Gas Hydrate Sites Research Articles

Salt Diapir‐Driven Recycling of Gas Hydrate

AbstractBy harnessing both hypothetical, synthetic basin and gas hydrate (GH) system models and real‐world models of well‐studied salt diapir‐associated GH sites at Green Canyon (Gulf of Mexico) and Blake Ridge (U.S. Atlantic coast), we propose and demonstrate salt movement (and in particular, diapirism) to be a new mechanism for the recycling of marine GH. At Green Canyon, for example, we show that by considering this newly proposed diapir‐driven recycling mechanism in conjunction with previously proposed lithological control on sandy‐reservoir‐hosted hydrate at the base of the GH stability zone (BGHSZ; ∼bottom‐simulating reflector, BSR), modeled GH saturations match drilling data. Overall, salt diapir movement‐induced GH recycling provides a temperature‐driven mechanism by which GH saturations at the BGHSZ may reach >90 vol. % and by which GH volumes near and free gas volumes beneath the BGHSZ may be increased significantly through time. Interestingly, comparison of salt diapir‐driven recycling and sediment burial‐driven recycling scenarios suggests notably higher rates of recycling via diapir‐driven versus burial‐driven processes. Our results suggest that GH and associated free gas accumulations above salt diapir crests represent particularly attractive targets for unconventional and conventional hydrocarbon resource exploration and for scientific and academic drilling expeditions aimed at exploiting GH systems. Salt basins containing GH systems—including passive margin basins of the Gulf of Mexico, southeastern Brazil, and southwestern Africa—are therefore compelling localities for studying salt‐driven GH recycling and for salt diapir‐associated natural gas exploration.

A Scheduling Model in Capturing Methane Gas from Methane Clathrates Deposits

The execution of any project type, especially engineering-based projects, is usually time-based, efficiency-driven, and cost-effective. These factors are the deterministic parameters that engineer successful project completion. The application of scheduling models remains the best technique for achieving these three factors to their best degrees. Therefore, this study was centered on the impact study of applying the scheduling model in harvesting methane gas from methane clathrates deposits. Various data on gas hydrate reserves in the Niger Delta region of Nigeria were collected from relevant literature, studied, and analyzed. Such data includes the pictorial representation and description of the gas hydrate site in the Niger Delta region of Africa and various shapes and sizes of gas hydrate perimeters in the studied region positions of the gas reserves. The normal faults are projected on a bathymetric map of the study area and the bathymetric map of the Pockmark (with the stippled black line indicating the sea floor projection of a prominent N-S trending fracture in 3-D seismic data). As a type of scheduling model, the critical path method (CPM) was applied to develop the project’s work sequence using the activity on node (AON) architectural technique and Primavera P6 software after carefully identifying the primary operations involved in the project and their respective sub-operations or work breakdown structure (WBS). The risks associated with each operation were meticulously identified, with their consequent impact and exposure matrix determined using probabilistic measures of 1-5 according to the degree of the risk. Mitigation strategies were recommended for all the identified risks. The cost benefits of the project were X-rayed using parameters such as net present value (NPV), project payback time, internal rate of return (IRR), and net cumulative cash flow. From the results obtained, the CPM schedule showed that the project execution would last approximately ten months. All the operations involved in the project execution plan were all critical, proving that each activity should be completed within the scheduled run period. Else, the entire project would be affected. Also, risks with a high exposure matrix of 25, 12, and 4 were mitigated to 5, 3, and 0 using the recommended strategies. In addition, the project yielded an NPV of $20,736,951.04for the run period of 22 years after the execution of the project, IRR of 14%, and a payback time of 8 years (adding 2023 – the year of project execution) provided the daily production rate is maintained within 60,000-65,000MSCF/day. If the daily production rate increases, the cash flow and payback time will decrease. Therefore, the application of CPM in extracting methane gas from gas hydrates positively affected the operation through the vivid insights provided in workflow pattern/methodology risks effects and cost benefits.

