Authigenic Mg-calcite at a cold methane seep site in the Laptev Sea

Authigenic minerals were studied in Holocene shelf sediments of the Laptev Sea (cold methane seep site, water depth 71 m). The study presents the first finds of large hard carbonate concretions with Mg-calcite cement in recent sediments of the Arctic shelf seas. These concretions differ from previously reported glendonites and concretions from bottom sediments of the White Sea, Kara Sea, Sea of Okhotsk, etc. A study of the morphology, microstructure, and composition of these newly reported concretions revealed the multistage formation of carbonates (structural varieties of Mg-calcite and aragonite). It was shown that organic matter played an important role in the formation of authigenic carbonates, i.e., in the formation of sedimentary–diagenetic Mg-calcite. The role of methane as a possible source for authigenic carbonate formation was estimated. It was found that methane-derived Mg-calcite accounts for 17–35% of concretion materials. Mg-calcite had δ¹³С-С_carb values between–24 and–23‰ and δ¹³С-С_org values between–44.5 and–88.5‰.     

Authigenic carbonates from active methane seeps offshore southwest Africa

The southwest African continental margin is well known for occurrences of active methane-rich fluid seeps associated with seafloor pockmarks at water depths ranging broadly from the shelf to the deep basins, as well as with high gas flares in the water column, gas hydrate accumulations, diagenetic carbonate crusts and highly diverse benthic faunal communities. During the M76/3a expedition of R/V METEOR in 2008, gravity cores recovered abundant authigenic carbonate concretions from three known pockmark sites—Hydrate Hole, Worm Hole, the Regab pockmark—and two sites newly discovered during that cruise, the so-called Deep Hole and Baboon Cluster. The carbonate concretions were commonly associated with seep-benthic macrofauna and occurred within sediments bearing shallow gas hydrates. This study presents selected results from a comprehensive analysis of the mineralogy and isotope geochemistry of diagenetic carbonates sampled at these five pockmark sites. The oxygen isotope stratigraphy obtained from three cores of 2–5?m length indicates a maximum age of about 60,000–80,000?years for these sediments. The authigenic carbonates comprise mostly magnesian calcite and aragonite, associated occasionally with dolomite. Their very low carbon isotopic compositions (–61.0?<?δ¹³C ‰ V-PDB?<?–40.1) suggest anaerobic oxidation of methane (AOM) as the main process controlling carbonate precipitation. The oxygen isotopic signatures (+2.4?<?δ¹⁸O ‰ V-PDB?<?+6.2) lie within the range in equilibrium under present-day/interglacial to glacial conditions of bottom seawater; alternatively, the most positive δ¹⁸O values might reflect the contribution of ¹⁸O-rich water from gas hydrate decomposition. The frequent occurrence of diagenetic gypsum crystals suggests that reduced sulphur (hydrogen sulphide, pyrite) from sub-seafloor sediments has been oxidized by oxygenated bottom water. The acidity released during this process can potentially induce the dissolution of carbonate, thereby providing enough Ca²⁺ ions for pore solutions to reach gypsum saturation; this is thought to be promoted by the bio-irrigation and burrowing activity of benthic fauna. The δ¹⁸O–δ¹³C patterns identified in the authigenic carbonates are interpreted to reflect variations in the rate of AOM during the last glacial–interglacial cycle, in turn controlled by variably strong methane fluxes through the pockmarks. These results complement the conclusions of Kasten et al. in this special issue, based on authigenic barite trends at the Hydrate Hole and Worm Hole pockmarks which were interpreted to reflect spatiotemporal variations in AOM related to subsurface gas hydrate formation–decomposition.     

Authigenic minerals from the Paola Ridge (southern Tyrrhenian Sea): Evidences of episodic methane seepage

