalt (Co), and between As and nickel (Ni) typify pyrite derived from both OSR and SD-AOM for both study sites, and As-rich pyrite from site DH-CL11 is characterized by a distinctly high Co/Ni ratio. Both patterns suggest that the presence of As affects the uptake of Co and Ni into pyrite. Our study documents that pyrite element contents in methane-rich environments are significantly influenced by different sulfate reduction processes during early diagenesis, allowing the differentiation of OSR-derived pyrite from SD-AOM-derived pyrite by means of trace element geochemistry.

Sulfur and Oxygen Isotope Records of Sulfate-Driven Anaerobic Oxidation of Methane in Diffusion-Dominated Marine Sediments

Organoclastic sulfate reduction (OSR) and sulfate-driven anaerobic oxidation of methane (SD-AOM) are the two major microbial pathways for sulfate consumption in marine sulfur cycle. The relative changes of sulfur and oxygen isotope ratios in pore water sulfate are affected by the mode of microbial sulfate reduction and have been applied as an indicator for assessing methane excess environments. However, so far, this isotope proxy fails to distinguish sulfate reduction processes fueled by the oxidation of organic matter or by diffusing methane. To better understand the mechanism of sulfur and oxygen isotope partitioning during OSR and SD-AOM, coupled sulfur and oxygen isotopic compositions of pore water sulfate (δ34SSO4 and δ18OSO4) were investigated from four methane diffusing sites (CL56, CL57, CL59, and CL60) of the South China Sea, supplemented by carbon isotopic composition of dissolved inorganic carbon (DIC) and sulfur isotopic composition of pyrite in bulk sediments. Pore water sulfate and DIC concentrations, as well as calculated net sulfate reduction rates suggest that the sulfate reduction at site CL57 was mainly dominated by OSR, whereas sites CL56, CL59, and CL60 were likely impacted by both OSR and SD-AOM. Furthermore, the trend of cross-plotting δ18OSO4 versus δ34SSO4 values from site CL57 was distinguishable from sites CL56, CL59, and CL60, although all study sites show similar patterns to those derived from methane limited environments. This further indicates the trajectory of sulfur and oxygen isotope partitioning was affected by the mode of sulfate reduction (i.e., OSR vs. SD-AOM). At site CL57, the low net sulfate reduction rate would lead to enhanced oxidation of intermediate sulfur species during OSR, thus leading to a higher slope in the δ18OSO4 vs. δ34SSO4 cross-plot (1.26). In contrast, the higher net sulfate reduction rates at sites CL56, CL59, and CL60 due to the impact from SD-AOM would lead to lower slopes in the δ18OSO4 vs. δ34SSO4 cross-plots (0.78 ± 0.11). This study provides new insights into the sulfur and oxygen isotope systematics during microbial sulfate reduction processes in methane diffusing environments.