Characterizing lipid biomarkers in methanotrophic communities of gas hydrate-bearing sediments in the Sea of Okhotsk

We studied specific lipid biomarkers of archaea and bacteria, that are associated with the anaerobic oxidation of methane (AOM) in a cold seep environment as well as the origin of sedimentary organic matter on the continental slope off NE Sakhalin in the Sea of Okhotsk. The organic geochemical parameters demonstrated that most of the sedimentary organic matter containing hydrate layers could be derived from marine phytoplankton and bacteria, except for a station (LV39-29H) which was remarkably affected by terrestrial vascular plant. Specific methanotrophic archaea biomarkers was vertically detected in hydrate-bearing cores (LV39-40H), coinciding with the negative excursion of the δ¹³C_org at core depths of 90–100 cm below the seafloor. These results suggest that methane provided from gas hydrates are already available substrates for microbes thriving in this sediment depth. In addition, the stable isotope mass balance method revealed that approximately 2.77–3.41% of the total organic carbon (or 0.036–0.044% dry weight sediment) was generated by the activity of the AOM consortium in the corresponding depth of core LV39-40H. On the other hand, the heavier δ¹³C values of archaeol in the gas hydrate stability zone may allow ongoing methanogenesis in deeper sediment depth.     

Lipid biomarkers for anaerobic oxidation of methane and sulphate reduction in cold seep sediments of Nyegga pockmarks (Norwegian margin): discrepancies in contents and carbon isotope signatures

Distributions and carbon isotopic compositions of microbial lipid biomarkers were investigated in sediment cores from the G11 and G12 pockmarks in the Nyegga sector of the Storegga Slide on the mid-Norwegian margin to explore differences in depth zonation, type and carbon assimilation mode of anaerobic methane-oxidizing archaea (ANMEs) and associated sulphate-reducing bacteria responsible for anaerobic oxidation of methane (AOM) in these cold seep environments. While the G11 site is characterised by black reduced sediments colonized by gastropods and Siboglinidae tubeworms, the G12 site has black reduced sediments devoid of fauna but surrounded by a peripheral occurrence of gastropods and white filamentous microbial mats. At both sites, bulk sediments contained abundant archaeal and bacterial lipid biomarkers substantially depleted in ¹³C, consisting mainly of isoprenoidal hydrocarbons and dialkyl glycerol diethers, fatty acids and non-isoprenoidal monoalkylglycerol ethers. At the G11 site, down-core profiles revealed that lipid biomarkers were in maximum abundance from 10 cm depth to the core bottom at 16 cm depth, associated with δ¹³C values of ?57 to ?136‰. At the G12 site, by contrast, lipid biomarkers were in high abundance in the upper 5 cm sediment layer, associated with δ¹³C values of ?43 to ?133‰. This suggests that, as expected from the benthic fauna characteristics of the sites, AOM takes place mainly at depth in the G11 pockmark but just below the seafloor in the G12 pockmark. These patterns can be explained largely by variable fluid flow rates. Furthermore, at both sites, a dominance of ANME-2 archaea accompanied by their bacterial partners is inferred based on lipid biomarker distributions and carbon isotope signatures, which is in agreement with recently published DNA analyses for the G11 pockmark. However, the present data reveal high discrepancies in the contents and δ¹³C values for both archaeal and bacterial lipid profiles, implying the possible involvement of at least two distinct AOM-related microbial consortia at the inferred AOM depth zonation of G11 and G12 pockmark sediments. In both sediment cores, the δ¹³C profiles for most archaeal lipids suggest a direct assimilation of dissolved inorganic carbon (DIC) in addition to methane by ANMEs (chemoautotrophy); constant and highly depleted δ¹³C profiles for PMI:3, an archaeal lipid biomarker presumably related to ANME-2, suggest a direct assimilation of ¹³C-depleted methane-derived carbon via AOM (methanotrophy). Evidently, the common approach of investigating lipid biomarker contents and δ¹³C signatures in cold seep sediments does not suffice to precisely discriminate between the carbon assimilation mode for each ANME archaeal group and associated bacteria. Rather, this needs to be combined with further specific labelling studies including different carbon sources (methane carbon, methane-derived organic intermediates and DIC) in order to unravel the metabolic pathways of each microbial consortium involved in AOM (ANME-1 vs. ANME-2 vs. ANME-3 archaeal group and associated bacteria).     