Paola Ridge, along the NW Calabrian margin (southern Tyrrhenian Sea), is one of the few reported deep sea sites of precipitation of authigenic carbonates in the Tyrrhenian Sea. Here, the changing composition of the seeping fluids and the dynamic nature of the seepage induced the precipitation of pyrite, siderite and other carbonate phases. The occurrence of this array of authigenic precipitates is thought to be related to fluctuation of the sulfate-methane transition zone (SMTZ).Concretions of authigenic minerals formed in the near sub-bottom sediments of the Paola Ridge were investigated for their geochemical and isotopic composition. These concretions were collected in an area characterized by the presence of two alleged mud volcanoes and three mud diapirs. The mud diapirs are dotted by pockmarks and dissected by normal faults, and are known for having been a site of fluid seepage for at least the past 40 kyrs. Present-day venting activity occurs alongside the two alleged mud volcanoes and is dominated by CO₂-rich discharging fluids. This discover led us to question the hypothesis of the mud volcanoes and investigate the origin of the fluids in each different domed structure of the study area.In this study, we used stable isotopes (carbon and oxygen) of carbonates coupled with rare earth element (REE) composition of different carbonate and non-carbonate phases for tracing fluid composition and early diagenesis of authigenic precipitates. The analyses on authigenic precipitates were coupled with chemical investigation of venting gas and sea-water.Authigenic calcite/aragonite concretions, from surficial sediments on diapiric structures, have depleted ¹³C isotopic composition and slightly positive δ¹⁸O values. By contrast, siderite concretions, generally found within the first 6 m of sediments on the alleged mud volcanoes, yielded positive δ¹³C and δ¹⁸O values. The siderite REE pattern shows consistent LREE (light REE) fractionation, MREE (medium REE) enrichment and positive Gd and La anomalies. As shown by the REE distribution, the ¹³C-depleted composition and their association with chemosymbiotic fauna, calcite/aragonite precipitated at time of moderate to high methane flux close to the seafloor, under the influence of bottom seawater. Authigenic siderite, on the other hand, formed in the subseafloor, during periods of lower gas discharges under prolonged anoxic conditions within sediments in equilibrium with ¹³C-rich dissolved inorganic carbon (DIC) and ¹⁸O-rich water, likely related to methanogenesis and intermittent venting of deep-sourced CO₂.     

Exhumed hydrocarbon-seep authigenic carbonates from Zakynthos Island (Greece): Concretions not archaeological remains

In Zakynthos Island (Greece), authigenic cementation of marine sediment has formed pipe-like, disc and doughnut-shaped concretions. The concretions are mostly composed of authigenic ferroan dolomite accompanied by pyrite. Samples with >80% dolomite, have stable isotope compositions in two groups. The more indurated concretions have δ¹⁸O around +4‰ and δ¹³C values between −8 and −29‰ indicating dolomite forming from anaerobic oxidation of thermogenic methane (hydrocarbon seep), in the sulphate-methane transition zone. The outer surfaces of some concretions, and the less-cemented concretions, typically have slightly heavier isotopic compositions and may indicate that concretion growth progressed from the outer margin in the ambient microbially-modified marine pore fluids, inward toward the central conduit where the isotopic compositions were more heavily influenced by the seep fluid. Sr isotope data suggest the concretions are fossil features, possibly of Pliocene age and represent an exhumed hydrocarbon seep plumbing system. Exposure on the modern seabed in the shallow subtidal zone has caused confusion, as concretion morphology resembles archaeological stonework of the Hellenic period.     

Enrichment of adsorbed methane in authigenic carbonate concretions of the Japan Trench

Substantial amounts of adsorbed methane were detected in authigenic carbonate concretions recovered from sedimentary layers from depths between 245 and 1,108 m below seafloor during Ocean Drilling Program Leg 186 to ODP sites 1150 and 1151 on the deep-sea terrace of the Japan Trench. Methane contents were almost two orders of magnitude higher in the concretions (291–4,528 nmol/g wet wt) than in the surrounding bulk sediments (5–93 nmol/g wet wt), whereas methane/ethane ratios and stable carbon isotopic compositions were very similar. Carbonate content of surrounding bulk sediments (0.02–3.2 wet wt%) and methane content of the surrounding bulk sediments correlated positively. Extrapolation of the carbonate contents of bulk sediments suggests that 100 wt% carbonate would correspond to 1,886±732 nmol methane per g bulk sediment, which is similar to the average value observed in the carbonate concretions (1,321±1,067 nmol/g wet wt, n = 13). These data support the hypothesis that, in sediments, adsorbed hydrocarbon gases are strongly associated with authigenic carbonates.     

