Microscale investigations of microbial communities in coastal surficial sediments

The upper millimeters of sediments are considered major locations of microbial colonization and activity. The goal of our study was to investigate variations of microbial communities in the uppermost sediment layers of the coastal Baltic Sea with emphasis on the complex interplay between microbiology and physico‐chemical sediment properties. We selected a high‐resolution methodological approach that combined the cryolanding sampling technique (spatial resolution of 250 μm) with microsensor‐, spectrophotometric and microscopic analyses. While the oxygen penetration depths in dark conditions ranged from 1.4 mm to 2.6 mm during the study period, this zone expanded by about 1 mm in light and could be divided into three micro‐horizons: (i) an upper zone with a high net O₂ production, (ii) an intermediate zone with increased O₂ consumption on account of light‐stimulated respiration and (iii) a lower zone with lower O₂ consumption. Time‐series experiments revealed a rapid response of the benthic microbial community to altered light intensities. In May and July, the net O₂ budget in the porewater of sediments was positive within 35 and 22 min after illumination, respectively, whereas in June O₂ production exceeded O₂ consumption after 112 min. The thickness of the O₂ production and O₂ consumption micro‐zones decreased from May to July coinciding with an increase in temperature. In May, sites of enhanced O₂ consumption were closely associated with subsurface maxima of microbial numbers and enzymatic activities indicating a tight coupling between photoautotrophic and heterotrophic processes between 1‐ and 2‐mm depth. In June and July, the microbial abundance and enzymatic activity hardly varied with depth. Spatial and temporal microheterogeneity of microbial distribution and activity in O₂ gradients was seen as a reflection of the complex interplay between microbiology and physico‐chemical sediment properties.     

Quantitative distribution of the meiobenthos in Baidaratskaya Bay (Kara Sea)

The quantitative characteristics and spatial distribution of the meiobenthos in Baidaratskaya Bay (Kara sea) were analyzed based on data collected in 1994–2007. The extremely high density of the meiobenthos (up to 8121 ind/10 cm², average 2318 ind/10 cm²) makes it possible to consider Baidaratskaya Bay among the most productive Arctic regions. The spatial distribution of the meiobenthos was mostly determined by the depth and sediment properties in the subtidal zone of the bay. The density of meiobenthic organisms decreased with depth, and with the increase of the small sediment fraction. The difference in the meiobenthic densities between the two coastal areas of the bay (Yamal and Jugora CAs) is also revealed. Such difference caused by the combined effects of small-scale and mesoscale factors, mainly by the grain size. Opposite changes in the meio- and macrobenthic biomass with depth is shown.     

Mineralogical and geochemical features of authigenic carbonates on seepings and hydrothermal fields (By the examples of the Black Sea reefs and the mounds of the lost city field)

Two genetically different types of authigenic carbonate mounds are studied: those within an active hydrothermal field related to serpentinite protrusions in the zone of intersection of a transform fracture zone and the Mid-Atlantic Ridge, and those in an active field of methane seepings in the Dnieper canyon of the Black sea. The general geochemical conditions under which authigenic carbonate formation occurs in the two fields considered were found. They include the presence of reduced H₂S, H₂, and CH₄ gases at the absence of free oxygen; the high alkalinity of the waters participating in the carbonate formation; the similarity of the textural and structural features of authigenic aragonite, which represents the initial mineral of the carbonate matter of the mounds; the paragenesis of aragonite with sulfide minerals; and the close relation of carbonate mounds with communities of sulfate-reducing and methane-oxidizing microorganisms. A new mechanism of formation of hydrothermal authigenic carbonates is suggested; it implies their microbial sulfate reduction over the hydrogen of the fluid in the subsurface zone (biosphere) of mixing between the hydrothermal solution and the adjacent seawater.     