南海东北部冷泉区沉积物中有机质来源的生物标志物分析与环境指示意义

Multi-biomarker indexes were analyzed for two piston cores from potential cold seep areas of the South China Sea off southwestern Taiwan. Total organic carbon(TOC) normalized terrestrial(n-alkanes) and marine(brassicasterol, dinosterol, alkenones and iso-GDGTs) biomarker contents and ratios(TMBR, 1/Pmar-aq, BIT) were used to evaluate the contributions of terrestrial and marine organic matter(TOM and MOM respectively) to the sedimentary organic matter, indicating that MOM dominated the organic sources in Core MD052911 and the sedimentary organic matter in Core ORI-_(86)0-22 was mainly derived from terrestrial inputs, and different morphologies were the likely reason for TOM percentage differences. BIT results suggested that river-transported terrestrial soil organic matter was not a major source of TOM of sedimentary organic matter around these settings.Diagnostic biomarkers for methane-oxidizing archaea(MOA) were only detected in one sample at 172 cm depth of Core ORI-_(86)0-22, with abnormally high iso-GDGTs content and Methane Index(MI) value(0.94). These results indicated high anaerobic oxidation of methane(AOM) activities at or around 172 cm in Core ORI-_(86)0-22.However in Core MD052911, MOA biomarkers were not detected and MI values were lower(0.19–0.38), indicated insignificant contributions of iso-GDGTs from methanotrophic archaea and the absence of significant AOM activities. Biomarker results thus indicated that the discontinuous upward methane seepage and insufficient methane flux could not induce high AOM activities in our sampling sites. In addition, the different patterns of TEX_(86) and U_(37)~(K′) temperature in two cores suggested that AOM activities affected TEX_(86)37 temperature estimates with lower values in Core ORI-_(86)0-22, but not significantly on TEX_(86) temperature estimates in Core MD052911.     

Variations of methane induced pyrite formation in the accretionary wedge sediments offshore southwestern Taiwan

The accretionary wedge of offshore southwestern Taiwan contains abundant deposits of gas hydrate beneath the sea floor. High concentrations of methane in pore waters are observed at several locations with little data concerning historical methane venting available. To understand temporal variation of methane venting in sediments over geologic time, a 23-m-long Calypso piston core (MD05-2911) was collected on the flank of the Yung-An Ridge. Pore water sulfate, dissolved sulfide, dissolved iron, methane, sedimentary pyrite, acid volatile sulfide, reactive iron, organic carbon and nitrogen as well as carbonate δ¹³C were analyzed.Three zones with markedly different pyrite concentration were found at the study site. Unit I sediments (>20 mbsf) were characterized with a high amount of pyrite (251–380 μmol/g) and a δ¹³C-depleted carbonate, Unit II sediments (15–20 mbsf) with a low pyrite (15–43 μmol/g) and a high content of iron oxide mineral and Unit III sediments (<10 mbsf) by a present-day sulfate–methane interface (SMI) at 5 m with a high amount of pyrite (84–221 μmol/g) and a high concentration of dissolved sulfide.The oscillation records of pyrite concentrations are controlled by temporal variations of methane flux. With an abundant supply of methane to Unit I and III, anaerobic methane oxidation and associated sulfate reduction favor diagenetic conditions conducive for significant pyrite formation. No AOM signal was found in Unit II, characterized by typical organically-limited normal marine sediments with little pyrite formation. The AOM induced pyrite formation near the SMI generates a marked pyrite signature, rendering such formation of pyrite as a useful proxy in identifying methane flux oscillation in a methane flux fluctuate environment.     

First biomarker evidence for methane oxidation at cold seeps in the Southeast Atlantic (REGAB pockmark)