Petrographic evidence of the past occurrence of gas hydrates in the Tertiary Piedmont Basin (NW Italy)

Methane-derived rocks in Monferrato and the Tertiary Piedmont Basin (NW Italy) consist of seep carbonates, formed by gas seepage at the seafloor, and macroconcretions resulting from the cementation of buried sediments crossed by gas-rich fluids. These rocks are characterized by both negative δ¹³C values and a marked enrichment in δ¹⁸O. Petrographic features not commonly described and that point to enigmatic depositional and diagenetic conditions have been observed in both types of rocks: inhomogeneous distribution of cements within cavities; dolomite crystals floating within cavity-filling calcite spar; non-gravitational fabrics of internal sediments plastering cavity walls; open framework within microbial crusts. These features suggest the former presence of gas hydrates in sediments. During their dissociation, new space was formed and filled with authigenic carbonates or injected sediments. Analogous mechanisms of clathrate freeze-and-thaw processes have been inferred for the genesis of zebra and stromatactis structures and particular kinds of carbonate breccias. The term melt-seal structure is proposed for this kind of diagenetic structure. The fabrics of gas hydrates and the geochemical conditions of sediments, in turn depending on the relative rates of supply of methane-rich fluids and normal seawater, conditioned the final aspect of the rocks.     

Methane-derived authigenic carbonates from active hydrocarbon seeps of the St. Lawrence Estuary,Canada

Nearly 2000 pockmarks with diameters ranging from a few tens of meters up to 700 m are present on the seafloor of the St. Lawrence Estuary in eastern Canada. Coring of some pockmarks resulted in the recovery of various-sized and shaped carbonate concretions in a predominantly silty mud matrix. Petrographic and geochemical data on four authigenic carbonate concretions are reported as well as data from shell material in the unconsolidated sediment. Video observations and echo-sounder images indicate that the sampled pockmarks are actively gas venting. The video images show significant look-alike microbial mats in areas where gas is venting. The carbonate concretions are primarily made up of carbonate cements with varying percentage of shell fragments, micrite particles and fine-grained clastics. Orthorhombic crystal morphology and diagenetic fabrics including isopachous layers and botryoids characterize the aragonite cement. Oxygen isotopes ratios for the cement crusts do not record any thermal anomaly at the site of precipitation with δ¹⁸O_VPDB ratios (+3‰) in equilibrium with cold (5 °C) deep marine waters, whereas significant negative δ¹³C_VPDB ratios (−9.9 to −33.5‰) for cement and shell material within concretions indicate that the carbonates largely derive from the microbial oxidation of methane. The δ¹³C_VPDB ratios of aragonite shells (−2.7 to −5.6‰) taken from unconsolidated sediments at some distance from the concretions/vents show variable dilution of HCO₃⁻ with negative δ¹³C_VPDB ratios derived from microbial oxidation of methane with isotopically normal (0‰) marine bicarbonate. These results are in agreement with other lines of evidence suggesting that pockmarks formed through the recent and still active release of gas from a reservoir within the Paleozoic sedimentary succession.     

Fluid sources and stable isotope signatures in authigenic carbonates from the Northern Apennines,Italy

Authigenic carbonates are frequently associated with methane cold-seep systems, which extensively occur in various geologic settings worldwide. Of interest is the relation between the fluids involved in their formation and the isotopic signals recorded in the carbonate cements. Along the Northern Apennines foothills (Italy), hydrocarbons and connate waters still seeping nowadays are believed to be the primary sources for the formation of fossil authigenic carbonate found in Plio-Pleistocene marine sediments. Four selected outcrops of dolomitic authigenic carbonates were analysed to compare signature of seeping fluids with fractionation of stable carbon and oxygen isotopes recorded in the carbonate.Along the foothills, deep methane-rich fluids spontaneously rise to the surface through mud volcanoes or are exploited in wells drilled nearby to the fossil Plio-Pleistocene authigenic carbonates. The plumbing system providing fluids to present-day cold seeps was structurally achieved in Late Miocene and Plio-Pleistocene. δ¹³C values of methane, which vary from −51.9 to −43.0‰ VPDB, indicate that gas composition from the deep hydrocarbon reservoirs is relatively uniform along the foothills. On the contrary, δ¹³C in fossil authigenic carbonates strongly varies among different areas and also within the same outcrop.The different carbon sources that fed the investigated carbonates were identified and include: thermogenic methane from the deep Miocene reservoirs, ¹³C-enriched CO₂ derived from secondary methanogenesis and microbial methane from Pliocene successions buried in the Po Plain. The δ¹³C variability documented among samples from a single outcrop testifies that the authigenic carbonates might represent a record of varying biogeochemical processes in the hydrocarbon reservoirs. The sources of stable oxygen isotopes in authigenic carbonates are often ascribed to marine water. Oxygen isotopic fractionation in the dolomite cements indicates that marine pore water couldn't be the sole source of oxygen. δ¹⁸O values provide a preliminary evidence that connate waters had a role in the carbonates precipitation. The concomitant occurrence of active cold seepages and fossil record of former plumbing systems suggests that generation and migration of hydrocarbons are long-lasting and very effective processes along the Northern Apennines foothills.     

