Methane-derived Authigenic Carbonates Research Articles

Lateral migration of methane at a cold seep: Evidence from U–Th dating of methane-derived authigenic carbonate in the Middle Okinawa Trough

Submarine methane seepages constitute an important part of global carbon cycle and may be promoted by the dissociation of gas hydrate. The migration pattern of a seepage is commonly dominated by vertical transport of methane-rich pore fluids, and then lateral migration of these fluids probably occurred due to self-sealing effect of carbonate crust above vertical migration conduit. Some studies found the evidence of this lateral migration, but the one from the record of seep carbonate in nature is very rare. In this study, we present the results of mineralogical, isotopic, and dating analyses of a core containing seep carbonates obtained from seafloor drilling site D5 in the Middle Okinawa Trough. The core contains 0.98-m-long carbonate interval that predominantly consists of aragonite, with an average content of ∼86.6%. The carbonate exhibits moderate depletion in 13C (δ13C values: −37.2‰ to −16.3‰ Vienna Pee Dee Belemnite; VPDB) and enrichment in 18O (δ18O values: 4.3‰–5.8‰ VPDB), with relatively constant 87Sr/86Sr values (0.709167–0.709197). These results suggest that the precipitation of the seep carbonate was induced by the sulfate-driven anaerobic oxidation of methane close to the seabed and this methane could be from the dissociation of gas hydrates. U–Th age–depth profile shows that two carbonate intervals grew downwards coevally to coalesce into a thicker crust, and its upper segment also grew upwards. We interpret that lateral migration of the fluid flows at two levels are responsible for the formation of upper and lower segments of carbonate intervals because they have (a) the distinct clustering of δ13C and δ18O values and (b) a coeval period of fast growth. It is likely that upward migration of methane was redirected by self-sealing of overlying carbonate crust, leading to lateral migration at the flank of seabed mound Db4 during 6.2–4.6 ka. Our findings highlight the interaction between fluid flows and authigenic carbonates during Late Quaternary, which implies that more methane could be consumed by oxidation because it takes longer time for methane to bypass self-sealing of carbonate to escape into the ocean.

Exploring the pore fluid origin and methane-derived authigenic carbonate properties in response to changes in the methane flux at the southern Ulleung Basin, South Korea

We investigated the geochemistry of gas, pore fluid, and methane-derived authigenic carbonate (MDAC) from four sites in the southern Ulleung Basin, South Korea. In contrast to Sites 16GH-P1 and 16GH-P5, Sites 16GH-P3, and 16GH-P4 are characterized by acoustic chimney structures associated with gas flux. The composition of gas and isotopic signatures of methane (CH4) (C1/C2+ > 300, δ13CCH4 < -60‰, δDCH4 ≤ -190‰) indicate microbial source CH4 at all sites. The upward migration of CH4 can affect the chemical and isotopic properties of pore fluid and gas-related byproducts (e.g., gas hydrate (GH) and MDAC) within the shallow sediments including the current sulfate-methane transition (SMT) (< 5 meters below seafloor). Although no GH was found, elevated Cl- concentrations (maximum = 609 mM) with low δD and δ18O values in Site 16GH-P4 pore fluids delineate the influence of massive GH formation in deeper sediment. In contrast, relatively constant Cl-, δD, and δ18O values in fluids from Sites 16GH-P1, 16GH-P3, and 16GH-P5 indicate a predominant origin from seawater. Pore fluids also exhibit higher concentrations of H4SiO4, B, Mg2+, and K+, along with increasing alkalinity compared to seawater. These observations suggest that marine silicate weathering alters fluid chemistry within the sediment, affecting element and carbon cycles. High alkalinity (up to 60 mM) and Mg2+/Ca2+ ratios (> 6) alongside decreasing Ca2+ and Sr2+ concentrations imply carbonate precipitation. MDACs with diverse morphologies, mainly composed of aragonite and magnesian calcite, and characterized by low carbon isotopic values (δ13CMDAC < -31.3‰), were found at Sites 16GH-P3 and 16GH-P4. Interestingly, δ13CMDAC values at Site 16GH-P3 are clearly differentiated above and below the current SMT. High δ13CMDAC values above the SMT (> -34.3‰) suggest the combined influence of seawater and CH4 migrating upward on MDAC precipitation, whereas low δ13CMDAC values below it (< -41.6‰) indicate a predominant impact of CH4 on MDAC formation. Additionally, the vertical variation of δ18OMDAC values at Site 16GH-P4, compared to the theoretical values, reflects an association with GH dissociation and formation. Our findings improve the understanding of fluid, gas, and MDAC geochemistry in continental margin cold seeps, providing insights into global carbon and element cycles.