Sediment cores from the REGAB pockmark, an active cold seep area in the southeast Atlantic, were analysed for their lipid biomarker distribution and associated stable carbon isotopic composition. Substantial amounts of diagnostic archaeal lipids were found, consisting mainly of archaeol, sn-2 hydroxyarchaeol and crocetane. All archaeal lipids were profoundly depleted in ¹³C with δ¹³C values as low as −133‰. Concurrently, abundant monoalkylglycerolethers (MAGE), assigned to sulphate-reducing bacteria, were identified and showed strong ¹³C-depletions (δ¹³C between −86‰ and −95‰). The structural and isotopic patterns of these microbial lipids provided compelling evidence for anaerobic oxidation of methane (AOM) occurring in REGAB sediments, mediated by archaea and sulphate reducing bacteria. Lipid fingerprints indicated that anaerobic methanotrophic archaea (ANME-2) and sulphate-reducing bacteria from the Desulfosarcina/Desulfococcus cluster are the dominant AOM assemblages. Depth profiles implied that highest AOM takes place below the upper 2 cm, mainly in the 6–12 cm depth interval. Significant abundances of ¹³C-depleted diploptene and 4α-methylsterols were found as well, inferring that aerobic methanotrophy occurs in the surface sediment interval. This first biomarker study at the recently investigated cold seeps in the SE Atlantic expand on existing work on AOM settings and add new evidence for aerobic and anaerobic methanotrophic communities occurring in close vicinity.     

Importance of seagrass as a carbon source for heterotrophic bacteria in a subtropical estuary (Florida Bay)

A stable carbon isotope approach was taken to identify potential organic matter sources incorporated into biomass by the heterotrophic bacterial community of Florida Bay, a subtropical estuary with a recent history of seagrass loss and phytoplankton blooms. To gain a more complete understanding of bacterial carbon cycling in seagrass estuaries, this study focused on the importance of seagrass-derived organic matter to pelagic, seagrass epiphytic, and sediment surface bacteria. Particulate organic matter (POM), seagrass epiphytic, seagrass (Thalassia testudinum) leaf, and sediment surface samples were collected from four Florida Bay locations with historically different organic matter inputs, macrophyte densities, and primary productivities. Bulk (observed and those reported previously) and compound-specific bacterial fatty acid δ¹³C values were used to determine important carbon sources to the estuary and benthic and pelagic heterotrophic bacteria. The δ¹³C values of T. testudinum green leaves with epiphytes removed ranged from −9.9 to −6.9‰. Thalassia testudinum δ¹³C values were significant more enriched in ¹³C than POM, epiphytic, and sediment samples, which ranged from −16.4 to −13.5, −16.2 to −9.6, and −16.7 to −11.0‰, respectively. Bacterial fatty acid δ¹³C values (measured for br14:0, 15:0, i15:0, a15:0, br17:0, and 17:0) ranged from −25.5 to −8.2‰. Assuming a −3‰ carbon source fractionation from fatty acid to whole bacteria, pelagic, epiphytic, and sediment bacterial δ¹³C values were generally more depleted in ¹³C than T. testudinum δ¹³C values, more enriched in ¹³C than reported δ¹³C values for mangroves, and similar to reported δ¹³C values for algae. IsoSource mixing model results indicated that organic matter derived from T. testudinum was incorporated by both benthic and pelagic bacterial communities, where 13–67% of bacterial δ¹³C values could arise from consumption of seagrass-derived organic matter. The IsoSource model, however, failed to discriminate clearly the fraction of algal (0–86%) and mangrove (0–42%) organic matter incorporated by bacterial communities. These results indicate that pelagic, epiphytic, and sediment surface bacteria consumed organic matter from a variety of sources. Bacterial communities incorporated consistently seagrass-derived organic matter, the dominant macrophyte in Florida Bay, but seagrass δ¹³C values alone could not account fully for bacterial δ¹³C values.     

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.     

Using sediment geochemistry to infer temporal variation of methane flux at a cold seep in the South China Sea

Release of methane from the seafloor throughout the world's oceans and the biogeochemical processes involved may have significant effects on the marine sedimentary environment. Identification of such methane release events in marine sediment records can hence provide a window into the magnitude of ancient seeps. Here, we report on analysis of the geochemical composition of samples in a 12.3 m long sediment core (DH-5) collected from a seep site in the South China Sea (SCS). Our aim has been to investigate whether the evidence for the presence of methane release event within sediments is discernible from solid-phase sediment geochemistry. We show that sedimentary total sulfur (TS), δ³⁴S values of chromium reducible sulfur (δ³⁴S_CRS) along with total organic carbon (TOC) and total inorganic carbon (TIC) content can be used to infer the presence of methane release events in cold seep settings. At least three methane release events were identified in the studied core (Unit I at 400–550 cm, Unit II at 740–820 cm, and Unit III at 1000–1150 cm). According to the characteristic of redox-sensitive elements (eg., Mo, U and Mn), we suggest that methane flux has been changed from relatively high (Unit I) to low (Unit II and III) rates. This inference is supported by the coupled occurrence of ³⁴S-enriched sulfides in Unit II and III. AMS ¹⁴C dates from planktonic foraminifera in Unit I suggest that high methane flux event occurred at ∼15.4–24.8 kyr BP, which probably resulted in locally-focused aerobic methane oxidation. Overall, our results suggest that TS, TOC, TIC and δ³⁴S_CRS have potential for identifying present and fossil methane release events in marine sediments.     