Methane seepage in the Shenhu area of the northern South China Sea: constraints from carbonate chimneys

Two authigenic carbonate chimneys were recovered from the Shenhu area in the northern South China Sea at approximately 400 m water depth. The chimneys’ mineralogy, isotopic composition, and lipid biomarkers were studied to examine the biogeochemical process that induced the formation of the chimneys. The two chimneys are composed mostly of dolomite, whereas the internal conduits and semi-consolidated surrounding sediments are dominated by aragonite and calcite. The specific biomarker patterns (distribution of lipids and their depleted δ¹³C values) indicate the low occurrence of methanotrophic archaea ANME-1 responsible for the chimneys’ formation via anaerobic oxidation of methane. A significant input of bacteria/planktonic algae and cyanobacteria to the carbon pool during the precipitation of the carbonate chimneys is suggested by the high contributions of short-chain n-alkanes (69% of total hydrocarbons) and long-chain n-alcohols (on average 56% of total alcohols). The oxygen isotopic compositions of the carbonate mixtures vary from 3.1‰ to 4.4‰ in the dolomite-rich chimneys, and from 2.1‰ to 2.5‰ in the internal conduits, which indicates that they were precipitated from seawater-derived pore waters during a long period covering the last glacial and interglacial cycles. In addition, the mixture of methane and bottom seawater dissolved inorganic carbon could be the carbon sources of the carbonate chimneys.     

Mechanism of carbonate cementation and its influence on reservoir in Pinghu Formation of Xihu Sag

Carbonate cements are the most abundant authigenic mineral and impact on physical properties greatly in sandstone reservoir. In this paper, Pinghu Formation of Xihu Sag was taken as a target. Characteristics,distribution and formation of carbonate cements were investigated via optical microscopy, cathodoluminescence(CL), electron probe and in-situ carbon-oxygen isotope. The results showed that carbonate cements varied in types and shapes. Calcite/dolomite mainly present as poikilotopic cements, ...     

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⁺.     

海底甲烷缺氧氧化与冷泉碳酸盐岩沉淀动力学研究进展

海底缺氧带甲烷氧化作用是一个重要的甲烷生物地球化学过程,已被许多地球化学现象所证实。甲烷缺氧氧化有效地减少了渗漏到海水和大气中的甲烷通量,但目前仅有的数据还不能很好地限定甲烷缺氧氧化在全球甲烷循环和全球碳循环中的作用。甲烷缺氧氧化的机理还存在争议,很可能是一个“反甲烷生成”过程。在许多天然气渗漏发育区域,由于甲烷缺氧氧化作用引起环境碱度的增加而沉淀冷泉碳酸盐岩,在海底表层沉积物中形成块状碳酸盐岩结壳。但冷泉碳酸盐岩生成所需的物理化学和生物地球化学条件在很大程度上还不清楚。数值计算表明,孔隙水中溶解足够量的甲烷、冷泉渗漏强度适中、较小的生物扰动作用有利于冷泉碳酸盐岩的生成,而过高的沉积速率则抑制冷泉碳酸盐岩结壳的生成。因此,海底发育冷泉碳酸盐岩可以指示天然气渗漏系统的演化特征。     

Isotopic composition of dissolved inorganic carbon in subsurface sediments of gas hydrate-bearing mud volcanoes, Lake Baikal: implications for methane and carbonate origin

We report on the isotopic composition of dissolved inorganic carbon (DIC) in pore-water samples recovered by gravity coring from near-bottom sediments at gas hydrate-bearing mud volcanoes/gas flares (Malenky, Peschanka, Peschanka 2, Goloustnoe, and Irkutsk) in the Southern Basin of Lake Baikal. The δ¹³C values of DIC become heavier with increasing subbottom depth, and vary between ?9.5 and +21.4‰ PDB. Enrichment of DIC in ¹³C indicates active methane generation in anaerobic environments near the lake bottom. These data confirm our previous assumption that crystallization of carbonates (siderites) in subsurface sediments is a result of methane generation. Types of methanogenesis (microbial methyl-type fermentation versus CO₂-reduction) were revealed by determining the offset of δ¹³C between dissolved CH₄ and CO₂, and also by using δ¹³C and δD values of dissolved methane present in the pore waters. Results show that both mechanisms are most likely responsible for methane generation at the investigated locations.     