Seafloor activity and deep-subsurface geology of gas hydrate areas revealed from δ13C of methane-derived authigenic carbonates along the eastern margin of the Sea of Japan

The collection of microbial CH4 hydrates and methane-derived authigenic carbonates (MDACs) around Sado Island in the Sea of Japan has recently increased. In this study, the carbon isotopic composition of CaCO3 in MDAC (δ13CCaCO3) within these microbial CH4 hydrate areas was compared to that observed at the thermogenic CH4 hydrate mounds of the Umitaka Spur offshore of Joetsu, Sea of Japan. δ13CCaCO3 from thermogenic CH4 hydrate mounds (‐39.1 to -6.1‰ Vienna Pee Dee Belemnite [VPDB]) was more enriched in 13C than those of microbial CH4 areas (‐57.6 to -41.0‰ VPDB). The δ13CCaCO3 variations represented by 2σ standard deviations were also greater for the thermogenic CH4 hydrate mounds (8–11‰) compared to those of the microbial CH4 areas (6–7‰). Because the precipitation of MDACs with various δ13CCaCO3 compositions can occur over areas undergoing dynamic geochemical changes, larger variations suggest that the current thermogenic CH4 hydrate mounds with active gas seepage must have been geochemically dynamic during past MDAC precipitation. Oil-containing gas hydrates in the thermogenic CH4 hydrate mounds suggest a link with deep oil and gas reservoirs. CH4 leakage from deep-subsurface gas reservoirs may drive the higher activity observed at shallow sediment depths in thermogenic CH4 hydrate mounds. δ13CCaCO3 variations revealed differences in paleogeochemical dynamics at shallow sediment depths, and the geochemical characteristics may provide insights into deep-subsurface geological situations for CH4 supply.

Fluid venting submarine structures in the middle slope of the Spanish continental margin of the Gulf of Cádiz: Geomorphology, internal structure, benthic features and control factors

This paper explains the current seafloor morphology and processes that affect the formation and evolution of three mud volcanoes and one mud volcano/mud diapir complex in the deepest sector of the Spanish margin of the Gulf of Cádiz. The present study provides novel results and interpretations based on an extensive multidisciplinary data set. New high resolution bathymetric and backscatter data from multibeam echosounders enabled a detailed geomorphological analysis aimed at identifying diverse seafloor features in the different edifices studied and their adjacent bottoms. These features are mainly related to fluid escape (e.g., mud volcanoes, mud flows and depressions), gravitational (e.g., slide deposits and scars), and tectonic (e.g., faults and uplifted antiforms) processes. Very high-resolution parametric profiles and single channel seismic reflection profiles were interpreted for further analysis of the internal structures, demonstrating their important interplay with diapiric processes. Box-corer and gravity-corer have been used to identify different sediment types that have been correlated with backscatter values. The dominant benthic species associated with fluid venting and also with different types of substrates (hard and soft) were characterized using submarine images obtained with an underwater camera deep-towed sled. The benthic species observed were contrasted, and added to those collected with beam trawl and box-corer for characterisation of the benthic and demersal communities. Different geological and biological indicators have been used as proxies of the interaction of these features with the geological processes (such as fluid-escape-related, gravitational, or structural) to characterise the environmental conditions that determine the geomorphology, substrates, habitats and their associated biota. Multivariate analyses combining faunistic and environmental data resulted in the presence of 3 main faunistic assemblages linked to different levels of fluid venting and the importance of depth and variables linked to fluid venting processes (e.g. mud breccia, Methane-derived authigenic carbonates) in the distribution of these assemblages. A conceptual model has been proposed to explain the actual seafloor morphology and the different processes that affect the formation and evolution of the fluid venting submarine structures studied.

Sedimentary deformation relating to episodic seepage in the last 1.2 million years: a multi-scale seismic study from the Vestnesa Ridge, eastern Fram Strait