Distribution and Variability of the Meiobenthic Assemblages near the Korean Polymetallic Nodule Claim Area of the Clarion-Clipperton Fracture Zone (Subequatorial NE Pacific)

This study was carried out as part of a baseline long-term environmental project in the proposed mining areas for an environmental impact assessment of future mining in the Clarion-Clipperton Fracture Zone (CCFZ). The community structure and distributional pattern of meiobenthos were investigated in the deep-sea bottom of the Clarion-Clipperton Fracture Zone of the northeastern Pacific in July 1998, 1999, 2001, 2003 and August 2004, 2005. Twenty one meiobenthic groups were found at the stations in the study area. The most abundant meiobenthos comprised nematodes followed by benthic foraminiferans and harpacticoid copepods. The maximum density of meiobenthos was 306 ind/10 cm² at the station located at 11°N (water depth, 4833 m), and the minimum density was 6 ind/10 cm² at the station located at 14°N (water depth, 5037 m). Oligotrophic conditions in the CCFZ seem to directly reflect the lower standing stocks of meiobenthos in the CCFZ compared to other deep-sea plains of similar depth. The latitudinal distribution pattern of meiobenthos in the study area seemed to be related with surface water primary productivity, which was connected to the water circulation pattern of the Pacific Ocean near the Equator, diverging at 8ºN latitude and converging at 5°N. The horizontal distribution of meiobenthic organisms in the study area showed high densities at the stations within 135–136°W. The densities of meiobenthic organismas within the CCFZ were high at stations with few manganese nodules on the sediment surface at low-latitude sites. In 1998, the observed relative high values of meiobenthic abundance were at stations from 5° to 6°N. Other stations from 7° to 10°N showed no significant fluctuations during the interannual sampling periods. It is considered that the inter-annual fluctuation of meiobenthos abundance is intimately related with a regime shift that may have occurred in the north Pacific between 1998 and 1999, the El Niño period. Vertical distribution of meiobenthic organisms showed the highest individual numbers in the surface sediment layers of 0～2 cm depth and a steep decreasing trend as sediment becomes deeper at the stations of high latitude located in 16～17°N. Size distribution analyses showed that organisms that fit into the sieve mesh size of 0.063 mm were abundant.     

Abundance of deep-sea meiobenthos off Sanriku,Northeastern Japan

Abundance of deep-sea meiobenthos off Sanriku, Northeastern Japan was studied quantitatively using sediment samples collected by box corers or an Okean grab. Sampling stations were established along a line transect which covered areas from off the mouth of Otsuchi Bay to the abyssal plain of the western Pacific crossing over the Japan Trench (water depths from 120 m to 7460 m). Abundance of meiobenthos decreased linearly with water depth down to 1503 m and became constant at stations deeper than 4130 m. Nematodes predominated over the other taxonomic groups at all stations. An equation to estimate meiofaunal abundance from several sediment characteristics, which was previously proposed by the first author based on data from tropical and subtropical regions of the western Pacific, was applied to the present boreal area. At one station where the Okean grab was used, the estimated value was 4.7 times more than the observed one. Except for the station, however, observed values fell within the confident range of estimated values. The estimated values were always higher than the observed ones at boxcorer stations, whereasvice versa at Okean-grab stations. These results suggested that keen attention is necessary in selecting sampling gear for ecological studies of deep-sea meiobenthos.     

Methane-dominated thermochemical sulphate reduction in the Triassic Feixianguan Formation East Sichuan Basin, China: towards prediction of fatal H2S concentrations

New sour pools have recently found in the Lower Triassic Feixianguan Fm carbonate reservoirs in the East Sichuan Basin in China with H₂S up to 17.4% by volume. A recent blowout from a well drilled into this formation killed hundreds of people as a result of the percentage concentrations of H₂S. In order to assess the origin of fatal H₂S as well as the cause of petroleum alteration, H₂S concentrations and the isotopes, δ³⁴S and δ¹³C have been collected and measured in gas samples from reservoirs. Anhydrite, pyrite and elemental sulphur δ³⁴S values have been measured for comparison. The high concentrations of H₂S gas are found to occur at depths >3000 m (temperature now at 100 °C) in evaporated platform facies oolitic dolomite or limestone that contains anhydrite nodule occurrence within the reservoirs. Where H₂S concentrations are greater than 10% its δ³⁴S values lie between +12.0 and +13.2‰ CDT. This is within the range of anhydrite δ³⁴S values found within the Feixianguan Fm (+11.0 to +21.7‰; average 15.5±3.5‰ CDT). Thus H₂S must have been generated by thermochemical sulphate reduction (TSR) locally within the reservoirs. Burial history analysis and fluid inclusion data reveal that the temperature at which TSR occurred was greater than about 130–140 °C, suggesting that the present depth-temperature minimum is an artifact of post-TSR uplift. Both methane and ethane were actively involved in TSR since the petroleum became almost totally dry (no alkanes except methane) and methane δ¹³C values become significantly heavier as TSR proceeded. Methane δ¹³C difference thus reflects the extent of TSR. While it is tempting to use a present-day depth control (>3000 m) to predict the distribution of H₂S in the Feixianguan Fm, this is an invalid approach since TSR occurred when the formation was buried some 1000–2000 m deeper than it is at present. The likelihood of differential uplift across the basin means that it is important to develop a basinal understanding of the thermal history of the Feixianguan Fm so that it is possible to determine which parts of the basin have been hotter than 130–140 °C.     