Gas flux and carbonate occurrence at a shallow seep of thermogenic natural gas

The Coal Oil Point seep field located offshore Santa Barbara, CA, consists of dozens of named seeps, including a peripheral ～200 m² area known as Brian Seep, located in 10 m water depth. A single comprehensive survey of gas flux at Brian Seep yielded a methane release rate of ～450 moles of CH₄ per day, originating from 68 persistent gas vents and 23 intermittent vents, with gas flux among persistent vents displaying a log normal frequency distribution. A subsequent series of 33 repeat surveys conducted over a period of 6 months tracked eight persistent vents, and revealed substantial temporal variability in gas venting, with flux from each individual vent varying by more than a factor of 4. During wintertime surveys sediment was largely absent from the site, and carbonate concretions were exposed at the seafloor. The presence of the carbonates was unexpected, as the thermogenic seep gas contains 6.7% CO₂, which should act to dissolve carbonates. The average δ¹³C of the carbonates was ?29.2?±?2.8‰ VPDB, compared to a range of ?1.0 to +7.8‰ for CO₂ in the seep gas, indicating that CO₂ from the seep gas is quantitatively not as important as ¹³C-depleted bicarbonate derived from methane oxidation. Methane, with a δ¹³C of approximately ?43‰, is oxidized and the resulting inorganic carbon precipitates as high-magnesium calcite and other carbonate minerals. This finding is supported by ¹³C-depleted biomarkers typically associated with anaerobic methanotrophic archaea and their bacterial syntrophic partners in the carbonates (lipid biomarker δ¹³C ranged from ?84 to ?25‰). The inconsistency in δ¹³C between the carbonates and the seeping CO₂ was resolved by discovering pockets of gas trapped near the base of the sediment column with δ¹³C-CO₂ values ranging from ?26.9 to ?11.6‰. A mechanism of carbonate formation is proposed in which carbonates form near the sediment–bedrock interface during times of sufficient sediment coverage, in which anaerobic oxidation of methane is favored. Precipitation occurs at a sufficient distance from active venting for the molecular and isotopic composition of seep gas to be masked by the generation of carbonate alkalinity from anaerobic methane oxidation.

南海神狐海域沉积物自生黄铁矿和石膏S同位素特征及对甲烷渗漏强度的示踪

The northern slope of the South China Sea is a gas-hydrate-bearing region related to a high deposition rate of organic-rich sediments co-occurring with intense methanogenesis in subseafloor environments.Anaerobic oxidation of methane(AOM) coupled with bacterial sulfate reduction results in the precipitation of solid phase minerals in seepage sediment,including pyrite and gypsum.Abundant aggregates of pyrites and gypsums are observed between the depth of 667 and 850 cm below the seafloor(cmbsf) in the entire core sediment of HS328 from the northern South China Sea.Most pyrites are tubes consisting of framboidal cores and outer crusts.Gypsum aggregates occur as rosettes and spheroids consisting of plates.Some of them grow over pyrite,indicating that gypsum precipitation postdates pyrite formation.The sulfur isotopic values(δ~(34) S) of pyrite vary greatly(from –46.6‰ to –12.3‰ V-CDT) and increase with depth.Thus,the pyrite in the shallow sediments resulted from organoclastic sulfate reduction(OSR) and is influenced by AOM with depth.The relative high abundance and δ~(34) S values of pyrite in sediments at depths from 580 to 810 cmbsf indicate that this interval is the location of a paleo-sulfate methane transition zone(SMTZ).The sulfur isotopic composition of gypsum(from–25‰ to –20.7‰) is much lower than that of the seawater sulfate,indicating the existence of a 34 S-depletion source of sulfur species that most likely are products of the oxidation of pyrites formed in OSR.Pyrite oxidation is controlled by ambient electron acceptors such as MnO_2,iron(Ⅲ) and oxygen driven by the SMTZ location shift to great depths.The δ~(34) S values of gypsum at greater depth are lower than those of the associated pyrite,revealing downward diffusion of 34 S-depleted sulfate from the mixture of oxidation of pyrite derived by OSR and the seawater sulfate.These sulfates also lead to an increase of calcium ions from the dissolution of calcium carbonate mineral,which will be favor to the formation of gypsum.Overall,the mineralogy and sulfur isotopic composition of the pyrite and gypsum suggest variable redox conditions caused by reduced seepage intensities,and the pyrite and gypsum can be a recorder of the intensity evolution of methane seepage.     