Seafloor hydrocarbon seepage is a natural fluid release process that occurs worldwide on continental shelves, slopes, and in deep oceanic basins. The Vestnesa sedimentary ridge in the eastern Fram Strait hosts a deep-water gas hydrate system that became charged with hydrocarbons ∼2.7 Ma and has experienced episodic seepage along the entire ridge until a few thousand years ago, when seepage activity apparently ceased in the west but persisted in the east. Although it has been documented that faults and fractures play a key role in feeding the seeps with thermogenic gases, the mechanisms controlling seepage periodicity remain poorly understood. Here we integrate high-resolution P-cable 3D seismic and Chirp data to investigate the spatial and temporal evolution of high-resolution fractures and fluid flow features in the west of the Vestnesa Ridge. We characterize sediment deformation using a fracture density seismic attribute workflow revealing two highly deformed stratigraphic intervals and associated small-scale pockmarks (<20 m diameter). Chronostratigraphic constraints from the region show that these two highly deformed intervals are influenced by at least three major climatic and oceanic events during the last 1.2 million years: the Mid-Pleistocene Transition (∼1.25–0.7 Ma), the penultimate deglaciation (∼130 ka) and the last deglaciation (Heinrich Stadial 1: ∼16 ka). These periods of deformation appear associated with seismic anomalies potentially correlated with buried methane-derived authigenic carbonate and have been sensitive to shifts in the boundary of the free gas-gas hydrate interface. Our results show shifts (up to ∼30 m) in the depth of the base of the gas hydrate stability zone (GHSZ) associated with major changes in ocean bottom water temperatures. This ocean-driven effect on the base of the GHSZ since the Last Glacial Maximum coincides with the already highly deformed Mid-Pleistocene Transition sedimentary interval and likely enhanced deformation and gas leakage along the ridge. Our results have implications for understanding how glacial cycles impact fracture formation and associated seepage activity.

Foraminifera associated with cold seeps in marine sediments

Cold seep foraminifera have attracted considerable attention as they provide valuable insights into the study of cold seeps. This study provides a comprehensive overview of the manifestations of foraminifera in cold seep environments and methane seepage activities. Certain taxa of benthic foraminifera, such as Uvigerina, Bolivina, Bulimina, Chilostomella, Globobulimina, Nonionella, Melonis, Epistominella, Cibicidoides, and Globocassidulina, are known to inhabit geochemical conditions induced by methane-rich environments and may feed on associated methanotrophic microbial communities. Secondary mineralization on foraminifera shells is a widespread manifestation in seep sediments, and alters the microstructure, elementary composition, and isotopic signatures of foraminifera. On one hand, the precipitation of secondary authigenic Mg-rich, Mn-rich, Sr-rich, and Ba-rich calcite coatings have been observed on microfossils. On the other hand, micron-sized crystal pyrite and gypsum aggregates can also grow on the foraminifera walls. The negative δ13C and positive δ18O anomalies in both planktonic and benthic foraminifera from seep-associated sediments can serve as proxies for tracing past seepage activities, either in their live form or being adulterated by methane-derived authigenic carbonate after deposition. Seeping activities are recognized with a significant impact on benthic foraminifera, and the presence of cold seep-related species and significant isotopic anomalies in shells can be used to reconstruct past methane seepage events. Intensive methane seepage tends to suppress benthic foraminifera populations, while moderate intensity seepage may lead to a thriving benthic foraminiferal community, with hypoxia-enduring taxa such as Uvigerina, Melonis, and Bulimina being predominant. In contrast, oxygen-loving epibenthic taxa such as Cibicidoides often occur in areas of low methane flux. Compared to planktonic foraminifera, the single species of benthic foraminifera can provide a more comprehensive record of seepage evolution. Live benthic specimens are preferred for in-situ seep studies, while the superimposition of secondary minerals on the original shells should not be ignored when observing dead individuals. The significance of the evolution of methane seepage, changes in environmental parameters of the living habitat, and species sensitivity in cold seeps are emphasized in explaining the variation in foraminiferal assemblages and fluctuations in stable isotopes.

APPLICATION OF MUD GAS DATA AND LEAKAGE PHENOMENA TO EVALUATE SEAL INTEGRITY OF POTENTIAL CO2 STORAGE SITES: A STUDY OF CHALK STRUCTURES IN THE DANISH CENTRAL GRABEN, NORTH SEA

