Sulfate-methane Transition Zone Research Articles

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.

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.

Potential coupling of microbial methane, nitrogen, and sulphur cycling in the Okinawa Trough cold seep sediments.

The Okinawa Trough (OT) is a back-arc basin with a wide distribution of active cold seep systems. However, our understanding of the metabolic function of microbial communities in the cold seep sediments of the OT remains limited. In this study, we investigated the vertical profiles of functional genes involved in methane, nitrogen, and sulphur cycling in the cold seep sediments of the OT. Furthermore, we explored the possible coupling mechanisms between these biogeochemical cycles. The study revealed that the majority of genes associated with the nitrogen and sulphur cycles were most abundant in the surface sediment layers. However, only the key genes responsible for sulphur disproportionation (sor), nitrogen fixation (nifDKH), and methane metabolism (mcrABG) were more prevalent within sulfate-methane transition zone (SMTZ). Significant positive correlations (P < 0.05) were observed between functional genes involved in sulphur oxidation, thiosulphate disproportionation with denitrification, and dissimilatory nitrate reduction to ammonium (DNRA), as well as between AOM/methanogenesis and nitrogen fixation, and between sulphur disproportionation and AOM. A genome of Filomicrobium (class Alphaproteobacteria) has demonstrated potential in chemoautotrophic activities, particularly in coupling DNRA and denitrification with sulphur oxidation. Additionally, the characterized sulfate reducers such as Syntrophobacterales have been found to be capable of utilizing nitrate as an electron acceptor. The predominant methanogenic/methanotrophic groups in the OT sediments were identified as H2-dependent methylotrophic methanogens (Methanomassiliicoccales and Methanofastidiosales) and ANME-1a. This study offered a thorough understanding of microbial ecosystems in the OT cold seep sediments, emphasizing their contribution to nutrient cycling.IMPORTANCEThe Okinawa Trough (OT) is a back-arc basin formed by extension within the continental lithosphere behind the Ryukyu Trench arc system. Cold seeps are widespread in the OT. While some studies have explored microbial communities in OT cold seep sediments, their metabolic potential remains largely unknown. In this study, we used metagenomic analysis to enhance comprehension of the microbial community's role in nutrient cycling and proposed hypotheses on the coupling process and mechanisms involved in biogeochemical cycles. It was revealed that multiple metabolic pathways can be performed by a single organism or microbes that interact with each other to carry out various biogeochemical cycling. This data set provided a genomic road map on microbial nutrient cycling in OT sediment microbial communities.

Formation of non-evaporitic gypsum in gas hydrate-bearing sediments at Håkon Mosby mud volcano, SW Barents sea

Authigenic minerals such as carbonate and iron sulfide are known features at cold seeps worldwide and form as a result of the anaerobic oxidation of methane in the sulfate-methane transition zone (SMTZ). Recent findings of seep-related non-evaporitic gypsum raise questions regarding its distribution, formation mechanisms, and relationships with the other proxies for confident paleo-seep reconstructions. Here, we report new findings of gypsum in the seep-impacted sediments of the hydrate-bearing Håkon Mosby mud volcano, SW Barents Sea. We combined sediment core logging (XRF, X-Ray) with optical microscopy and scanning electron microscopy - electron dispersive energy to characterize the authigenic mineral fraction of the sediment. Three paleo-SMTZs marked by the co-occurrence of pyrite and gypsum accumulations were found at 7–10 cm, 13–18 cm and 19–21 cm, above the modern one (at ∼50 cm) and match with carbonate-poor and foraminifera-free sediment intervals. Our results indicate that gypsum formation required a descending SMTZ (decreasing methane flux), triggering the oxidation of previously-formed pyrite which supplied extra SO42− to the pore water. Acidic conditions caused by pyrite oxidation would have promoted the dissolution of carbonate particles, thus releasing Ca2+ that is available for gypsum formation. As seen in other studies, the presence of shallow gas hydrates seems to play an important role as a calcium source for gypsum precipitation, via ion exclusion during hydrate formation. HMMV represents an optimal natural laboratory to investigate the interplay between different processes in gypsum biogeochemistry and its potential use as a proxy for methane seeps in modern and ancient settings.