天然气水合物赋存区甲烷渗漏活动的地球化学响应特征

综述了天然气水合物赋存区甲烷渗漏活动的地球化学响应指标的研究进展,分析了应用单一指标识别甲烷渗漏活动各自所存在的问题,包括浅表层沉积物孔隙水中CH_4、SO_4~(2–)、Cl~–等离子浓度随深度的变化;浅层沉积物全岩W_(TOC)(W表示质量分数,TOC表示总有机碳)和W_(TS)(TS表示总硫)之间的相关性及比值;自生碳酸盐岩δ~(13)C和δ~(18)O;自生矿物重晶石、黄铁矿、自生石膏的δ~(34)S;有孔虫壳体和生物标志化合物的δ~(13)C等。结果表明孔隙水中的CH_4、SO4_~(2–)浓度及溶解无机碳的碳同位素组成可以用来识别目前正在发生的甲烷渗漏活动;而沉积物中的WTS、自生矿物的δ~(34)S、钡含量及其异常峰值和生物标志化合物的δ~(13)C等指标的联合使用可以更真实准确地反映地质历史时期天然气水合物赋存区的甲烷渗漏活动。因此,在实际研究过程中,可将孔隙水和沉积物两种介质的多种指标相结合。随着非传统稳定同位素(Fe、Ca、Mg等)和沉积物氧化还原敏感元素(Mo、V、U等)等研究的发展,甲烷渗漏活动地球化学响应指标的研究也将得到拓展,而多种地球化学指标的联合使用将为天然气水合物勘探及其形成分解过程识别研究提供重要的科学依据。     

Methane sources in gas hydrate-bearing cold seeps: Evidence from radiocarbon and stable isotopes

Fossil methane from the large and dynamic marine gas hydrate reservoir has the potential to influence oceanic and atmospheric carbon pools. However, natural radiocarbon (¹⁴C) measurements of gas hydrate methane have been extremely limited, and their use as a source and process indicator has not yet been systematically established. In this study, gas hydrate-bound and dissolved methane recovered from six geologically and geographically distinct high-gas-flux cold seeps was found to be 98 to 100% fossil based on its ¹⁴C content. Given this prevalence of fossil methane and the small contribution of gas hydrate (≤ 1%) to the present-day atmospheric methane flux, non-fossil contributions of gas hydrate methane to the atmosphere are not likely to be quantitatively significant. This conclusion is consistent with contemporary atmospheric methane budget calculations.In combination with δ¹³C- and δD-methane measurements, we also determine the extent to which the low, but detectable, amounts of ¹⁴C (~ 1–2% modern carbon, pMC) in methane from two cold seeps might reflect in situ production from near-seafloor sediment organic carbon (SOC). A ¹⁴C mass balance approach using fossil methane and ¹⁴C-enriched SOC suggests that as much as 8 to 29% of hydrate-associated methane carbon may originate from SOC contained within the upper 6 m of sediment. These findings validate the assumption of a predominantly fossil carbon source for marine gas hydrate, but also indicate that structural gas hydrate from at least certain cold seeps contains a component of methane produced during decomposition of non-fossil organic matter in near-surface sediment.     