Depleted chalk oilfields and chalk structures in the Danish Central Graben, North Sea, are potential CO2 storage sites. In most of these fields, the main reservoir is the Upper Cretaceous – Danian Chalk Group and the Eocene – Miocene mudstones of the Horda and Lark Formations constitute the primary seal. In a few fields, the reservoir is composed of the Lower Cretaceous Tuxen and Sola Formations. Here the main seal is assumed to be the Chalk Group which however has poor gas sealing characteristics; the Horda and Lark Formations constitute an efficient secondary seal although they are quite high in the section. This study documents a workflow that may help to evaluate the seal integrity of the structures from an integration of mud gas data from wells with seismic data. Mud gas data provide detailed information about the distribution and types of gas (biogenic or thermogenic) throughout the seal section and overburden. The presence of higher carbon number gases (C3–C5, propane to pentane) in the seal indicates migration of thermogenic gas into the thermally immature sealing mudstones; whereas the dominance of C1 (methane) and partly C2 (ethane) likely reflects the presence of in situ generated biogenic gas in the mudstones, thus indicating that there are no seal integrity issues. The vertical thermogenic gas migration front has been determined, and a “traffic light” indicator system has been used for seal integrity evaluation. Where no or minor migration of thermogenic gas into the primary seal has occurred and a primary seal >30 m thick is present, the seal is considered to have good matrix seal integrity (green). If some significant thermogenic gas migration has occurred into the primary seal but more than 30 m of primary seal is present above the thermogenic gas migration front, the seal integrity is reduced (yellow). In structures where thermogenic gas migration is recorded through the primary seal and into the overburden, seal integrity is considered to be poor (red). In areas where significant leakage of thermogenic gas has occurred into the seal, high density, low porosity carbonate beds frequently occur encapsulated within the sealing mudstones and are interpreted to be composed of methane‐derived authigenic carbonates (MDACs). Seismic data show that there is a convincing correlation between leakage as indicated from mud gas data and the presence of vertical wipe‐out zones (gas chimneys), bright zones (gas‐charged sediments or MDACs), and depressions (pockmarks). In general, potential CO2 storage sites in the study area in tectonically inverted structures show good seal integrity, but this may locally be reduced and require additional analyses. Storage sites associated with salt diapirs generally show poor seal integrity and are likely to be poor candidates for CO2 storage. In combination, mud gas and seismic data are therefore powerful tools to investigate (palaeo‐) leakage phenomena and provide support for seal integrity evaluation at local to regional scales.

Visualization of shallow subseafloor fluid migration in a shallow gas hydrate field using high-resolution acoustic mapping and ground-truthing and their implications on the formation process: a case study of the Sakata Knoll on the eastern margin of the Sea of Japan

Acoustic mapping enables an understanding of the surface distribution of shallow gas hydrate (GH) and related products. Acoustically characteristic materials such as fluid-seepage-related methane-derived authigenic carbonate and/or shallow GHs, may be widely distributed beneath the shallow seafloor of the Sakata Knoll. High-amplitude reflectors over the knoll are the top of gas-bearing permeable layers and connect to the reverse fault at the foot of the knoll. Shallow GH and bacterial mats were observed at the high-amplitude layer cut by depression and/or the locally disturbed seafloor. Acoustic blanking zones observed on the sub-bottom profiler sections are current gas migration routes from the depth to the seafloor. Optical observations indicate that fluid seepage is not active in the current seafloor, and it is not necessarily observed above the acoustic blanking zones or shallow faults reaching the seafloor. In the Sakata Knoll, the tectonically formed reverse fault and gas-bearing permeable layers play more important roles in fluid migration from depth to the summit area of the knoll compared to acoustic blanking and shallow faults. The depression at the summit area of the Sakata Knoll was formed by the dissociation of a shallow GH at around the last glacial maximum. Limited fluid seepage is currently witnessed within and around the depression and it is less extensive than that in the past. Such knolls, with tectonically formed large faults and an anticline are abundant in the area and they can be good reservoirs for shallow GH along the eastern margin of the Sea of Japan.

Impact of High Methane Flux on the Properties of Pore Fluid and Methane-Derived Authigenic Carbonate in the ARAON Mounds, Chukchi Sea

We investigated the pore fluid and methane-derived authigenic carbonate (MDAC) chemistry from the ARAON Mounds in the Chukchi Sea to reveal how methane (CH4) seepage impacts their compositional and isotopic properties. During the ARA07C and ARA09C Expeditions, many in situ gas hydrates (GHs) and MDACs were found near the seafloor. The fluid chemistry has been considerably modified in association with the high CH4 flux and its related byproducts (GHs and MDACs). Compared to Site ARA09C-St 08 (reference site), which displays a linear SO42- downcore profile, the other sites (e.g., ARA07C-St 13, ARA07C-St 14, ARA09C-St 04, ARA09C-St 07, and ARA09C-St 12) that are found byproducts exhibit concave-up and/or kink type SO42- profiles. The physical properties and fluid pathways in sediment columns have been altered by these byproducts, which prevents the steady state condition of the dissolved species through them. Consequently, chemical zones are separated between bearing and non-bearing byproducts intervals under non-steady state condition from the seafloor to the sulfate-methane transition (SMT). GH dissociation also significantly impacts pore fluid properties (e.g., low Cl-, enriched δD and δ18O). The upward CH4 with depleted δ13C from the thermogenic origin affects the chemical signatures of MDACs. The enriched δ18O fluid from GH dissociation also influences the properties of MDACs. Thus, in the ARAON Mounds, the chemistry of the fluid and MDAC has significantly changed, most likely responding to the CH4 flux and GH dissociation through geological time. Overall, our findings will improve the understanding and prediction of the pore fluid and MDAC chemistry in the Arctic Ocean related to CH4 seepage by global climate change.