Diagenetic analysis of shallow and deep-seated gas hydrate systems from the Bay of Bengal

This is the first systematic high-resolution rock magnetic study complemented by mineralogical and petrological observations conducted on sediment cores representing shallow (active cold seep; SSD-45/Stn-4/GC-01) and deep-seated (NGHP-01–15A) gas hydrate systems in the Bay of Bengal which addresses two key questions: (i) how magnetic minerals respond to the geochemical environment at two different diagenetic settings experiencing variable fluid sequence, and (ii) elucidates the control on the magnetite and greigite authigenesis in sulfidic, methanic, and gas hydrate bearing sediments. Titanomagnetite is the dominant detrital magnetic mineral identified in the studied cores from the Krishna-Godavari (K-G) basin along with diagenetic (pyrite) and authigenic (magnetite, greigite) minerals. Large detrital titanomagnetite and silicate-hosted (fine-grained) magnetic inclusions survived diagenetic dissolution during high sedimentation events. Magnetic proxies (ARM/SIRM and SIRM/χlf) provided useful insights on the diagenetic and authigenic formation and preservation of magnetic particles in the studied cores. Preferential diagenetic dissolution of finer (detrital) magnetic particles in sulfidic and authigenic formation of magnetite in methanic environment is clearly evident in the ARM/SIRM record of cores from both sites. Elevated values of SIRM/χlf in cores SSD-45/Stn-4/GC-01 (sulfidic and hydrate bearing) and NGHP-01–15A (methanic) indicate formation and preservation of ferrimagnetic authigenic (SP) greigite particles. Based on the magnetic proxies, we demonstrated that the formation of authigenic magnetite in the methanic environment of both sites is tightly linked with the microbial iron-reduction process. Multiple occurrences of authigenic carbonate provided evidence on the episodic intensification of anaerobic oxidation of methane (AOM) at active seep and silicate weathering coupled to microbial methanogenesis at deep-seated gas hydrate site respectively.

Cultivation and biogeochemical analyses reveal insights into methanogenesis in deep subseafloor sediment at a biogenic gas hydrate site

Gas hydrates deposited in subseafloor sediments are considered to primarily consist of biogenic methane. However, little evidence for the occurrence of living methanogens in subseafloor sediments has been provided. This study investigated viable methanogen diversity, population, physiology and potential activity in hydrate-bearing sediments (1–307 m below the seafloor) from the eastern Nankai Trough. Radiotracer experiments, the quantification of coenzyme F430 and molecular sequencing analysis indicated the occurrence of potential methanogenic activity and living methanogens in the sediments and the predominance of hydrogenotrophic methanogens followed by methylotrophic methanogens. Ten isolates and nine representative culture clones of hydrogenotrophic, methylotrophic and acetoclastic methanogens were obtained from the batch incubation of sediments and accounted for 0.5–76% of the total methanogenic sequences directly recovered from each sediment. The hydrogenotrophic methanogen isolates of Methanocalculus and Methanoculleus that dominated the sediment methanogen communities produced methane at temperatures from 4 to 55 °C, with an abrupt decline in the methane production rate at temperatures above 40 °C, which is consistent with the depth profiles of potential methanogenic activity in the Nankai Trough sediments in this and previous studies. Our results reveal the previously overlooked phylogenetic and metabolic diversity of living methanogens, including methylotrophic methanogenesis.