Molecular and isotopic characteristics of gas hydrate-bound hydrocarbons in southern and central Lake Baikal

We investigated the molecular composition (methane, ethane, and propane) and stable isotope composition (methane and ethane) of hydrate-bound gas in sediments of Lake Baikal. Hydrate-bearing sediment cores were retrieved from eight gas seep sites, located in the southern and central Baikal basins. Empirical classification of the methane stable isotopes (δ¹³C and δD) for all the seep sites indicated the dominant microbial origin of methane via methyl-type fermentation; however, a mixture of thermogenic and microbial gases resulted in relatively high methane δ¹³C signatures at two sites where ethane δ¹³C indicated a typical thermogenic origin. At one of the sites in the southern Baikal basin, we found gas hydrates of enclathrated microbial ethane in which ¹³C and deuterium were both highly depleted (mean δ¹³C and δD of –61.6‰ V-PDB and –285.4‰ V-SMOW, respectively). To the best of our knowledge, this is the first report of C₂ δ¹³C–δD classification for hydrate-bound gas in either freshwater or marine environments.     

Last glacial emplacement of methane-derived authigenic carbonates in the Sea of Japan constrained by diatom assemblage,carbon-14, and carbonate content

We studied diatom assemblages and CaCO₃ contents of methane-derived authigenic carbonates from the eastern margin of the Sea of Japan and assessed the formation time of these samples. Radioactive ¹⁴C date was determined in selected samples to obtain the maximum age of the time. The results of our study suggest mass formation of carbonate nodules in a glacial period within ∼40 ky, consistent with a published U/Th dating result of carbonate nodules in the study area. Diatom assemblages and contents in the carbonate nodules (abundance of ∼10⁶/g, dominance of neritic-littoral species, warm/cold water species ratio lower than ∼25) differ from the near-seafloor sediments in the study area, which have characteristics of Holocene sediments in the Sea of Japan, and suggest cementation of glacial sediments. Laminated sediments in some nodule samples are glacial sediments because laminations are records of a low sea level period in the semi-enclosed ocean. Similarity of diatom assemblages and contents in all carbonate samples is another evidence of glacial sediments in nodules. Glacial sediments with oceanic cold water species as low as Holocene sediments restricts the sediment age to before 20 cal. ky BP. Carbonate contents higher than 78 wt% suggest the cementation of poorly compacted sediments near the seafloor, and the date of carbonate cementation is, therefore, close to that of the cemented sediments. Most carbonate nodule samples in this study were formed in a glacial period and detection of ¹⁴C restricts this period to within ∼40 ky.     

Sequentially sampled gas hydrate water,coupled with pore water and bottom water isotopic and ionic signatures at the Kukuy mud volcano,Lake Baikal: ambiguous deep-rooted source of hydrate-forming water