Biological and paleoceanographic controls on the postglacial sulfur isotope records in Arctic shelf sediments

The Arctic Ocean has experienced environmental fluctuations during the Pleistocene glacial-interglacial cycles. Since the last deglaciation, the reinundation of the Bering Strait and regional transgression have led to dramatic changes in the western Arctic Ocean, affecting coastal landscapes, depositional processes, marine ecosystem, and, inherently, biogeochemical element cycles. Here, we investigate the records of sulfur, carbon, and iron cycles in the Chukchi Sea of the western Arctic, with a primary focus on microbial sulfate reduction and subsequent pyrite formation. Variations in the pyrite abundance and sulfur isotopic composition, derived from a 10-m sediment core, demonstrate that dynamic changes in the factors governing pyrite formation – organic electron donor, reactive iron, and sulfate – are closely linked to the regional environmental conditions. In the early Holocene sediment, pyrite precipitation was impeded by the lack of organic matter, even in the presence of abundant sulfate and reactive iron. In the overlying sediment, pyrite contents increased due to vigorous microbial sulfate reduction fueled by enhanced availability of organic substrate and additional methane from the sulfate-methane transition zone. In general, the increased supply of organic matter to the Chukchi Shelf sediments can be attributed to the resumed inflow of nutrient-rich Pacific Water through the flooded Bering Strait. The increase in pyrite content, however, does not correlate exactly with either the increase in TOC or the opening of the Bering Strait, both of which precede the increased pyrite formation. These lags reflect the balance between marine primary production and terrestrial carbon sources, as well as the balance between the Pacific Inflow and the Beaufort Gyre. While a comparable increase in pyrite and TOC contents during the Holocene deglaciation has also been reported in the Black and Baltic Sea sediments, their distinct sulfur isotope records, contingent upon the availability of sulfate and reactive iron, highlight that pyrite can serve as a valuable proxy for tracking past climate and environmental change, especially in barren sedimentary records such as those found in the Arctic Ocean.

The relationships between vertical variations of shallow gas and pore water geochemical characteristics in boreholes from the inner shelf of the East China Sea

Shallow gas was widely recognized in the coastal region, especially in the estuarine delta areas with high organic matter (OM) burial flux. In this study, the vertical variations of shallow gas and the related geochemical indicators from two boreholes in the coastal region of the East China Sea (ECS) were investigated. Two gas-bearing layers were identified in the sediments from the Holocene and late Pleistocene series. Both boreholes exhibit a “typical” and an “inverse” Sulfate Methane Transition Zone (SMTZ). The “typical” SMTZs (SMTZ1 and SMTZ3) were in the upper part of the gas-bearing layers, where sulfate levels decrease and methane levels increase with depth. Conversely, the “inverse” SMTZs (SMTZ2 and SMTZ4) were in the lower part of the gas-bearing layers, exhibiting an increase in sulfate levels and a decrease in methane levels with depth, a phenomenon rarely documented in previous research. The downward variations of pore water geochemical characteristics indicates that these ions were related to Anaerobic Oxidation of Methane (AOM) processes. The increase in Ca2+ and Ba2+ concentrations and the gradual decrease in sulfate at the SMTZ reflect a series of biogeochemical processes resulting from the dissolution of carbonate and other minerals by AOM. The research indicates that sulfate in AOM may originate from multiple sources. Through analyzing the vertical distribution of shallow gas and the geochemical properties of pore water, this study elucidates the shallow gas formation mechanism and the features of the SMTZ, laying the groundwork for further investigations.

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.