Interpreting Molecular and Isotopic Biosignatures in Methane-Derived Authigenic Carbonates in the Light of a Potential Carbon Cycle in the Icy Moons.

Finding evidence of life beyond Earth is the aim of future space missions to icy moons. Icy worlds with an ocean underlying the icy crust and in contact with a rocky subsurface have great astrobiological interest due to the potential for water-rock interactions that may provide a source of nutrients necessary to sustain life. Such water-rock interactions in icy moons can be indirectly investigated using analogous environments on the deep seafloor on Earth. Here, we investigate the presence of molecular and isotopic biomarkers in two submarine cold seep systems with intense rock-fluid interactions and carbon sink as carbonates with the aim of gaining understanding of potential carbon cycles in the icy worlds' oceans. Authigenic carbonates associated to cold seeps (a chimney from the Gulf of Cádiz and a clathrite from the Pacific Hydrate Ridge) were investigated for their mineralogical composition and lipid biomarker distribution. Molecular and compound-specific isotopic composition of lipid biomarkers allowed us to infer different carbonate origins in both carbonate scenarios: biogenic methane (clathrite) versus thermogenic methane together with allochthonous carbon (chimney). In the Pacific cold seep, carbonate precipitation of the clathrite was deduced to result from the anaerobic oxidation of methane by syntrophic action of methanotrophic archaea with sulfate-reducing bacteria. The distinct carbon sources (thermogenic methane, pelagic biomass, etc.) and sinks (gas clathrates, clathrite, chimney carbonates) were discussed in the light of potentially similar carbon cycling pathways in analogous icy-moon oceans. We show how the isotopic analysis of carbon may be crucial for detecting biosignatures in icy-world carbon sinks. These considerations may affect the strategy of searching for biosignatures in future space missions to the icy worlds.

Influence of methane seepage on isotopic signatures in living deep-sea benthic foraminifera, 79\xb0 N

Fossil benthic foraminifera are used to trace past methane release linked to climate change. However, it is still debated whether isotopic signatures of living foraminifera from methane-charged sediments reflect incorporation of methane-derived carbon. A deeper understanding of isotopic signatures of living benthic foraminifera from methane-rich environments will help to improve reconstructions of methane release in the past and better predict the impact of future climate warming on methane seepage. Here, we present isotopic signatures (δ13C and δ18O) of foraminiferal calcite together with biogeochemical data from Arctic seep environments from c. 1200 m water depth, Vestnesa Ridge, 79° N, Fram Strait. Lowest δ13C values were recorded in shells of Melonis barleeanus, − 5.2‰ in live specimens and − 6.5‰ in empty shells, from sediments dominated by aerobic (MOx) and anaerobic oxidation of methane (AOM), respectively. Our data indicate that foraminifera actively incorporate methane-derived carbon when living in sediments with moderate seepage activity, while in sediments with high seepage activity the poisonous sulfidic environment leads to death of the foraminifera and an overgrowth of their empty shells by methane-derived authigenic carbonates. We propose that the incorporation of methane-derived carbon in living foraminifera occurs via feeding on methanotrophic bacteria and/or incorporation of ambient dissolved inorganic carbon.

Boron concentrations and isotopic compositions in methane-derived authigenic carbonates: Constraints and limitations in reconstructing formation conditions

The boron content and isotopic composition (δ11B), of marine carbonates have the potential to constrain CO2 chemistry during carbonate growth conditions. However, obtaining and interpreting boron compositions from authigenic carbonates in geological archives present several challenges that may substantially limit their application. In particular, contamination from non-carbonate phases during sample preparation must be carefully avoided, and a variety of controls on boron composition during authigenic growth conditions must be evaluated. To advance understanding of the use and limitations of boron in authigenic carbonates, we present data and modelling results on methane-derived authigenic carbonate (MDAC), a by-product of microbially mediated anaerobic oxidation of methane, taken from three cold seep sites along the Norwegian margin. We present a novel sequential leaching method to isolate the boron signals from the micritic (Mg-calcite) and cavity-filling (aragonitic) MDAC cements in these complex multi-phase samples. This method successfully minimizes contamination from non-carbonate phases. To investigate the factors that could potentially contribute to the observed boron signals, we construct a numerical model to simulate the evolution of MDAC δ11B and B/Ca ratios over its growth history. We show that diagenetic fluid composition, depths of precipitation, the physical properties of sediments (such as porosity), and mineral surface kinetics all contribute to the observed boron compositions in the different carbonate cements. While broad constraints may be placed on fluid composition, the multiple competing controls on boron in these diagenetic settings limit the ability to place unique solutions on fluid CO2 chemistry using boron in these authigenic carbonates.