Combination of Silica Gel and Surfactin Promoting Methane Hydrate Formation

Abstract Recently, gas hydrates based technologies have been exploited for few novel applications such as storage and transpiration of natural gas, gas mixtures separation, CO2 capture, and seawater desalination. Most of these applications are currently facing a challenge of low rate of gas hydrate formation. Chemical additives like surfactants can play a role of a good kinetic promoter for gas hydrate formation. The present study reports the application of biosurfactant for enhancing gas hydrate formation. Biosurfactant was produced by Bacillus subtilis strain A21. These types of microbes show their presence in the real gas hydrate sites also. The surfactin was characterized using many sophisticated techniques, conforming the formation of surfactin. It was used in the presence of fixed bed media of silica gel, and it was observed that surfactin in the presence of silica gel increased the consumption of moles of methane as well as reduced the induction time also as well as the conversion was also increased up to 27.9% for 390 min for 1000 ppm surfactin hence indicating it to be a clean and novel promoter of methane hydrate formation in combination with silica gel which can replace its synthetic counterparts which have environmental concerns.

Thermogenic gas controls high saturation gas hydrate distribution in the Pearl River Mouth Basin: Evidence from numerical modeling and seismic anomalies

We integrate three-dimensional (3D) seismic data, well log and two-dimensional (2D) modeling to understand the accumulation and saturation of gas hydrates and their relationships with biogenic and thermogenic gases in the Pearl River Mouth Basin, South China Sea (Sites SH2, SH5, W17, and W19). The model based on physical, geochemical and geological parameters from shallow gas hydrate sites, deep oil sites and seismic interpretation, and it is tied to well-log and seismic quantitative interpretation, to predict the main controlling factors for gas hydrate distribution. The modeling results show that the biogenic methane generation is distributed within the strata shallower than 1500 mbsf (meters below the seafloor), whereas thermogenic gas generation ranges from 2300 mbsf to 6000 mbsf. The erosion surfaces of migrating canyons represent important pathways for upward migration of biogenic gas resulting in average hydrate saturation <20% below the ridges of canyons. The total organic carbon content is an important factor related to biogenically-sourced gas hydrate distribution. Higher gas saturation (>40%) at the base of gas hydrate stability zone (BGHSZ) is related to the focused migration of thermogenic gas along faults and throughout permeable carrier beds. Although gas chimneys are widely identified from the coherence attribute extracted from 3D seismic data, their impact on the obviously higher (locally up to 60%) gas hydrate saturations in the fine-grained sediments appears site-dependent and associated with fault activity. By comparing well log-derived gas hydrate saturations, our modeling shows that about 80% of the methane-forming hydrate is thermogenically-sourced at Sites W19 and W17. The integrated modeling effort presented in this work, based on provides a better understanding of the different contributions from different gas sources for gas hydrate accumulation along the northern slope of the South China Sea.

A Shallow Seabed Dynamic Gas Hydrate System off SW Taiwan: Results From 3‐D Seismic, Thermal, and Fluid Migration Analyses

AbstractLarge amounts of methane, a potent greenhouse gas, are stored in hydrates beneath the seafloor. Sea level changes can trigger massive methane release into the ocean. It is not clear, however, whether surficial seafloor processes can cause comparable discharge. Previously, fluid migration was difficult to study due to a lack of spatially dense seismic and thermal observations. Here we examine a gas hydrate site at Four‐Way‐Closure Ridge off SW Taiwan using a high‐resolution 3‐D seismic cube, together with bottom‐simulating reflections (BSRs) mapped in the cube, a thermal probe data set, and 3‐D thermal modeling results. We document, on a scale of tens of meters, the interaction between surficial sedimentary processes, fluid flow, and a dynamic gas hydrate system. Fluid migrates upward through dipping permeable strata in the limb, the slope basin, and along thrust faults and ridge‐top normal faults. The seismic data also reveal several double BSRs that underlie seabed sedimentary sliding and depositional features. Abrupt changes in subsurface pressure and temperature due to the rapid seabed sedimentary processes can cause a rapid shift of the base of the gas hydrate stability zone. This shift may be either downward or upward and would result in the accumulation or dissociation of hydrate in sediments sandwiched by the double BSRs, respectively. We propose that dynamic surficial processes on the seafloor together with shallow focused fluid flow affect hydrate distribution and saturation at depth and may even result in methane expulsion into the ocean if such localized features are common along convergent plate boundaries.