The Meiobenthos Along a Mediterranean Deep-Sea Transect off Calvi (Corsica) and in an Adjacent Canyon

Abstract. Meiobenthos densities (excluding hard-shcllcd foraminifcrans) were compared along a Mediterranean deep-sea transect off Calvi (Corsica) and in an adjacent canyon. Chloroplastic Pigment Equivalent values (CPE) provided an estimate of the amount of primary production reaching the bottom.
The stations along the transect were characterized by a low CPE content of the sediment, decreasing with increasing station depth. CPE values in the canyon were much higher, which probably resulted from import of material from the adjacent bay of Calvi. Similarly, meiobenthos densities along the transect were much lower than at comparable depths along the canyon.
Meiobenthos density was significantly and positively correlated with CPE values.
Nematodes were the most abundant taxon at all stations, followed by copepods + nauplii and the soft-shelled foraminiferans. The meiobenthos was most abundant in the upper half centimeter. Nematode and foraminiferan densities tended to decline less rapidly with increasing depth into the sediment. Specimens belonging to the recently described phylum Loricifera, larvae of the parasitic crustacean class Tantulocarida, and fragments of an infaunal Xenophyophoria (large protozoans) are reported for the first time from the Mediterranean.     

Comparison of marine gas hydrates in sediments of an active and passive continental margin

Two sites of the Deep Sea Drilling Project in contrasting geologic settings provide a basis for comparison of the geochemical conditions associated with marine gas hydrates in continental margin sediments. Site 533 is located at 3191 m water depth on a spit-like extension of the continental rise on a passive margin in the Atlantic Ocean. Site 568, at 2031 m water depth, is in upper slope sediment of an active accretionary margin in the Pacific Ocean. Both sites are characterized by high rates of sedimentation, and the organic carbon contents of these sediments generally exceed 0.5%. Anomalous seismic reflections that transgress sedimentary structures and parallel the seafloor, suggested the presence of gas hydrates at both sites, and, during coring, small samples of gas hydrate were recovered at subbottom depths of 238m (Site 533) and 404 m (Site 568). The principal gaseous components of the gas hydrates wer methane, ethane, and CO₂. Residual methane in sediments at both sites usually exceeded 10 mll^?1 of wet sediment. Carbon isotopic compositions of methane, CO₂, and ΣCO₂ followed parallel trends with depth, suggesting that methane formed mainly as a result of biological reduction of oxidized carbon. Salinity of pore waters decreased with depth, a likely result of gas hydrate formation. These geochemical characteristics define some of the conditions associated with the occurrence of gas hydrates formed by in situ processes in continental margin sediments.     