Review of Methane Seepages in the Okinawa Trough: Progress and Outlook

It has been two decades since the cold seeps were firstly found in the Okinawa Trough (OT). The scientific cruises and the geological surveys since then have unveiled the currently active submarine methane seeps and significantly improved the understanding of methane seeps in the back-arc basin of the OT. In this paper, we review the up-to-date progress of the research of methane seepages then put forward the promising, yet challenging, outlook by listing the unsolved questions of the cold seeps in the OT. Multiple approaches and techniques, including seismic and echo-sounder recording, dredging, gravity-piston and ROV coring, seafloor drilling, and isotopic and microarray-based genomic analysis, have been used to reveal the geological processes responsible for the seeping activities and the biogeochemical processes related to them. The geophysical signature associated with gas seeps mainly includes the acoustic turbidity in the subsurface, the anomaly of the backscattering intensity at the seabed, and the gas plumes observed in the water column. Pore water and methane-derived authigenic carbonate archive the intensification of methane seepage and the paleoenvironment changes at different time scales. The methane feeding of the seeps in the OT was generated mostly via the microbially mediated process and has an origin mixed by thermogenic hydrocarbon gas in the middle OT. Sulfate-driven and Fe-driven anaerobic oxidations of methane are suggested to be the key biogeochemical processes, which would shape the material cycling in the seeping environment. The future research on the cold seeps in the OT is worth looking forward to due to its geographic and potential geologic links with the nearby hydrothermal activities. Multidisciplinary studies are expected to concentrate on their link with the undiscovered gas hydrates, the amount of methane transferring into the oceans and its impact on the climatic change, and the evolution of the seeping activities accompanied by the biogeochemical processes.

Geochemical comparison of ikaite and methane-derived authigenic carbonates recovered from Echigo Bank in the Sea of Japan

This study compares the geochemistry of ikaite (CaCO3·6H2O) with that of nearby (< 500 m in distance) recovered methane-derived authigenic carbonates (MDACs) of ~10 mol% Mg-calcite. The carbon isotopic composition (δ13C) of MDACs (lower than −49‰ Vienna Pee Dee Belemnite or VPDB) suggests a more prominent influence of anaerobic oxidation of methane (AOM) than that of ikaite (approximately −35‰ VPDB). The higher δ13C value of ikaite is attributed to its growth at sediment depths closer to the seafloor, where the proportion of seawater HCO3− relative to methane-derived HCO3− was higher. Assuming that seawater and AOM are the major sources of HCO3− for ikaite growth, the actual 14C age was estimated to be ~14 cal ky before present, close to the age of the sediments observed around the ikaite. For alkalinity increase at shallower sediment depths by the AOM, a higher methane flux is necessary. However, attributing the ikaite growth at shallower sediment depths to higher methane flux alone posed an issue, as no traces of gas hydrate growth were found in the laminated sediments. The oxygen isotopic composition (δ18O) of the freeze-dried ikaite (ikaite-CO3) was ~2‐3‰ VPDB, which is lower than the corresponding value of ~4.0‰ VPDB for the Mg-calibrated MDACs. It is characteristic of ikaite-CO3 to exhibit such low δ18O values, indicating a unique oxygen isotope fractionation factor for ikaite. The preferential H218O uptake of ikaite for growth also influenced the δ18O value of ikaite-CO3. Hence, owing to H218O depletion in the ambient interstitial water, the δ18O value of the ikaite-CO3 tended to decrease from the interior to the margin. The δ18O values of the ikaite-CO3 were archived in yellowish calcite grains that were formed in the pores after patchy dissociation of the ikaite. The δ18O values of the grains were close to those of ikaite-CO3. Therefore, the δ18O-temperature equation for ikaite is necessary for geochemical interpretation of the calcite δ18O values.