A gas hydrate site with bi-verging folding in the outer wedge offshore SW Taiwan: Results from kinematic structural modeling and finite strain analysis

Understanding the structural evolution of complex convergent plate boundaries could contribute to linking the anticipated fluid production and transportation at depth to the measured amounts of fluid stored in hydrate methane. To better understand fluid behavior within a complex convergent boundary, we propose an evolution model for a set of doubly plunging, oppositely-verging structures referred to as Ridge A and the Four-Way Closure Ridge (FWCR), located offshore southwestern Taiwan. The structures exhibit 1) initial deformation along a decollement forming a seaward (westward)-verging detachment fold, followed by 2) a landward (eastward)-verging fault propagation fold (trishear) about 8 km west of the detachment fold, and 3) a westward-verging low-angle thrusting modifying the previous structures. Furthermore, finite strain analyses based on the kinematic model suggest high pore space reduction between the detachment and fault propagation folds. The volume of methane possibly expelled during the pore space reduction is not enough to explain the high hydrocarbon concentration necessary for hydrate formation. Kinematic modeling along with finite strain analyses support the possibility of deep sourced fluid migration along such bi-vergent structures at this hydrate-rich site.

Learning features from georeferenced seafloor imagery with location guided autoencoders

AbstractAlthough modern machine learning has the potential to greatly speed up the interpretation of imagery, the varied nature of the seabed and limited availability of expert annotations form barriers to its widespread use in seafloor mapping applications. This motivates research into unsupervised methods that function without large databases of human annotations. This paper develops an unsupervised feature learning method for georeferenced seafloor visual imagery that considers patterns both within the footprint of a single image frame and broader scale spatial characteristics. Features within images are learnt using an autoencoder developed based on the AlexNet deep convolutional neural network. Features larger than each image frame are learnt using a novel loss function that regularises autoencoder training using the Kullback–Leibler divergence function to loosely assume that images captured within a close distance of each other look more similar than those that are far away. The method is used to semantically interpret images taken by an autonomous underwater vehicle at the Southern Hydrates Ridge, an active gas hydrate field and site of a seafloor cabled observatory at a depth of 780 m. The method's performance when applied to clustering and content‐based image retrieval is assessed against a ground truth consisting of more than 18,000 human annotations. The study shows that the location based loss function increases the rate of information retrieval by a factor of two for seafloor mapping applications. The effects of physics‐based colour correction and image rescaling are also investigated, showing that the improved consistency of spatial information achieved by rescaling is beneficial for recognising artificial objects such as cables and infrastructures, but is less effective for natural objects that have greater dimensional variability.

Modeling of rising methane bubbles during production leaks from the gas hydrate sites of India

ABSTRACTNatural gas hydrates is considered as a strategic unconventional clean hydrocarbon resource in the energy sector. Understanding the behavior of the rising methane gas bubbles during production leaks from the deep marine gas hydrate reservoirs well head is essential for environmental impact studies and to design environmental monitoring systems. Numerical model for quantitatively characterizing the vertical dissolution pattern of the wellhead released methane gas bubbles is analyzed for three potential gas hydrate locations in India. Simulation results indicate that the methane bubbles with diameter of 10 mm can transport methane gas till 650, 800, and 750 m from the seabed in the Krishna–Godavari(KG), Mahanadi and Andaman basins respectively. Results brought out that potential well head damage during methane hydrate production at 1050 m water depth could release up to 28 m3 of methane gas, in which 50% of the molar mass shall get dissolved within 40 m of water column from the seafloor.