Bathymetric variations in vertical distribution patterns of meiofauna in the surface sediments of the deep Arctic ocean (HAUSGARTEN,Fram strait)

Deep-sea benthic communities and their structural and functional characteristics are regulated by surface water processes. Our study focused on the impact of changes in water depth and food supplies on small-sized metazoan bottom-fauna (meiobenthos) along a bathymetric transect (1200–5500 m) in the western Fram Strait. The samples were collected every summer season from 2005 to 2009 within the scope of the HAUSGARTEN monitoring program. In comparison to other polar regions, the large inflow of organic matter to the sea floor translates into relatively high meiofaunal densities in this region. Densities along the bathymetric gradient range from approximately 2400 ind. 10 cm^-2 at 1200 m to approximately 300 ind. 10 cm^-2 at 4000 m. Differences in meiofaunal distribution among sediment layers (i.e., vertical profile) were stronger than among stations (i.e., bathymetric gradient). At all the stations meiofaunal densities and number of taxa were the highest in the surface sediment layer (0–1 cm), and these decreased with increasing sediment depth (down to 4–5 cm). However, the shape of the decreasing pattern differed significantly among stations. Meiofaunal densities and taxonomic richness decreased gradually with increasing sediment depth at the shallower stations with higher food availability. At deeper stations, where the availability of organic matter is generally lower, meiofaunal densities decreased sharply to minor proportions at sediment depths already at 2–3 cm. Nematodes were the most abundant organisms (60–98%) in all the sediment layers. The environmental factors best correlated to the vertical patterns of the meiofaunal community were sediment-bound chloroplastic pigments that indicate phytodetrital matter.     

Organic geochemistry of sediments from chemosynthetic communities,Gulf of Mexico slope

We used a research submersible to obtain 33 sediment samples from chemosynthetic communities at 541–650 m water depths in the Green Canyon (GC) area of the Gulf of Mexico slope. Sediment samples from beneath an isolated mat of H₂S-oxidizing bacteria at GC 234 contain oil (mean = 5650 ppm) and C₁–C₅ hydrocarbons (mean = 12,979 ppm) that are altered by bacterial oxidation. Control cores away from the mat contain lower concentrations of oil (mean = 2966 ppm) and C₁–C₅ hydrocarbons (mean = 83.6 ppm). Bacterial oxidation of hydrocarbons depletes O₂ in sediments and triggers bacterial sulfate reduction to produce the H₂S required by the mats. Sediment samples from GC 185 (Bush Hill) contain high concentrations of oil (mean = 24,775 ppm) and C₁–C₅ hydrocarbons (mean = 11,037 ppm) that are altered by bacterial oxidation. Tube worm communities requiring H₂S occur at GC 185 where the sea floor has been greatly modified since the Pleistocene by accumulation of oil, thermogenic gas hydrates, and authigenic carbonate rock. Venting to the water column is suppressed by this sea-floor modification, enhancing bacterial activity in sediments. Sediments from an area with vesicomyid clams (GC 272) contain lower concentrations of oil altered by bacterial oxidation (mean = 1716 ppm) but C₁–C₅ concentrations are high (mean = 28,766 ppm). In contrast to other sampling areas, a sediment associated with the methanotrophic Seep Mytilid I (GC 233) is characterized by low concentration of oil (82 ppm) but biogenic methane (C₁) is present (8829 ppm).     

Chemical and microbiological aspects of acoustically turbid sediments: Preliminary investigations

Abstract

Chemical, microbiological, and geophysical measurements have been carried out on sediment cores collected from Holyhead Harbour and the Western Irish Sea, where acoustic subbottom profiling has established the presence of large areas of acoustically turbid sediments, commonly referred to as “gassy” sediments. Gas analysis of these cores have shown that the acoustic turbidity was most probably due to high concentrations (>100 nM/mL) of methane occurring at subsurface depths.

Microcosm experiments on sediment slurries from Holyhead Harbour confirm that acetate and H₂/CO₂ are important precursors for methane generation. In sediments from Holyhead Harbour methanogenesis could be slightly stimulated by the addition of H₂/CO₂ and sulfate (1 mM). This suggested that in surface sediments sulfate reduction and methanogenesis can occur concurrently. Such a situation may explain the appearance of gas plumes and gas pockets detected acoustically at the sediment surface in several regions of the Western Irish Sea. More detailed studies are needed to evaluate fully why some sedimentary environments in the Western Irish Sea are more prone than others to gas accumulation.     