Origin and geological significance of the first discovered seafloor oil seepage in the Beikang Basin, southern South China Sea

Seafloor oil seepage, resulting from fluids migration from depth, provides valuable insights into the characteristics of potential source rocks and hydrocarbons. For the first time, seafloor seepage oils were obtained by piston coring in the Beikang Basin, southern South China Sea (SSCS). Based on integrated analysis of the seismic data, core sediments, porewater, headspace gas and heat flow, the geochemical characteristics of seafloor seepage oils and their geological implications were elucidated. Results indicate that deep-sourced hydrocarbons intruded into subsurface sediments via paleo-uplift-related faults, fluid seepage pipes and mixed with in-situ modern marine sediments. Biomarkers suggest the presence of both marine and terrestrial organic matter, as well as a diverse range of thermal maturity levels from immature to mature. The seafloor seepage oil was most likely originated from coal-related source rocks in the Oligocene-Lower Miocene. Deep hydrocarbons were expelled through fractures induced by hydrocarbon-generating overpressure, as well as source rock-connecting faults and finally accumulated atop the paleo-uplift beneath the T3 unconformity. The gradually increased fluid pressure ultimately leads to the fracturing of overlying caprocks, resulting in the formation of fluid seepage pipe and the occurrence of oil seepage on the seafloor. Seafloor oil seepage and the accompanied high methane flux caused biogeochemical process, elements cycling and shoaled the depth of sulfate-methane transition zone (SMTZ), which provides valuable information in indicating gas hydrates occurrence. This study offers significant geological and geochemical information to reveal potential origin of source rocks and hydrocarbons, particularly in the case of limited drilling wells in the SSCS. In addition, this study also advances the understanding of gas-bearing fluids activity and the coupling relationship between deep and shallow strata under a focused fluid seepage background.

The influence of cold seepage on the grain size and geochemistry of sediments from the Laptev Sea shelf

The East Siberian Arctic shelf is renowned for its active methane-rich fluid seeps, confirmed by numerous gas flares in the water column and direct observations of methane release from the seafloor. These cold-seep sites serve as natural laboratories for studying the impact of methane seepage on early diagenesis, authigenic mineral formation, and the geochemical cycles of carbon, sulfur, and other elements. This study examines the grain size and chemical composition of two sediment types from the Laptev Sea shelf: cold-seep sediments influenced by sulfate-driven anaerobic methane oxidation, and unaffected “seep-free” sediments (i.e., control site). High methane concentrations (up to 649 μM/L) in the surface layer of sediments indicate that the sulfate–methane transition zone is found close to the sediment–water interface approximately 5–6 cm below the seabed. At the cold-seep site, thin layers containing up to 40% sand fraction were discovered among the fine-grained sediments. We infer that upward-migrating fluids may contribute to the remobilization of the fine fraction, resulting in concentration of coarse particles. Cold-seep sediments are characterized by molybdenum (Mo) enrichment compared to the lithological background, although one “seep-free” core exhibits evidence of authigenic Mo deposition. The Mo concentration (up to 16.8 ppm) indicates that enrichment occurs under sulfidic conditions restricted to pore water, which are caused by anaerobic methane oxidation. The high Mo concentration in one “seep-free” core likely implies past cold-seep activity. A general Mo–U covariation indicates that the molybdenum enrichment in cold-seep sediments from the Laptev Sea outer shelf is controlled by a weak particulate shuttle process.

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.

Anabolic and Catabolic Microbial Activity in Hydrocarbon-rich Sediments of Guaymas Basin