Organic matter in surface sediments from the Gulf of Mexico and South China Sea: Compositions, distributions and sources

Sediments from the Gulf of Mexico (GOM) and the South China Sea (SCS) were analyzed. The low δ13 C values of pentamethylicosane (PMIs) and fatty acids (−81.3 to −85.2‰) were found in only the S-1 sample collected from the GOM, indicating that methanogenic archaea associated with gas hydrate formation contributed to the sediment organic matter. Principle component analysis of fatty acids suggested that similar microbial biomass was found in the S-1, S-9, O-3 and O-5 samples. However, a comparison of the alkanes, fatty acids, and alcohols indicated that the percentage of n-alkan-2-ols in the S-1 sample from the GOM was the highest, while n-alkanes and n-fatty acids were the highest percentages in other samples from the GOM and SCS. This finding suggests that microbial species or the oxidation/reduction environment of the sample site of S-1 were different from those of the other samples. The present study provides a basis for detecting gas hydrate sites on the seafloor of the SCS.

A case study on pseudo 3-D Chirp sub-bottom profiler (SBP) survey for the detection of a fault trace in shallow sedimentary layers at gas hydrate site in the Ulleung Basin, East Sea

A pseudo 3-D Chirp sub-bottom profiler (SBP) survey was conducted to define the extension of a fault that was previously identified on low-resolution 2-D seismic data with an emphasis on the shallow sedimentary layers and to determine if the fault extends to the seafloor. The geophysical survey was conducted as part of an environmental impact assessment for a proposed gas hydrate production test in the Ulleung Basin, East Sea. The Chirp SBP raw data were acquired over an area of 1km×1km with an average line spacing of 20m. To produce a 3-D Chirp SBP volume, we developed an optimal processing sequence that was divided into two steps. The first phase of 2-D data processing included a sweep signature estimation, correlation, deconvolution, swell effect correction, and migration. The second phase of 3-D data processing was composed of a bin design, bin gathering of the final processed 2-D data set, amplitude normalization, and residual statics correction. The 3-D Chirp SBP volume provides enhanced imaging especially due to the residual static processing using a moving average method and shows better continuity of the sedimentary layers and consistency of the reflection events than the individual 2-D lines. Deformation of the seafloor as a result of the fault was detected, and the fault offset increases in the deeper sedimentary layers. We also determined that the fault strikes northwest-southeast. However, the shallow sub-seafloor sediments have high porosities and therefore do not exhibit brittle fault-behavior but rather deform continuously due to fault movement.

Time integrated variation of sources of fluids and seepage dynamics archived in authigenic carbonates from Gulf of Mexico Gas Hydrate Seafloor Observatory

Authigenic carbonate rocks recovered from the Gulf of Mexico Gas Hydrate Seafloor Observatory in Mississippi Canyon block 118 (MC118) at approximately 900m water depth were studied using mineralogical, bulk geochemical, and lipid biomarker analyses. Carbonate rocks occurred as fractured blocks and nodular masses incorporated in carbonate breccias. The carbonates were comprised mainly of high-Mg-calcite and aragonite. The stable carbon isotope composition (δ13C) of authigenic carbonate varied from −29.8‰ to −18.1‰ vs. V-PDB, suggesting a complex mixture of various carbon sources, including dissolved marine inorganic carbon (DIC), oil, as well as methane. Oxygen isotopes (δ18O) varied from +3.4‰ to +5.8‰. The observed 18O-enrichment in relation to calculated equilibrium values in the carbonates probably reflects decomposition of gas hydrates. The most abundant lipid biomarkers in the carbonates were isoprenoidal glycerol dibiphytanyl glycerol tetraethers (GDGTs), predominated by GDGT-2 and GDGT-3, which are typically indicators of anaerobic methane oxidizing archaea (ANMEs). Mono- and bicyclic biphytanes (derived after ether cleavage of GDGT-2 and GDGT-3) showed strong 13C-depletion, which is characteristic for ANMEs. Interestingly, large differences between the δ13C values of the archaeal diether archaeol and acyclic biphytane on the one hand and monocyclic biphytane on the other hand suggest the presence of archaea other than ANMEs. Archaeol and GDGT-0 (containing two acyclic biphytane moieties) are commonly assigned to various methanogenic archaea. Where methane seepage activity is intermediate or low within acoustic wipeout zones at the MC118 gas hydrate site nowadays, microbial communities must have coped with changing conditions as well as longer-term fluctuations in oil and gas seepage or the temporary cessation of hydrocarbon flux in the past. The change from methane seepage to oil seepage or vice versa in addition to flux variability apparently favors the establishment of complex prokaryotic communities dominated by archaea. In addition to anaerobic oxidation of methane, local production of methane is apparently prominent at the study site based on the occurrence of biomarkers of methanogens in the authigenic carbonate. This finding adds to the ongoing multidisciplinary effort to better constrain the environment at the MC118 observatory site and to determine the locally dominant biogeochemical processes.