Gas and fluid venting at the Makran accretionary wedge off Pakistan

The Makran accretionary complex shows a distinct bottom-simulating reflector, indicating a thick gas-hydrate-bearing horizon between the deformational front and about 1350 m water depth which seals off the upward flow of gas-charged fluids. A field of presently inactive mud diapirs with elevations up to 65 m was discovered in the abyssal plain seawards of the deformation front, suggesting that in the past conditions were favorable for periodic but localized vigorous mud diapirism. Regional destabilization of the gas hydrate leading to focused flow was observed where deep-penetrating, active faults reach the base of the gas-hydrate layer, as in a deeply incised submarine canyon (2100–2500 m water depth). At this location we discovered seeps of methane and H₂S-rich fluids associated with chemoautotrophic vent faunas (e.g., Calyptogena sp.). Driven by the accretionary wedge dynamics, the landward part of the gas-hydrate layer below the Makran margin is being progressively uplifted. Due to reduced hydrostatic pressure and rising ocean bottom-water temperatures, gas hydrates are progressively destabilized and dissociated into hydrate water, methane and H₂S. Sediment temperatures lie outside the methane stability field wherever water depth is less than 800 m. Above this depth, upward migration of fluids to the seafloor is unimpeded, thus explaining the abundance of randomly distributed gas seeps observed at water depths of 350 to 800 m. Received: 14 June 1999 / Revision accepted: 6 February 2000     

Microbially mediated methane and sulfur cycling in pockmark sediments of the Gdansk Basin, Baltic Sea

In the Russian sector of the Gdansk Basin (Baltic Sea), high organic matter influx fuels microbial processes resulting in the formation of reduced sediments with elevated methane concentrations. Investigated areas of geoacoustic anomalies (～245 km²) were found to contain three distinct geomorphologic structures (pockmarks), with a total area of ～1 km². Methane anomalies recorded in the water above one of these pockmarks were traced as high as 10 m above the bottom. In pockmark sediments, sulfate reduction and anaerobic oxidation of methane (AOM) occurred at high rates of 33 and 50 µmol dm^?3 day^?1, respectively. Integrated over 0–180 cm sediment depths, AOM exceeded methanogenesis almost tenfold. High AOM rates resulted from methane influx from deeper sediment layers. The δ¹³C signature of methane carbon (?78.1 to ?71.1‰) indicates the biogenic origin of pockmark methane. In pockmark sediments, up to 70% of reduced sulfur compounds was possibly produced via AOM.     

Sediment Flux of Particulate Organic Phosphorus in the Open Black Sea

The interannual variation of the monthly average (weighted average) concentrations of particulate organic phosphorus (P_POM) in the photosynthetic layer, oxycline, redox zone, and H₂S zone in the open Black Sea is estimated based on long-term observation data. The suspension sedimentation rates from the studied layers are assessed using model calculations and published data. The annual variation of P_POM sediment fluxes from the photosynthetic layer, oxycline, redox zone, and upper H₂S zone to the anaerobic zone of the sea and the correspondingly annual average values are estimated for the first time. A regular decrease in the P_POM annual average flux with depth in the upper active layer is demonstrated. A correlation between the annual average values of P_POM sediment flux from the photosynthetic layer and ascending phosphate flux to this layer is shown, which suggests their balance in the open sea. The results are discussed in terms of the phosphorus biogeochemical cycle and the concept of new and regenerative primary production in the open Black Sea.     

Effect of barite on meiofauna in a flow-through experimental system

The effects of barite (94–96% BaSO₄), a major constituent of drilling muds used in marine oil drilling operations, on meiofauna were studied in an experimental flow-through system. Aquaria containing sand or varying proportions of barite and sand received a continuous supply of unfiltered seawater from Santa Rosa Sound, Florida, for ten weeks. At the end of this period the composition, biomass and vertical distribution of the meiofauna were determined. Most of the meiofauna (>99%) occurred in the highly aerobic upper 2 cm portion of the substratum. Rotifera, Foraminifera, Hydrozoa, Turbellaria, Ostracoda, Polychaeta and Bivalvia did not exhibit significant differences between control and experimental aquaria. However, the densities of Nematoda, Copepoda and Copepoda nauplii varied with the substrate composition. The meiofaunal densities in the aquaria containing 1:10 or 1:3 mixtures of barite and sand were greater than that in aquaria containing sand alone. A marked decrease in meiofaunal density was evident in aquaria containing 5·5 cm of sand covered with a 0·5 cm layer of barite.     