The isotopic and ionic composition of pure gas hydrate (GH) water was examined for GHs recovered in three gravity cores (165–193 cm length) from the Kukuy K-9 mud volcano (MV) in Lake Baikal. A massive GH sample from core St6GC4 (143–165 cm core depth interval) was dissociated progressively over 6 h in a closed glass chamber, and 11 sequentially collected fractions of dissociated GH water analyzed. Their hydrogen and oxygen isotopic compositions, and the concentrations of Cl^– and HCO₃ ^– remained essentially constant over time, except that the fraction collected during the first 50 minutes deviated partly from this pattern. Fraction #1 had a substantially higher Cl^– concentration, similar to that of pore water sampled immediately above (135–142 cm core depth) the main GH-bearing interval in that core. Like the subsequent fractions, however, the HCO₃ ^– concentration was markedly lower than that of pore water. For the GH water fractions #2 to #11, an essentially constant HCO₃ ^–/Cl^– ratio of 305 differed markedly from downcore pore water HCO₃ ^–/Cl^– ratios of 63–99. Evidently, contamination of the extracted GH water by ambient pore water probably adhered to the massive GH sample was satisfactorily restricted to the initial phase of GH dissociation. The hydrogen and oxygen isotopic composition of hydrate-forming water was estimated using the measured isotopic composition of extracted GH water combined with known isotopic fractionation factors between GH and GH-forming water. Estimated δD of ?126 to ?133‰ and δ¹⁸O of ?15.7 to ?16.7‰ differed partly from the corresponding signatures of ambient pore water (δD of ?123‰, δ¹⁸O of ?15.6‰) and of lake bottom water (δD of ?121‰, δ¹⁸O of ?15.8‰) at the St6GC4 coring site, suggesting that the GH was not formed from those waters. Observations of breccias in that core point to a possible deep-rooted water source, consistent with published thermal measurements for the neighboring Kukuy K-2 MV. By contrast, the pore waters of core St6GC4 and also of the neighboring cores GC2 and GC3 from the Kukuy K-9 MV show neither isotopic nor ionic evidence of such a source (e.g., elevated sulfate concentration). These findings constrain GH formation to earlier times, but a deep-rooted source of hydrate-forming water remains ambiguous. A possible long-term dampening of key deep-water source signatures deserves further attention, notably in terms of diffusion and/or advection, as well as anaerobic oxidation of methane.     

南海东沙东北部甲烷缺氧氧化作用的生物标志化合物及其碳同位素组成

南海东沙东北部碳酸盐岩和泥质沉积物中的生物标志化合物组合及其碳同位素组成分析表明,研究区内甲烷缺氧氧化作用(anaerobic oxidation of methane-AOM)发育.研究区内碳酸盐岩中含丰富的AOM标志化合物,2,6,11,15-四甲基十六烷(Crocetane-Cr.)、2,6,10,15,19-五甲基番茄烷(Pentamethylicosane-PMI)和2,6,10,15,19,23-六甲基二十四烷(Squalane-Sq角鲨烷)的13C亏损强烈(δ13C值介于-74.2‰~-119.0‰PDB之间),表明碳酸盐岩形成于AOM,同时反映该研究区曾发生过强烈、持续的富CH₄流体释放活动.柱状泥质沉积物中,AOM生物标志化合物在硫酸岩-甲烷过渡带(SMI-Sulfate-Methane Interface)边界附近相对丰度高,SMI之上样品中含量低,或未检出,表明现代环境在SMI附近有大量嗜甲烷微生物生长,使得深部上升的甲烷被大量消耗,很少有甲烷逸出海底.AOM生物标志化合物可用来指示SMI边界.不同站位、不同岩性AOM生物标志化合物组成(包括碳同位素组成)的差异反映了嗜甲烷古细菌组成的不同.     

Formation of methane-related authigenic carbonates in a highly dynamic biogeochemical system in the Krishna–Godavari Basin,Bay of Bengal

We report the abundant occurrence of authigenic Fe-rich carbonate, high Mg-calcite (HMC) and low Mg-calcite from 11 cores recovered from the Krishna–Godavari Basin (K–G Basin), Bay of Bengal. The cores were collected as part of the Indian gas hydrate exploration program on board R/V Marion Dufresne (MD-161: May, 2007) in different environments, including mounds (mud diapirs), mass flows, and hemipelagic sediments over a range of water depths from 647 to 2079 m. Authigenic carbonates range in size from 1 mm to 12 cm and display various morphologies like roundish or platy (micro-) nodules and tube-like forms. From the cores, 173 carbonate samples have been investigated for their depth distribution, mineralogy, geochemical and stable isotopic composition. The stable carbon isotopic composition of 46 out of 88 measured carbonate samples are around −50‰ which allows the differentiation into methane-related carbonates (HMC), especially at Sites 8 and 15, but also in low abundance at Sites 1, 5, 9 and 12. Results indicate that the carbonates at Site 8 and 15 represent paleo methane seepage locations. The Fe-rich carbonates occur abundantly at many sites in the K–G Basin. Their varying carbon isotopic composition indicates that probably not only sulfate reduction through organic matter degradation but also methanogenesis are the responsible processes for their formation.