Two dimensional fluid flow models at two gas hydrate sites offshore southwestern Taiwan

Fluid migration patterns are important for understanding gas hydrate and hydrocarbon systems. However, conducting experiments on or below the seafloor is difficult because crustal fluid flow rates are usually very slow, so long term observations are needed. Temperature can be used as a good tracer for studying fluid flows. Temperatures derived from bottom-simulating reflectors (BSRs) might help to understand fluid migration patterns in shallow marine sediments. In this study, we studied 2D fluid flow patterns in two potential gas hydrate provinces offshore southwestern Taiwan: the Yung-An Ridge in the active margin and Formosa Ridge in the passive margin. We used 2D bathymetry, average seafloor temperatures and regional geothermal gradients measured by thermal probes, as constraints to construct 2D theoretical conductive temperature fields using finite element methods. We then compared the BSR-based temperature with the theoretical conductive temperature field. The results show a temperature discrepancy attributed to advective heat transfer due to fluid migration. For the Yung-An Ridge, the BSR-based temperatures are about 2°C higher than the model: Especially in (1) near a fault zone, (2) under the eastern flank where there are strong seismic reflectors in a pseudo-3D seismic dataset, and (3) near a fissure zone. For the Formosa Ridge, our results showed a distinct decrease in temperatures around the southern peak of the ridge, where an active gas plume was found. BSR-based temperatures predict on average 2°C lower than the model. At these two sites, the shallow temperature fields are strongly affected by 2D bathymetry. However, new insights regarding fluid flow patterns can be obtained using this model approach.

Molecular and isotopic signatures in sediments and gas hydrate of the central/southwestern Ulleung Basin: high alkalinity escape fuelled by biogenically sourced methane

Natural marine gas hydrate was discovered in Korean territorial waters during a 2007 KIGAM cruise to the central/southwestern Ulleung Basin, East Sea. The first data on the geochemical characterization of hydrate-bound water and gas are presented here for cold seep site 07GHP-10 in the central basin sector, together with analogous data for four sites (07GHP-01, 07GHP-02, 07GHP-03, and 07GHP-14) where no hydrates were detected in other cores from the central/southwestern sectors. Hydrate-bound water displayed very low concentrations of major ions (Cl−, SO 4 2− , Na+, Mg2+, K+, and Ca2+), and more positive δD (15.5‰) and δ18O (2.3‰) signatures compared to seawater. Cl– freshening and more positive isotopic values were also observed in the pore water at gas hydrate site 07GHP-10. The inferred sulfate–methane interface (SMI) was very shallow ( 40 mM), but the carbon isotopic ratios of dissolved inorganic carbon (δ13CDIC) did not show minimum values typical of AOM. Moreover, macroscopic authigenic carbonates were not observed at any of the core sites. This can plausibly be explained by carbon with high δ13C values diffusing upward from below the SMI, increasing alkalinity via deep methanogenesis and eventually escaping as alkalinity into the water column, with minor precipitation as solid phase. This contrasts, but is not inconsistent with recent reports of methane-fuelled carbonate formation at other sites in the southwestern basin sector. Methane was the main hydrocarbon component (>99.85%) of headspace, void, and hydrate-bound gases, C1/C2+ ratios were at least 1,000, and δ13CCH4 and δDCH4 values were in the typical range of methane generated by microbial reduction of CO2. This is supported by the δ13CC2H6 signatures of void and hydrate-bound gases, and helps clarify some contradictory interpretations existing for the Ulleung Basin as a whole. In combination, these findings suggest that deep biogenic gas and pore waters migrate upward through pathways such as hydrofractures, and measurably influence the shallow carbon cycle. As a result, cation-adjusted alkalinity/removed sulfate diagrams cannot always serve to estimate the degree of alkalinity produced by sulfate reduction and AOM in high methane flux areas.