Methane-Derived Authigenic Carbonates on the Seafloor of the Laptev Sea Shelf

Seafloor authigenic carbonate crusts are widespread in various oceanic and marine settings, excluding high-latitude basins that are corrosive to carbonate precipitation. Newly formed carbonate formations are relatively rare in modern Arctic marine sediments. Although the first-order principles of seep carbonate formation are currently quite well constrained, little is known regarding the duration or mode of carbonate formation in the Siberian Arctic shelf. Large (massive slabs or blocks) and small crusts that were micrite cemented have been recently discovered on the seafloor of the Siberian Arctic seas within the area of known seep activity in the outer Laptev Sea shelf. Cold methane seeps were detected in the area due to the presence of an acoustic anomaly in the water column (gas flares). Microbial mats, methane gas bubbles, and carbonate crusts were observed using a towed camera platform. Here, we report new geochemical and mineralogical data on authigenic shallow Siberian Arctic cold-seep carbonate crusts to elucidate its genesis. The Laptev Sea carbonate crusts mainly consist of high-Mg calcite (up to 23 mol % MgCO3). The δ13C values in carbonates range significantly (from –40.1 to –25.9‰ VPDB), while the δ18O values vary in a narrow range (+4.4 ± 0.2‰ VPDB). The δ13C values of Corg that was determined from carbonates range from –40.2 to –31.1‰ VPDB. Using the isotope data and taking into account the geological setting, we consider that not only microbial but possibly thermogenic methane participated in the authigenic carbonate precipitation. Carbonate crust formation occurred below the water/sediment interface of the shallow Siberian Arctic shelf as a result of gas hydrate dissociation during Holocene warming events. The studied carbonate crusts were exhumated after precipitation into shallow subsurface shelf sediments.

The Interactive Role of Hydrocarbon Seeps, Hydrothermal Vents and Intermediate Antarctic/Mediterranean Water Masses on the Distribution of Some Vulnerable Deep-Sea Habitats in Mid Latitude NE Atlantic Ocean

In this work, we integrate five case studies harboring vulnerable deep-sea benthic habitats in different geological settings from mid latitude NE Atlantic Ocean (24–42° N). Data and images of specific deep-sea habitats were acquired with Remoted Operated Vehicle (ROV) sensors (temperature, salinity, potential density, O2, CO2, and CH4). Besides documenting some key vulnerable deep-sea habitats, this study shows that the distribution of some deep-sea coral aggregations (including scleractinians, gorgonians, and antipatharians), deep-sea sponge aggregations and other deep-sea habitats are influenced by water masses’ properties. Our data support that the distribution of scleractinian reefs and aggregations of other deep-sea corals, from subtropical to north Atlantic could be dependent of the latitudinal extents of the Antarctic Intermediate Waters (AAIW) and the Mediterranean Outflow Waters (MOW). Otherwise, the distribution of some vulnerable deep-sea habitats is influenced, at the local scale, by active hydrocarbon seeps (Gulf of Cádiz) and hydrothermal vents (El Hierro, Canary Island). The co-occurrence of deep-sea corals and chemosynthesis-based communities has been identified in methane seeps of the Gulf of Cádiz. Extensive beds of living deep-sea mussels (Bathymodiolus mauritanicus) and other chemosymbiotic bivalves occur closely to deep-sea coral aggregations (e.g., gorgonians, black corals) that colonize methane-derived authigenic carbonates.

Ice-sheet melt drove methane emissions in the Arctic during the last two interglacials

AbstractCircum-Arctic glacial ice is melting in an unprecedented mode, and release of currently trapped geological methane may act as a positive feedback on ice-sheet retreat during global warming. Evidence for methane release during the penultimate (Eemian, ca. 125 ka) interglacial, a period with less glacial sea ice and higher temperatures than today, is currently absent. Here, we argue that based on foraminiferal isotope studies on drill holes from offshore Svalbard, Norway, methane leakage occurred upon the abrupt Eurasian ice-sheet wastage during terminations of the last (Weichselian) and penultimate (Saalian) glaciations. Progressive increase of methane emissions seems to be first recorded by depleted benthic foraminiferal δ13C. This is quickly followed by the precipitation of methane-derived authigenic carbonate as overgrowth inside and outside foraminiferal shells, characterized by heavy δ18O and depleted δ13C of both benthic and planktonic foraminifera. The similarities between the events observed over both terminations advocate for a common driver for the episodic release of geological methane stocks. Our favored model is recurrent leakage of shallow gas reservoirs below the gas hydrate stability zone along the margin of western Svalbard that can be reactivated upon initial instability of the grounded, marine-based ice sheets. Analogous to this model, with the current acceleration of the Greenland ice melt, instabilities of existing methane reservoirs below and nearby the ice sheet are likely.