Origins and maturity of organic matter in mid-Cretaceous black shales from ODP Site 1138 on the Kerguelen Plateau

We have conducted elemental, isotopic, and Rock-Eval analyses of Cenomanian–Santonian sediment samples from ODP Site 1138 in the southern Indian Ocean to assess the origin and thermal maturity of organic matter in mid-Cretaceous black shales found at this high-latitude location. Total organic carbon (TOC) concentrations range between 1 and 20 wt% in black to medium-gray sediments deposited around the Cenomanian–Turonian boundary. Results of Rock-Eval pyrolysis indicate that the organic matter is algal Type II material that has experienced modest alteration. Important contributions of nitrogen-fixing bacteria to the amplified production of organic matter implied by the high TOC concentrations is recorded in δ¹⁵N values between −5 and 1‰, and the existence of a near-surface intensified oxygen minimum zone that favored organic carbon preservation is implied by TOC/TN ratios between 20 and 40. In contrast to the marine nature of the organic matter in the Cenomanian–Turonian boundary section, deeper sediments at Site 1138 contain evidence of contributions land-derived organic matter that implies the former presence of forests on the Kerguelen Plateau until the earliest Cenomanian.     

Bulk organic δC and C/N as indicators for sediment sources in the Pearl River delta and estuary,southern China

Preservation of organic matter in estuarine and coastal areas is an important process in the global carbon cycle. This paper presents bulk δ¹³C and C/N of organic matter from source to sink in the Pearl River catchment, delta and estuary, and discusses the applicability of δ¹³C and C/N as indicators for sources of organic matter in deltaic and estuarine sediments. In addition to the 91 surface sediment samples, other materials collected in this study cover the main sources of organic material to estuarine sediment. These are: terrestrial organic matter (TOM), including plants and soil samples from the catchment; estuarine and marine suspended particulate organic carbon (POC) from both summer and winter. Results show that the average δ¹³C of estuarine surface sediment increases from −25.0 ± 1.3‰ in the freshwater environment to −21.0 ± 0.2‰ in the marine environment, with C/N decreasing from 15.2 ± 3.3 to 6.8 ± 0.2. In the source areas, C₃ plants have lower δ¹³C than C₄ plants (−29.0 ± 1.8‰ and −13.1 ± 0.5‰ respectively). δ¹³C increases from −28.3 ± 0.8‰ in the forest soil to around −24.1‰ in both riverbank soil and mangrove soil due to increasing proportion of C₄ grasses. The δ¹³C_POC increases from −27.6 ± 0.8‰ in the freshwater areas to −22.4 ± 0.5‰ in the marine-brackish-water areas in winter, and ranges between −24.0‰ in freshwater areas and −25.4‰ in brackish-water areas in summer. Comparison of the δ¹³C and C/N between the sources and sink indicates a weakening TOM and freshwater POC input in the surface sedimentary organic matter seawards, and a strengthening contribution from the marine organic matter. Thus we suggest that bulk organic δ¹³C and C/N analysis can be used to indicate sources of sedimentary organic matter in estuarine environments. Organic carbon in surface sediments derived from anthropogenic sources such as human waste and organic pollutants from industrial and agricultural activities accounts for less than 10% of the total organic carbon (TOC). Although results also indicate elevated δ¹³C of sedimentary organic matter due to some agricultural products such as sugarcane, C₃ plants are still the dominant vegetation type in this area, and the bulk organic δ¹³C and C/N is still an effective indicator for sources of organic matter in estuarine sediments.     

Facies evolution and stratigraphic correlation in the early Oligocene Tard Clay of Hungary as revealed by maceral,biomarker and stable isotope composition

Hydrocarbon source rocks (i.e. Tard Clay Formation), containing type-II organic matter, were deposited in the Hungarian Paleogene Basin during Lower Oligocene. A major contribution of aquatic organisms (green algae, dinoflagellates, Chrysophyte algae) and minor inputs from macrophytes and land plants to organic matter accumulation is indicated by n-alkane distribution patterns, composition of steroids, and δ¹³C of hydrocarbon biomarkers. Microbial communities included heterotrophic bacteria, cyanobacteria, chemoautotrophic bacteria, as well as green sulphur bacteria. The presence of methanotrophic bacteria is indicated by ¹³C-depleted hop-17(21)-ene. Higher inputs of terrestrial organic matter occurred during deposition of the lower and uppermost units of the Tard Clay Formation. The terpenoid hydrocarbon composition argues for angiosperm-dominated vegetation in the area of the Hungarian Paleogene Basin. Diterpenoid hydrocarbons, derived from the resins of conifers, are about 2–3‰ enriched in ¹³C compared to the angiosperm biomarkers.Environmental conditions changed from marine to brackish, accompanied by oxygen-depletion in the lower parts of the water column. Organic carbon accumulation during this period was a consequence of stagnant bottom water conditions in the Hungarian Paleogene Basin due to salinity stratification. This is indicated by low pristane/phytane ratios (varying from 0.27 to 1.44), enhanced ratios of dimethylated versus trimethylated MTTCs (0.14–0.59), and the presence of aryl isoprenoids (from 0.4 to 14.1 μg/g TOC). A major marine incursion is evidenced by stable isotope ratios of organic matter and carbonates. In the uppermost member of the Tard Clay, a transition from brackish towards normal marine conditions is proposed.Up to 3 anoxic cycles are recognized in the drill core sections, separated by minima in pristane/phytane ratios and maxima in the depth trends of di-/tri-methylated MTTCs and aryl isoprenoid concentrations. In combination with the position of maxima of δ¹³C of carbonate and organic matter and an abrupt decrease in perylene concentrations, the cycles can be used for intra-formational correlation of the Tard Clay.     