Direct analysis of sulfate reducing bacterial communities in gas hydrate‐impacted marine sediments by PCR–DGGE

Molecular investigations of the sulfate reducing bacteria that target the dissimilatory sulfite-reductase subunit A gene (dsr A) are plagued by the nonspecific performance of conventional PCR primers. Here we describe the incorporation of the FailSafe PCR System to optimize environmental analysis of dsr A by PCR amplification and denaturing gradient gel electrophoresis. PCR-DGGE analysis of dsr A composition revealed that SRB diversity was greater and more variable throughout the vertical profile of a marine sediment core obtained from a gas hydrate site (GC234) in the Gulf of Mexico than in a sediment core collected from a nearby site devoid of gas hydrates (NBP). Depth profiled dsr B abundance corresponded with sulfate reduction rates at both sites, though measurements were higher at GC234. This study exemplifies the numerical and functional importance of sulfate reducing bacteria in deep-sea sedimentary environments, and incremental methodological advancements, as described herein, will continue to streamline the analysis of sulfate reducer communities in situ.

Petrographic and geochemical characterization of seep carbonate from Bush Hill (GC 185) gas vent and hydrate site of the Gulf of Mexico

Authigenic carbonates are common at cold seep sites as a result of microbial oxidation of hydrocarbons. Seep carbonate samples were collected from the surface of the Bush Hill (Green Canyon Block 185, Gulf of Mexico), a mound containing gas hydrate. The carbonates consisted of oily, porous limestone slabs and blocks containing bioclasts and matrix. Analysis by X-ray diffraction shows that aragonite is the dominant mineral (89–99 wt% with an average of 94 wt%) in the matrix of seep carbonate. This cement occurs in microcrystalline, microspar, and sparite forms. The moderate 13C depletion of the seep carbonate (the most depleted one has δ 13C value of −29.4‰, and 26 of 38 subsamples have δ 13C values >−20.0‰) indicates that the non-methane hydrocarbons was incorporated during seep carbonate precipitation. Relative enrichment of 18O may be related to localized destabilization of gas hydrate or derived from 18O-enriched pore water originated from smectite–illite transition in the deep sediments. The total content of rare earth elements (REE) of the 5% HNO 3-treated solution of the carbonates is from 0.40 ppm to 30.9 ppm. The shale-normalized REE patterns show varied Ce anomalies from significantly negative, slightly negative, and no to positive Ce anomalies. Variable content of trace elements, total REE, and Ce anomalies in different samples and even in the different carbonate mineral forms (microcrystalline, microspar and sparite) of the same sample suggest that the formation condition of the Bush Hill seep carbonate is variable and complex, which is possibly controlled by the rate of fluid flux.

Mud volcanoes and gas hydrates in the Anaximander mountains (Eastern Mediterranean Sea)