Temperatures of Late Cretaceous (Campanian) methane-derived authigenic carbonates from the Western Interior Seaway, South Dakota, USA, using clumped isotopes

Abstract Methane seep deposits, comprising large, carbonate-rich mounds formed from hydrocarbon seepage, were widely distributed in the Late Cretaceous Western Interior Seaway (WIS) of North America. Well-preserved, methane-derived authigenic carbonates (MDACs) from these deposits have been shown to retain petrological, paleontological, and geochemical imprints of their ancient depositional setting, all of which are important for understanding the dynamics and evolution of the shallow, epeiric WIS. To better characterize the environmental conditions of WIS seeps, we applied clumped isotope paleothermometry to magnesium calcite MDAC samples from five seep localities in the upper Campanian Pierre Shale, South Dakota, USA. We measured 21 subsamples, including 18 micritic carbonates and demonstrated apparent clumped isotope equilibrium between MDACs and WIS bottom waters. Extreme 13C depletion in most samples (δ13C ranging to −45.44‰) indicates they were precipitated with oxidized methane as a major source of dissolved inorganic carbon, which itself implies a close association with ancient methanotrophic metabolism. The average clumped isotope paleotemperature from the micritic carbonates is 23 ± 7 °C (1σ standard deviation), which agrees with bottom water paleotemperatures inferred from δ18O measurements of MDACs and well-preserved mollusk shells at similar localities in the WIS. The calculated average δ18Ow value for these samples is −0.5 ± 1.7‰ (1σ SD), which is indistinguishable from previously reported calculation on Campanian seawater δ18Ow from fossil mollusk shells, but elevated above younger fossils collected from other locations in the WIS. Our conclusions are inconsistent with previously hypothesized disequilibrium for WIS MDAC clumped isotope and therefore we propose that fossil MDAC deposits may be used as paleotemperature archives.

The Plio-Pleistocene seepage history off western Svalbard inferred from 3D petroleum systems modelling

Methane seepage off the coast of Svalbard is demonstrated by active gas flares in the water column today and through precipitation of methane-derived authigenic carbonates (MDAC) over the past 160 000 years. Though submarine discharge of thermogenic methane is well documented, the geological history of past leakage is still debated, largely due to unconstrained free gas sources and seepage trigger mechanisms. We have assembled a high-resolution 3D petroleum systems model to evaluate the impact and charge of potential thermogenic hydrocarbons on the Vestnesa Ridge, NW Svalbard. We show that gaseous hydrocarbons, originating from Miocene age terrigenous organic matter, accumulates largely in ~2 million-year-old (Ma) sedimentary sequences underneath the pockmark system on the ridge's crest. These traps are constantly charged until present day. The supply of free gas to the gas hydrate stability zone (GHSZ) initiated the hydrate formation at ~3.0 Ma. We also show that gas leakage to the seafloor is governed by fault corruption of the hydrocarbon traps and not by excess pore fluid pressure. The onset of episodic seafloor seepage on Vestnesa Ridge can be associated with the first shelf edge glaciation of the Svalbard-Barents Sea ice sheet (SBIS), ~1.5 Ma ago. The results of the modelled petroleum system are consistent with the notion that repeated forebulge uplift and subsidence, due to cyclic SBIS build-up and decay, can be advocated as a mechanism that repeatedly caused extensional fracturing of the eastern Vestnesa Ridge segment. This fault damage affected modelled gas accumulations and led to the formation of hydrocarbon migration pathways to the seafloor. Repeated tapping into hydrocarbon reservoirs due to (a) fracture formation promoted by glacial isostatic adjustments (GIA) and (b) fracture re-activation could explain recent observations of multiple seepage events on Vestnesa Ridge during episodes of intense cooling over the past 160.000 years.

Dynamic and history of methane seepage in the SW Barents Sea: new insights from Leirdjupet Fault Complex

Methane emissions from Arctic continental margins are increasing due to the negative effect of global warming on ice sheet and permafrost stability, but dynamics and timescales of seafloor seepage still remain poorly constrained. Here, we examine sediment cores collected from an active seepage area located between 295 and 353 m water depth in the SW Barents Sea, at Leirdjupet Fault Complex. The geochemical composition of hydrocarbon gas in the sediment indicates a mixture of microbial and thermogenic gas, the latter being sourced from underlying Mesozoic formations. Sediment and carbonate geochemistry reveal a long history of methane emissions that started during Late Weichselian deglaciation after 14.5 cal ka BP. Methane-derived authigenic carbonates precipitated due to local gas hydrate destabilization, in turn triggered by an increasing influx of warm Atlantic water and isostatic rebound linked to the retreat of the Barents Sea Ice Sheet. This study has implications for a better understanding of the dynamic and future evolution of methane seeps in modern analogue systems in Western Antarctica, where the retreat of marine-based ice sheet induced by global warming may cause the release of large amounts of methane from hydrocarbon reservoirs and gas hydrates.