Gas hydrates from the continental slope,offshore Sakhalin Island,Okhotsk Sea

Ten gas-vent fields were discovered in the Okhotsk Sea on the northeast continental slope offshore from Sakhalin Island in water depths of 620—1040 m. At one vent field, estimated to be more than 250 m across, gas hydrates, containing mainly microbial methane (¹³C = –64.3), were recovered from subbottom depths of 0.3–1.2 m. The sediment, having lenses and bedded layers of gas hydrate, contained 30–40% hydrate per volume of wet sediment. Although gas hydrates were not recovered at other fields, geochemical and thermal measurements suggest that gas hydrates are present.     

Cycling of dissolved and particulate nitrogen and carbon in the Framvaren Fjord, Norway: stable isotopic variations

The reaction pathways of nitrogen and carbon in the Framvaren Fjord (Norway) were studied through stable isotope analysis (δ¹⁵N and δ¹³C) of dissolved inorganic and particulate organic matter (POM). The variations in the isotopic compositions of the various C and N pools within the water column were use to evaluate the historical deposition of material to the sediments. The high δ¹⁵N-NH₄⁺ at the O₂/H₂S interface, as a consequence of microbial uptake between 19 and 25 m, results in extremely depleted δ¹⁵N-particulate nitrogen (PN) of approximately 1‰ within the particulate maximum at approximately 19 m. The carbon isotopic distribution of dissolved inorganic carbon (DIC) and particulate organic carbon (POC) within the interface suggests that the distinct microbial flora (Chromatium sp. and Chlorobium sp.) fractionate inorganic carbon to different degrees. The extremely light δ¹³C-POC within the interface (−31‰) appears to be a result of carbon uptake by Chromatium sp. while δ¹³C-POC of −12‰ is more indicative of Chlorobium sp. Nitrogen isotopic mass balance calculations suggested that approximately 75% of the material sinking to the sediments was derived from the dense particulate maximum between 19 and 25 m. The sediment distribution of nitrogen isotopes varied from 2‰ at the surface to approximately 6‰ at 30 cm. The nitrogen isotopic variations with depth may be an indicator of the depth or position of the O₂/H₂S interface in the fjord. Low sediment δ¹⁵N indicated that the interface was within the photic zone of the water column, while more enriched values suggested that the interface was lower in the water column potentially allowing for less fractionation during biological incorporation of dissolved inorganic nitrogen. Results indicate that the dense layers of photo-autotrophic bacteria in the upper water column impart unique carbon and nitrogen isotopic signals that help follow processes within the water column and deposition to the sediments.     

Meiobenthos assemblages in the mekong estuarine system with special focus on free-living marine nematodes

Meiobenthos assemblages in eight estuaries of the Mekong river system were investigated in August 2008 (from the Cua Tieu estuary to the Tran De estuary). In each estuary, one sampling station was established for meiobenthos sampling. Twelve major taxa of meiobenthos were recorded in this estuarine system, including Nematoda, Copepoda, Turbellaria, Polychaeta, Oligochaeta, Tardigrada, Bivalvia, Ostracoda, Amphipoda, Cumacea, Gastrotricha, Gastropoda, and Crustacean Nauplii larvae. The densities of the meiobenthos range from 581 to 3168 inds/10 cm². Nematodes always occupy the highest numbers with a percentage ranging from 64–99%. There are 135 nematode genera recorded in this study with the following as dominant genera Desmodora, Leptolaimus, Halalaimus, Thalassomonhystera, Theristus, Daptonema, Rhynchonema, Parodontophora, and Oncholaimus. Although the biodiversity of the meiobenthos at higher taxa level is not high compared to other marine environments, the estimates of nematode biodiversity at the genus level indicates high values. The increase in number of genera with increasing sampling intensity illustrate that the diversity is underestimated and would have been higher if the authors had considered a larger number of individuals, more replicates per station, and more sampling stations.     