Guaymas Basin, located in the Gulf of California, Mexico, is a young marginal ocean basin with high sedimentation rates of &amp;gt;1 mm/year, active seafloor spreading, and steep geothermal gradients in its sediment. It hosts a unique microbial subseafloor biosphere as these conditions lead to thermal cracking of sedimentary organic matter and the production of bioavailable organic carbon compounds and hydrocarbons already at shallow depths. The abundance and diversity of potential microbial substrates raise the question of which substrates are being used for catabolic and anabolic microbial metabolism. We thus analyzed the microbial uptake of hydrocarbons and inorganic nitrogen using nanoscale secondary ion mass spectrometry (NanoSIMS) analysis after incubation with stable-isotope labeled substrates. Incubations were carried out with samples from two International Ocean Discovery Program (IODP) Exp. 385 drill sites. Site U1545 is characterized by undisturbed sedimentary strata and a temperature gradient of 225°C/km, whereas Site U1546 has experienced a sill intrusion at greater depth, below the cored interval. The intrusion led to temporary heating of the sediment, but a temperature gradient of 221°C/km indicates thermal equilibration with the surrounding sediment since sill emplacement. Incubations were carried out with 13C-benzene + 2H-hexadecane + 15NH4Cl or 13C-methane + 15NH4Cl at in-situ temperature (4-62°C) and pressure (25 MPa) for 42 days. Additionally, sulfate reduction rates (SRR) were measured by incubating the samples with four aliphatic hydrocarbons + four aromatic hydrocarbons or methane and radioisotope-labeled 35SO42- for 10 days, also at in-situ temperature and pressure. The NanoSIMS analyses reveal that a few samples showed detectable microbial assimilation of hydrocarbons. Nitrogen was significantly assimilated in some samples incubated with methane. The assimilation mostly occurred in samples from near the seafloor (2 and 44 meter below seafloor (mbsf)). Our results indicate that anaerobic microorganisms in Guaymas Basin take up measurable amounts of hydrocarbons and inorganic nitrogen even in the relatively short incubation time of 42 days. The results of the SRR measurements indicate that a mixture of hydrocarbons and methane increases the SRR in samples from near the seafloor (2 mbsf) and around the sulfate-methane transition zone (44 and 55 mbsf) but not in samples from greater depths. Our results show that anaerobic microorganisms in Guaymas Basin can use hydrocarbons for anabolic and catabolic metabolism in this extreme environment. Given the high abundance of various carbon compounds, nitrogen appears to be a limiting factor for cellular growth.

Anaerobic methanotrophy is stimulated by graphene oxide in a brackish urban canal sediment.

Anthropogenic activities are influencing aquatic environments through increased chemical pollution and thus are greatly affecting the biogeochemical cycling of elements. This has increased greenhouse gas emissions, particularly methane, from lakes, wetlands, and canals. Most of the methane produced in anoxic sediments is converted into carbon dioxide by methanotrophs before it reaches the atmosphere. Anaerobic oxidation of methane requires an electron acceptor such as sulphate, nitrate, or metal oxides. Here, we explore the anaerobic methanotrophy in sediments of three urban canals in Amsterdam, covering a gradient from freshwater to brackish conditions. Biogeochemical analysis showed the presence of a shallow sulphate-methane transition zone in sediments of the most brackish canal, suggesting that sulphate could be a relevant electron acceptor for anaerobic methanotrophy in this setting. However, sediment incubations amended with sulphate or iron oxides (ferrihydrite) did not lead to detectable rates of methanotrophy. Despite the presence of known nitrate-dependent anaerobic methanotrophs (Methanoperedenaceae), no nitrate-driven methanotrophy was observed in any of the investigated sediments either. Interestingly, graphene oxide stimulated anaerobic methanotrophy in incubations of brackish canal sediment, possibly catalysed by anaerobic methanotrophs of the ANME-2a/b clade. We propose that natural organic matter serving as electron acceptor drives anaerobic methanotrophy in brackish sediments.

Influence of sedimentary deposition on the microbial assembly process in Arctic Holocene marine sediments.