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.     

九龙江河口沉积物中硫酸盐还原与甲烷厌氧氧化:同位素地球化学证据

通过沉积物柱孔隙水中甲烷,SO2-4,Cl-,δc(34S-SO2-4)、δc(13 C-CH4)的垂直分布特征,研究了硫酸盐还原和甲烷厌氧氧化(anaerobic oxidation of methane,简称AOM)过程在九龙江河口沉积物中的分布规律.测定结果显示两个站位(J-A和J-E)间隙水中SO2-4浓度随深...     

~(35)SO_4~(2-)示踪法测定九龙江河口沉积中硫酸盐还原速率

在2011年7月利用35SO2-4培养示踪法测定九龙江河口两个站位(A站位位于咸淡混合区,盐度3~5;B站位位于海相区,盐度20~25)沉积柱中硫酸盐还原速率的垂直分布。结果显示A站位沉积柱中硫酸盐还原速率变化范围为54~2 345nmol/(cm3·d),从表层到底部先增大后减小,最大值出现在20cm深度附近;B站位硫酸盐还原速率在24~987nmol/(cm3·d)之间,分别在10cm和78cm深度附近出现两个峰值,分别为876nmol/(cm3·d)和987nmol/(cm3·d)。综合分析两个站位孔隙水中SO2-4、甲烷浓度和沉积物中总有机碳、温度和氧化还原电位的垂直变化趋势与其硫酸盐还原速率的分布规律,表明A站位沉积物中硫酸盐还原以有机矿化为主;B站位受到有机质矿化和甲烷厌氧氧化的共同作用;两个站位硫酸盐还原速率及垂直分布趋势受孔隙水中SO2-4浓度、有机质活性和温度的共同影响;根据各个层位硫酸盐还原速率估算两个站位硫酸盐还原通量(以硫计)分别为527.9mmol/(m2·d)和357.1mmol/(m2·d),表明硫酸盐还原是九龙江河口有机质厌氧矿化的重要路径。     

The characteristics of gas hydrates recovered from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

Systematic analyses have been carried out on two gas hydrate-bearing sediment core samples, HYPV4, which was preserved by CH₄ gas pressurization, and HYLN7, which was preserved in liquid-nitrogen, recovered from the BPXA-DOE-USGS Mount Elbert Stratigraphic Test Well. Gas hydrate in the studied core samples was found by observation to have developed in sediment pores, and the distribution of hydrate saturation in the cores imply that gas hydrate had experienced stepwise dissociation before it was stabilized by either liquid nitrogen or pressurizing gas. The gas hydrates were determined to be structure Type I hydrate with hydration numbers of approximately 6.1 by instrumentation methods such as powder X-ray diffraction, Raman spectroscopy and solid state ¹³C NMR. The hydrate gas composition was predominantly methane, and isotopic analysis showed that the methane was of thermogenic origin (mean δ¹³C = −48.6‰ and δ_D = −248‰ for sample HYLN7). Isotopic analysis of methane from sample HYPV4 revealed secondary hydrate formation from the pressurizing methane gas during storage.     