Gas hydrates in shallow deposits of the Amsterdam mud volcano, Anaximander Mountains, Northeastern Mediterranean Sea

We investigated gas hydrate in situ inventories as well as the composition and principal transport mechanisms of fluids expelled at the Amsterdam mud volcano (AMV; 2,025 m water depth) in the Eastern Mediterranean Sea. Pressure coring (the only technique preventing hydrates from decomposition during recovery) was used for the quantification of light hydrocarbons in near-surface deposits. The cores (up to 2.5 m in length) were retrieved with an autoclave piston corer, and served for analyses of gas quantities and compositions, and pore-water chemistry. For comparison, gravity cores from sites at the summit and beyond the AMV were analyzed. A prevalence of thermogenic light hydrocarbons was inferred from average C₁/C₂₊ ratios <35 and δ¹³C-CH₄ values of ?50.6‰. Gas venting from the seafloor indicated methane oversaturation, and volumetric gas–sediment ratios of up to 17.0 in pressure cores taken from the center demonstrated hydrate presence at the time of sampling. Relative enrichments in ethane, propane, and iso-butane in gas released from pressure cores, and from an intact hydrate piece compared to venting gas suggest incipient crystallization of hydrate structure II (sII). Nonetheless, the co-existence of sI hydrate can not be excluded from our dataset. Hydrates fill up to 16.7% of pore volume within the sediment interval between the base of the sulfate zone and the maximum sampling depth at the summit. The concave-down shapes of pore-water concentration profiles recorded in the center indicate the influence of upward-directed advection of low-salinity fluids/fluidized mud. Furthermore, the SO ₄ ^2? and Ba²⁺ pore-water profiles in the central part of the AMV demonstrate that sulfate reduction driven by the anaerobic oxidation of methane is complete at depths between 30 cm and 70 cm below seafloor. Our results indicate that methane oversaturation, high hydrostatic pressure, and elevated pore-water activity caused by low salinity promote fixing of considerable proportions of light hydrocarbons in shallow hydrates even at the summit of the AMV, and possibly also of other MVs in the region. Depending on their crystallographic structure, however, hydrates will already decompose and release hydrocarbon masses if sediment temperatures exceed ca. 19.3°C and 21.0°C, respectively. Based on observations from other mud volcanoes, the common occurrence of such temperatures induced by heat flux from below into the immediate subsurface appears likely for the AMV.     

Authigenic barite nodules and carbonate concretions in the Upper Devonian shale succession of western New York – A record of variable methane flux during burial

Authigenic barite nodules associated with modestly ¹³C-depleted calcium carbonate concretions and ³⁴S-enriched pyrite at the bottom of the Upper Devonian Hanover Shale of western New York provide evidence of sulfate reduction coupled with anaerobic oxidation of methane (AOM). The methane, much of it biogenic in origin, may have diffused upward from Middle Devonian Marcellus Shale and perhaps the Upper Ordovician Utica Shale. Strong ³⁴S enrichment and high δ³⁴S/δ¹⁸O values of the barite nodules reflect: (1) substantial kinetic fractionation induced by microbial sulfate reduction perhaps intensified by a low seawater sulfate recharge rate and (2) upward delivery of Ba²⁺- and CH₄- bearing pore fluid sourced within underlying sulfate-depleted deposits. However, the association of authigenic calcium carbonate and barite in the same stratigraphic interval, especially the presence of barite overgrowths on carbonate concretions, is not consistent with what is known of AOM-related mineralization of a sediment column passing downward through the sulfate–methane transition (SMT). The documented early formation of authigenic carbonate followed by barite observed relations may reflect a diminished rate of methanogenesis and/or CH₄ supply. The tempered methane flux would have induced the SMT to descend the sediment column enabling barite to form within the same stratigraphic horizon that ¹³C-depleted calcium carbonate had most recently precipitated. Diminished methane flux may have been caused by burial-related passage of the organic-rich Marcellus Shale below the depth of peak biogenic methane generation and its replacement at that depth interval by organic-lean deposits of the upper part of the Hamilton Group. Subsidence of the SMT would have increased the preservation potential of authigenic barite. However, continued survival of the labile barite as it eventually moved through the SMT suggests that the underlying sulfate-depleted zone was strongly enriched in Ba²⁺.