The sea-level rise during the Holocene (11-0 ky BP) and its resulting sedimentation and biogeochemical processes may control microbial life in Arctic sediments. To gain further insight into this interaction, we investigated a sediment core (up to 10.7 m below the seafloor) from the Chuckchi Shelf of the western Arctic Ocean using metabarcoding-based sequencing and qPCR to characterize archaeal and bacterial 16S rRNA gene composition and abundance, respectively. We found that Arctic Holocene sediments harbor local microbial communities, reflecting geochemical and paleoclimate separations. The composition of bacterial communities was more diverse than that of archaeal communities, and specifically distinct at the boundary layer of the sulfate-methane transition zone. Enriched cyanobacterial sequences in the Arctic middle Holocene (8-7 ky BP) methanogenic sediments remarkably suggest past cyanobacterial blooms. Bacterial communities were phylogenetically influenced by interactions between dispersal limitation and environmental selection governing community assembly under past oceanographic changes. The relative influence of stochastic and deterministic processes on the bacterial assemblage was primarily determined by dispersal limitation. We have summarized our findings in a conceptual model that revealed how changes in paleoclimate phases cause shifts in ecological succession and the assembly process. In this ecological model, dispersal limitation is an important driving force for progressive succession for bacterial community assembly processes on a geological timescale in the western Arctic Ocean. This enabled a better understanding of the ecological processes that drive the assembly of communities in Holocene sedimentary habitats affected by sea-level rise, such as in the shallow western Arctic shelves.

Diagenetic effect on barium isotope compositions of barites in the lower Cambrian successions

The pelagic barite precipitation in the seawater column is tightly associated with the biological pump, and thus the barite Ba isotope composition (δ138/134Ba) has been advocated as a novel paleo-productivity proxy. However, pelagic barites in sediments are susceptible to diagenetic processes that may modify primary δ138/134Ba signals and hamper the application. To constrain the diagenetic effect, we report δ138/134Ba data of diagenetic barites from the black shales of the lower Cambrian Yurtus Formation in the Aksu area of the Tarim Basin. The δ138/134Ba values vary within a large range from −0.15‰ to +0.49‰ and show a generally positive correlation with the 87Sr/86Sr ratios, indicating the mixing of two end-members. The samples with 87Sr/86Sr ratios close to the coeval seawater value record relatively low δ138/134Ba values from −0.15‰ to +0.14‰, which are inferred to inherit from the primary barites; whereas the samples with 87Sr/86Sr ratios exceeding the coeval seawater value record higher δ138/134Ba values from −0.05‰ to +0.49‰, which may have resulted from the alteration by the host black shales during early diageneses. Based on these investigations, we propose that pore waters below the sulfate-methane transition zone may provide an additional source of Ba (enriched in heavy isotopes) for the formation of diagenetic barites. We suggest to combine barite 87Sr/86Sr ratio with δ138/134Ba value to evaluate diagenetic influence on primary Ba isotope signatures especially for an over-determined system, which is important for applying Ba isotope compositions of barites to understand paleo-oceanic evolution.

Methane Index: Towards a quantitative archaeal lipid biomarker proxy for reconstructing marine sedimentary methane fluxes