Influence of submarine fumaroles on the distribution of mercury in the sediment of Kagoshima Bay,Japan

To estimate the influence of mercury emitted from submarine fumaroles, the horizontal and vertical distribution of mercury in sediment of Kagoshima Bay was studied. The fumaroles are located in the northern bay head area, and the sediment samples had been taken from 52 points throughout the bay with a gravity core sampler. The core samples obtained were cut at a thickness of 1–2 cm and used for measurements. The total concentration of mercury in surface sediment in the northern and central areas of the bay was 51–679 μg kg^− 1 (average 199 μg kg^− 1, n = 22) and 23–100 μg kg^− 1 (average 55 μg kg^− 1, n = 30), respectively. The highest value was obtained in the vicinity of the fumaroles. The mercury concentration in sediment near the fumaroles varied with depth, which may reflect the variation in fumarolic activity. A successive extraction method was applied to the speciation of mercury in the sediment. The results showed that sediment taken in the vicinity of submarine fumaroles contained a higher percentage of mercury bound with organic matter.     

Core lithologies and their constraints on gas-hydrate occurrence in the East Sea, offshore Korea: Results from the site UBGH1-9

Drilling at the site UBGH1-9, offshore Korea in 2007, revealed varied gas-hydrate saturation with depth and a wide variety of core litholgies, demonstrating how the variations in the lithology are linked with those in gas-hydrate saturation and morphology. Discrete excursions to low chlorinity values from in situ background chlorinity level occur between 63 and 151 mbsf. In this occurrence zone, gas-hydrate saturations estimated from the low chlorinity anomalies range up to 63.5% of pore volume with an average of 9.9% and do not show a clear depth-dependent trend. Sedimentary facies analysis based on grain-size distribution and sedimentary structures revealed nine sediment facies which mainly represent hemipelagic muds and fine- to medium-grained turbidites. According to the sedimentary facies distribution, the core sediments are divided into three facies associations (FA): FA I (0–98 mbsf) consisting mainly of alternating thin- to medium-bedded hemipelagic mud and turbidite sand or mud beds, FA II (98–126 mbsf) dominated by medium- to very thick-bedded turbidite sand or sandy debris flow beds, and FA III (126–178 mbsf) characterized by thick hemipelagic mud without intervening discrete turbidite sand layers. Thermal anomalies from IR scan, mousse-like and soupy structures on split-core surfaces, non-destructive measurements of pressure cores, and comparison of gas-hydrate saturations with sand contents of corresponding pore-water squeeze cakes, collectively suggest that the gas hydrate at the site UBGH1-9 generally occurs in two different types: “pore-filling” type preferentially associated with thin- to medium-turbidite sand beds in the FA I and “fracture-filling” type which occurs as hydrate veins or nodules in hemipelagic mud of the FA III. Gas-hydrate saturation in the FA II is generally anomalously low despite the dominance of turbidite sand or sandy debris flow beds, suggesting insufficient methane supply.     

Characterisation and preliminary quantification of the methane reservoir in a coastal sedimentary source: San Simón Bay,Ría de Vigo,NW Spain

Ría de Vigo is a river valley flooded by the sea, with a bay (San Simón Bay) at its innermost part. The accumulation of Holocene sediment in San Simón Bay has been studied by the integration of 1) large scale high resolution seismic data, and 2) detailed geochemical analysis of a gravity core. In San Simón Bay the majority of the seismic records are obscured by acoustic turbidity which represents gassy sediments, but on records from Rande Strait it is possible to distinguish two Quaternary seismic sequences; an Upper Pleistocene sequence (SQ1) and a Holocene sequence (SQ2). Only SQ2 is recognized in San Simón Bay where it is comprised of two seismic units; the upper unit represents the HST sediment, i.e. the period of highest sea level. A gravity core taken within the gassy zone at 10 m water depth provided 3.55 m of fine-grained sediments (muds) from the youngest seismic unit (4 m thick). Geochemical analysis show high values (4 to 10%) of TOC. Sediment and porewater analyses indicate a distinct sulphate–methane transition zone (SMTZ) between 60 and 80 cm where sulphate is depleted (to <1.7 mM) and methane increases (to >0.4 mM). The top of the acoustic turbidity (the gas front) at 80 cm corresponds to the lower limit of the SMTZ. The methane cannot have been derived from the underlying metamorphic and granitic rocks, but was probably derived by microbial degradation of the organic matter in the Holocene sediments. We estimate that the sediments of the Bay contain approximately 1.8 × 10⁶ m³ of organic carbon and 275 ton of methane.