Detailed multibeam, sedimentological, and geophysical surveys provide ample new data to confirm that the Anaximander Mountains (Eastern Mediterranean) are an important area for active mud volcanism and gas hydrate formation. More than 3000 km of multibeam track length was acquired during two recent missions and 80 gravity and box cores were recovered. Morphology and backscatter data of the study area have better resolution than previous surveys, and very detailed morphology maps have been made of the known targeted mud volcanoes (Amsterdam, Kazan and Kula), especially the Amsterdam “crater” and the related mud breccia flows. Gas hydrates collected repeatedly from a large area of Amsterdam mud volcano at a sub-bottom depth of around 0.3–1.5 m resemble compacted snow and have a rather flaky form. New gas hydrate sites were found at Amsterdam mud volcano, including the mud flow sloping off to the south. Gas hydrates sampled for the first time at Kazan mud volcano are dispersed throughout the core samples deeper than 0.3 m and display a ‘rice’-like appearance. Relative chronology and AMS dating of interbedded pelagic sediments (Late Holocene hemipelagic, sapropel layer S1 and ash layers) within the mud flows indicate that successive eruptions of Kula mud volcano have a periodicity of about 5–10 kyrs. New mud volcanoes identified on the basis of multibeam backscatter intensity were sampled, documented as active and named “ Athina” and “ Thessaloniki”. Gas hydrates were sampled also in Thessaloniki mud volcano, the shallowest (1264 m) among all the active Mediterranean sites, at the boundary of the gas hydrate stability zone. Biostratigraphical analyses of mud breccia clasts indicated that the source of the subsurface sedimentary sequences consists of Late Cretaceous limestones, Paleocene siliciclastic rocks, Eocene biogenic limestones and Miocene mudstones. Rough estimations of the total capacity of the Anaximander mud volcanoes in methane gas are 2.56–6.40 km 3.

Pyrite crystallization in seep carbonates at gas vent and hydrate site

Pyrite formed by the synergistic metabolism of methane oxidizing archaea and sulfate reducing bacteria has been found in seep carbonates where hydrates usually occur in the subsurface and gas vents out from seafloor in many places worldwide. These bacteria collaborate to oxidize venting methane and reduce seawater sulfate. The hydrogen sulfide and carbon dioxide produced in this process causes pyrite and calcite crystallization (seep carbonate precipitation). We show, using the microscope analysis, that the pyrite crystallization has both bacterial fossilization and crystallization in seep carbonates collected from gas vent and hydrate sites off Louisiana Coast in the Gulf of Mexico and near Dongsha Island in the South China Sea. The pyrite shows bacterial and crystal forms scattered in the calcites. The crystal pyrite occurs as cubic crystals to construct framboid. The bacterial pyrite causes spheroids, rods in nanometer scale to aggregate to layered spheroids, rod-chains, and worm-like forms. These bacterial forms are identical to the characteristic form of live MOA/SRB colonies observed in gas vent and hydrate sites.

Molecular biogeochemistry of sulfate reduction, methanogenesis and the anaerobic oxidation of methane at Gulf of Mexico cold seeps

The anaerobic oxidation of methane in aquatic environments is a globally significant sink for a potent greenhouse gas. Significant gaps remain in our understanding of the anaerobic oxidation of methane because data describing the distribution and abundance of putative anaerobic methanotrophs in relation to rates and patterns of anaerobic oxidation of methane activity are rare. An integrated biogeochemical, molecular ecological and organic geochemical approach was used to elucidate interactions between the anaerobic oxidation of methane, methanogenesis, and sulfate reduction in sediments from two cold seep habitats (one brine site, the other a gas hydrate site) along the continental slope in the Northern Gulf of Mexico. The results indicate decoupling of sulfate reduction from anaerobic oxidation of methane and the contemporaneous occurrence of methane production and consumption at both sites. Phylogenetic and organic geochemical evidence indicate that microbial groups previously suggested to be involved in anaerobic oxidation of methane coupled to sulfate reduction were present and active. The distribution and isotopic composition of lipid biomarkers correlated with microbial distributions, although concrete assignment of microbial function based on biomarker profiles was complicated given the observed overlap of competing microbial processes. Contemporaneous activity of anaerobic oxidation of methane and bicarbonate-based methanogenesis, the distribution of methane-oxidizing microorganisms, and lipid biomarker data suggest that the same microorganisms may be involved in both processes.