In marine sediments, anaerobic methane oxidation (AOM) carried out by consortia of methanotrophic archaea (ANME groups) and sulfate reducing bacteria (SRB) represents a major sink for methane (40–290 Tg of C yr−1). The variability of seafloor methane seepage and AOM is crucial to sedimentary biogeochemistry and global carbon/sulfur cycling, yet poorly constrained for Earth’s history. Based on the rationale that a major group of ANME preferentially synthesizes certain tetraether lipids, Methane Index (MI) measured from sedimentary archaeal lipid biomarkers called GDGTs (glycerol dialkyl glycerol tetraethers) has been widely used as a qualitative indicator for methane-impact on sediments. However, it was unclear whether small amounts of diagenetic methane in porewater could cause high MI values or that high methane flux associated with, for example cold seeps, is required. Since not all ANME groups synthesize GDGTs, another contested issue is whether this index is broadly representative of AOM. Here, we use modern porewater and sedimentary lipid profiles from the world’s ocean to further explore MI’s potential to address these questions. The new data show that MI is quantitatively linked to sedimentary methane diffusive flux and the depth of sulfate-methane transition zone (SMTZ) which is the diagenetic front where AOM activity is mostly concentrated. In particular, high MI values (>0.3–0.5) are strongly associated with high methane fluxes (>∼0.1 mmol m−2 d−1) and shallow SMTZ depths (<1–3 m) commonly linked to gas hydrate dissociations. Sensitivity analyses suggest that when the variability of several key parameters (e.g., seawater sulfate concentration, geothermal gradient, and sediment porosity) is small, modern MI – methane flux and MI – SMTZ depth relationships can be applied to reconstruct methane history and diagenetic zonation of the geological past. Although only Group I of ANME archaea synthesizes GDGTs, the co-occurrence of AOM biomarkers (e.g., crocetane, PMI, and hydroxyarchaeol) that are attributed to ANME-2 or ANME-3 and high MI values suggest that MI is broadly representative of AOM. Lastly, we applied MI to probe the methane venting history by using new data from a Cascadia Margin site (Hydrate Ridge, IODP U1328) since the penultimate interglacial, and reinterpreted recently reported MI data from three Southern Ocean sites (ODP 1168, 1170, and IODP U1356) during the late Oligocene – early Miocene. Overall, these applications demonstrate that MI can serve as a sensitive and quantitative proxy to help broadly establish Cenozoic and Mesozoic history of marine methane biogeochemical cycling.

The marine redox evolution and the formation model for the early Cambrian Gongxi-Tianzhu barite deposits in the South China Block

Late Ediacaran to early Cambrian is marked as a vital ore-formation interval of the Earth’s history, particularly for the bedded barite deposits hosted in cherts and shales. Although plenty of work has been carried out, controversies still exist, such as how the marine paleoenvironment changed in this critical interval, and where the origin of ore-formation materials (i.e., barium ions) was. To address these questions, here, we conducted systematic geochemical research on Gongxi-Tianzhu barite deposits in the South China Block, using redox proxies (MoEF-UEF, Mo-TOC, U-TOC patterns, and elemental ratios), REY patterns, and Sr isotopes. Redox proxies were used to reconstruct the paleoenvironment evolution in the Gongxi-Tianzhu region during the early Cambrian interval. Redox proxy results revealed that the bottom water was oxygen-depleted during most of the depositional time of the Niutitang Formation. The bedded and nodular barites in the Niutitang Formation were formed in the Sulfate-Methane Transition Zone (SMTZ) during the synsedimentary and early diagenetic processes. Formation of the barite ores depended greatly on the redox state variation of the bottom water and the barium remobilization in the sediments. The ore-formation event ceased when the supply of oxygen and sulfate from the upper water stopped, and the pre-stored Ba ions in the anoxic bottom seawater were exhausted and the SMTZ rose back into the water again. REY patterns and 87Sr/86Sr values recorded coeval seawater signals without hydrothermal activities during the studied interval. Based on the elemental and isotopic evidence, a three-stage redox-diagenetic model was established for the formation of the barite deposits in South China.

Formation process of Pliocene cold seep carbonates from the southern Western Foothills, Southwestern Taiwan: A synthetical rare earth element and C–O–Sr–Nd isotope study

In this work, the Pliocene dolomitic carbonate concretions and pipes from Chiahsien of the Western Foothills, southwestern Taiwan were studied. We conducted a synthetical analysis of stable carbon and oxygen isotopes, rare earth element (REE) contents, and Sr and Nd isotopes, to trace the compositions and sources of pore fluids from which carbonates have precipitated and reconstruct the carbonate formation processes. The carbonates with low δ13C values (as low as −48.6‰) are promoted by the anaerobic oxidation of biogenic methane. The 87Sr/86Sr ratios of samples reflect the mixing of coeval bottom seawater and seep fluid enriched in 87Sr. The Nd isotopic signatures of studied carbonates indicate multiple Nd sources, including detrital components, Fe–Mn oxyhydroxides, organic matter, and seawater. The MREE-bulge patterns in samples are typical of anoxic conditions, which are supported by Ce anomalies. Our results demonstrate that the seepage intensity played a key role in the formation processes of concretions and pipes by controlling the depth of the sulfate-methane transition zone (SMTZ). The concretions characterized by the lowest δ13C values formed at a deeper depth in sediments under low methane flux, which suffered no/less influence of seawater. The representative pipe with obvious concentric lamination grew in a rim-to-core pattern. In the early stage, the variable flux of highly channelized seepage caused the fluctuation of carbon and oxygen isotopes. During the later stage, the modification of isotopic compositions in the core part were resulted from meteoric alteration. Our work provides insights into the formation process related to seepage evolution in ancient cold seeps on Taiwan Island.

The Characteristics and Origin of Barite in the Giant Mehdiabad Zn-Pb-Ba Deposit, Iran

Abstract Mehdiabad is the world’s largest Mississippi Valley-type (MVT) Zn-Pb deposit (394 million tonnes [Mt] of metal ore at 4.2% Zn, 1.6% Pb) and contains significant barite resources (&amp;gt;40 Mt). Such large accumulations of barite are not common in carbonate-hosted Zn-Pb deposits. Therefore, the origin of the barite and its association with the Zn-Pb mineralization is of significant interest for further investigation. Field work and petrographic studies indicate that the Zn-Pb-Ba orebodies in the Mehdiabad deposit are hosted by Lower Cretaceous carbonate units of the Taft and Abkuh Formations. Fine- to coarse-grained barite with lesser siderite formed in three stages (S1, S2, and S4), along with a quartz-sulfide stage (S3) with minor quartz, sphalerite, galena, chalcopyrite, and pyrite, and the main Zn-Pb sulfide stage (S5) with massive sphalerite and galena. The barites have δ34S values from 17.7 to 20.6‰, δ18O values from 13.2 to 16.8‰, Δ33SV-CDT values from –0.001 to 0.036‰, and initial 87Sr/86Sr ratios from 0.707327 ± 0.000008 to 0.708593 ± 0.000008 (V-CDT = Vienna-Canyon Diablo Troilite). The siderites have δ13CV-PDB values from –3.8 to –2.7‰, and δ18OV-SMOW values from 18.2 to 20.9‰ (V-PDB = Vienna-Pee Dee Belemnite, V-SMOW = Vienna-standard mean ocean water). These geochemical data, and the barite morphology, point to a diagenetic origin for all stages of barite. We suggest that S1 and S2 barite precipitated from pore fluids at the sulfate-methane transition zone in a methane-diffusion-limited environment with increasing methane content. S4 barite precipitated when the methane- and barium-bearing cold-seep fluid migrated to the shallow carbonate sediments and formed a methane-in-excess setting. For the three stages, the SO42- in barite came from the residual SO42- in pore fluids undergoing sulfate-driven anaerobic oxidation of methane, and the Ba2+ came from dissolved biogenic barite and terrigenous materials in the Taft and Sangestan Formations. Primary fluid inclusions trapped in S3 quartz have salinities of 5.6 to 8.1 wt % NaCl equiv and homogenization temperatures of 143.8° to 166.1°C. The quartz has δ18OV-SMOW values ranging from 9.8 to 22.5‰ and δ30Si values from –1.3 to –0.9‰. These data indicate hydrothermal fluid flow occurred between the diagenetic S2 and S4 events. Secondary fluid inclusions with salinities of 17.70 to 19.13 wt % NaCl equiv and homogenization temperatures of 123.0° to 134.0°C are found in the S3 quartz, too. They might represent the hydrothermal event formed by basinal brines in S5. According to the ore textures and the comparison of the sulfur isotopes between S5 Zn-Pb sulfides and the digenetic barites, the barite provided a host and a sulfur source for the later Zn-Pb mineralization. The relationship between barite and the Zn-Pb mineralization indicates that significant accumulations of sulfates may be a critical exploration target for this kind of giant deposit.

Quantification of the sources of sedimentary organic carbon at methane seeps: A case study from the South China Sea

Large amounts of methane are stored along continental margins in the form of methane hydrate. Methane hydrate is sensitive to environmental change, resulting in the release of substantial quantities of methane upon its destabilization. In the marine subsurface, microorganisms consume most of the methane in the sulfate-methane transition zone and convert a certain amount of methane into organic matter. Burial of such organic matter deriving from methane oxidation represents a long-term carbon sink, therefore mitigating the effect of a prominent greenhouse gas on global warming. However, the controls on the formation and consumption of sedimentary organic matter at marine seeps remain poorly constrained, impeding accurate quantification of carbon burial at seeps and its role in the marine carbon cycle. To gain new insight on the effect of seeps on carbon burial, sediments from two seep sites of the South China Sea (Site F, Haiyang 4) and a nearby reference site (Jiulong canyon) were analyzed for total organic carbon contents (TOC), δ13CTOC and Δ14C values, total inorganic carbon contents (TIC) and δ13CTIC values, as well as organic nitrogen (N) contents. Depth distributions reveal that the TOC at seeps (Site F, 0.55% ± 0.08%, Haiyang 4, 0.67% ± 0.11%) is higher than in sediments not affected by seepage (Jiulong canyon, 0.50% ± 0.10%). The enrichment of total sulfur, high TIC, and negative δ13CTIC values in sediments from Site F and Haiyang 4 agrees with locally prominent sulfate-driven anaerobic oxidation of methane (AOM) and resultant precipitation of authigenic carbonate. At the two seep sites, the sediments are characterized by more negative δ13CTOC and Δ14C values and a lower TOC/N ratio, indicating a contribution of the microbial fixation of 13C-depleted methane to the local pool of sedimentary organic matter. A linear increase in 14C ages of organic carbon with sediment depth at the reference site indicates steady depositional conditions, whereas the 14C age of organic carbon at seeps is typified by contributions of methanotrophy-derived carbon. A Δ14C mass balance approach shows that carbon derived from fossil methane accounts for at least 10 to 20% of the organic carbon preserved in the sediments. By comparing seeps, hydrate-bearing sediments, modern coastal sediments, and Archaean rocks, it becomes apparent that the carbon stable isotope composition of organic carbon in seep sediments is mainly controlled by the rate of methane oxidation and marine primary productivity.

Methane release effects on foraminiferal tests in northern South China Sea

Upward diffusing methane in gas hydrate geological systems is consumed in the sediment and water column by a series of biogeochemical reactions, which not only affect living foraminifera but also lead to early diagenetic alteration of buried foraminiferal tests. Previous studies of the impact of methane release events on fossil foraminifera focused mainly on carbon and oxygen isotopes, with little attention given to other geochemical proxies to date. Here, we examine the test wall microstructure and analyze the elemental and stable carbon-oxygen isotopic compositions of buried foraminifera from gas hydrate-bearing sediments at Site GMGS2-16 in the northern South China Sea. Our results show that diagenetic alteration of foraminiferal tests at Site GMGS2-16 is mainly linked to high-Mg calcite overgrowths. Test δ13C covaries negatively with the degree of diagenetic alteration (based on petrographic characteristics) but positively with Mg/Ca ratios. With increasing diagenetic alteration, Ba/Ca, Mn/Ca, Fe/Ca, Mo/Ca, U/Ca, V/Ca, Ni/Ca and Co/Ca also generally increase, but Sr/Ca and Cu/Ca exhibit variable changes. We infer that foraminiferal tests are highly susceptible to alteration by methane-bearing fluids, and that the elemental ratios of diagenetically altered tests are potentially reliable proxies for paleo-methane release events. At Site GMGS2-16, the overall pattern of diagenetic alteration of foraminiferal tests records frequent vertical fluctuations of the sulfate-methane transition zone (SMTZ) caused by variable fluid flux and methane release rates, with two discrete large-scale methane release events having maximum ages of ~0.47 ka and ~170 ka.