Authigenic carbonates related to active seepage of methane-rich hot brines at the Cheops mud volcano,Menes caldera (Nile deep-sea fan,eastern Mediterranean Sea)

On the passive margin of the Nile deep-sea fan, the active Cheops mud volcano (MV; ca. 1,500 m diameter, ~20–30 m above seafloor, 3,010–3,020 m water depth) comprises a crater lake with hot (up to ca. 42 °C) methane-rich muddy brines in places overflowing down the MV flanks. During the Medeco2 cruise in fall 2007, ROV dives enabled detailed sampling of the brine fluid, bottom lake sediments at ca. 450 m lake depth, sub-surface sediments from the MV flanks, and carbonate crusts at the MV foot. Based on mineralogical, elemental and stable isotope analyses, this study aims at exploring the origin of the brine fluid and the key biogeochemical processes controlling the formation of these deep-sea authigenic carbonates. In addition to their patchy occurrence in crusts outcropping at the seafloor, authigenic carbonates occur as small concretions disseminated within sub-seafloor sediments, as well as in the bottom sediments and muddy brine of the crater lake. Aragonite and Mg-calcite dominate in the carbonate crusts and in sub-seafloor concretions at the MV foot, whereas Mg-calcite, dolomite and ankerite dominate in the muddy brine lake and in sub-seafloor concretions near the crater rim. The carbonate crusts and sub-seafloor concretions at the MV foot precipitated in isotopic equilibrium with bottom seawater temperature; their low δ¹³C values (–42.6 to –24.5‰) indicate that anaerobic oxidation of methane was the main driver of carbonate precipitation. By contrast, carbonates from the muddy lake brine, bottom lake concretions and crater rim concretions display much higher δ¹³C (up to –5.2‰) and low δ¹⁸O values (down to –2.8‰); this is consistent with their formation in warm fluids of deep origin characterized by ¹³C-rich CO₂ and, as confirmed by independent evidence, slightly higher heavy rare earth element signatures, the main driver of carbonate precipitation being methanogenesis. Moreover, the benthic activity within the seafloor sediment enhances aerobic oxidation of methane and of sulphide that promotes carbonate dissolution and gypsum precipitation. These findings imply that the coupling of carbon and sulphur microbial reactions represents the major link for the transfer of elements and for carbon isotope fractionation between fluids and authigenic minerals. A new challenge awaiting future studies in cold seep environments is to expand this work to oxidized and reduced sulphur authigenic minerals.     

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.     

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.     

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.     

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.

A contribution to the reconstruction of Miocene seepage from authigenic carbonates of the northern Apennines (Italy)

Authigenic carbonates from outcrops of the northern Apennines consist of small and irregular lenses and exhibit numerous features indicative of cold-seep settings. Detailed petrographic, mineralogical and geochemical studies from two Miocene deposits are presented. The first carbonate outcrop, named Fosso Riconi, is located in the foredeep basin of the Apenninic chain, whereas the second deposit represents a satellite basin called Sarsetta. The stable isotope data from specific carbonate minerals show a wide range of values well known from other palaeoseeps of the Apennine Mountains. The majority of seep carbonates are formed by low-Mg calcite and ankerite. Those minerals have δ¹³C values between ?7 and ?23‰ V-PDB, suggesting variable amounts of carbonate derived from oxidized methane, seawater (dissolved inorganic carbon) and sedimentary organic matter. Dolomite samples have the lowest δ¹³C values (?30.8 to ?39.0‰ V-PDB), indicating methane as the main carbon source. The findings suggest an evolutionary formation of the seeps and development of authigenic carbonates influenced by the activity of chemosynthetic organisms, of which large lucinid clams are preserved. Bioirrigation by the clams controlled the sediment–water exchange, and is here considered as an explanation for the anomalous Mg content of the calcite. We hypothesize that the seep carbonates were formed during periods of active methane-rich seepage, whereas during periods of slow seepage carbonate formation was reduced. Despite different geological settings, the two examined deposits of Sarsetta and Fosso Riconi show similar features, suggesting that a common pattern of fluid circulation played a major role in carbonate formation at both seep sites.     

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⁺.     

Geochemical and microbiological characteristics of sediments near the Malenky mud volcano (Lake Baikal, Russia), with evidence of Archaea intermediate between the marine anaerobic methanotrophs ANME-2 and ANME-3

Detailed lithological, biogeochemical and molecular biological analyses of core sediments collected in 2002–2006 from the vicinity of the Malenky mud volcano, Lake Baikal, reveal considerable spatial variations in pore water chemical composition, with total concentrations of dissolved salts varying from 0.1 to 1.8‰. Values of methane δ¹³С in the sediments suggest a biogenic origin (δ¹³С_min. ?61.3‰, δ¹³С_max. ?72.9‰). Rates of sulphate reduction varied from 0.001 to 0.7 nmol cm^?3 day^?1, of autotrophic methanogenesis from 0.01 to 2.98 nmol CH₄ cm^?3 day^?1, and of anaerobic oxidation of methane from 0 to 12.3 nmol cm^?3 day^?1. These results indicate that methanogenic processes dominate in gas hydrate-bearing sediments of Lake Baikal. Based on clone libraries of 16S rRNA genes amplified with Bacteria- and Archaea-specific primers, investigation of microbial diversity in gas hydrate-bearing sediments revealed bacterial 16S rRNA clones classified as Deltaproteobacteria, Gammaproteobacteria, Chloroflexi and OP11. Archaeal clone sequences are related to the Crenarchaeota and Euryarchaeota. Baikal sequences of Archaea form a distinct cluster occupying an intermediate position between the marine groups ANME-2 and ANME-3 of anaerobic methanotrophs.     

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.     

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.     

Molecular signals for anaerobic methane oxidation in Black Sea seep carbonates and a microbial mat

Linked to gas seeps on the Ukrainian shelf (northwestern Black Sea), massive authigenic carbonates form as a result of anaerobic methane oxidation. Lipid distributions in these ‘cold seep’ carbonates and an associated microbial mat were investigated for process markers reflecting the presence and metabolic activity of distinctive methane-related biota. The samples contain free, irregular isoprenoid hydrocarbons, namely the tail-to-tail linked acyclic C₂₀-isoprenoid 2,6,11,15-tetramethylhexadecane (crocetane), its C₂₅-homologue 2,6,10,15,19-pentamethylicosane (PMI), and several unsaturated derivatives thereof. Furthermore, specific acyclic and cyclic C₄₀-isoprenoids were released upon ether cleavage of the polar fraction from the carbonate. The abundance of these compounds indicates a pronounced role of particular Archaea in the biogeochemical cycling of carbon at methane seeps. Stable carbon isotopic analyses of these lipids reveal extraordinary depletions in ¹³C corresponding to δ-values in the range of −100±30‰ PDB, whereas other compounds show isotopic compositions normally observed for marine lipids (around −30‰ PDB). The isotope data imply that the biosynthesis of the archaeal isoprenoids occurred in situ and involved the utilization of isotopically depleted, i.e. methane-derived, carbon. Apart from archaeal markers, the carbonate and the mat contain authigenic, framboidal pyrite and isotopically depleted fatty acids, namely iso-, and anteiso-branched compounds most likely derived from sulphate-reducing bacteria (SRB). The indications for a tight association of these normally competitive organisms support a model invoking a syntrophic relationship of SRB with Archaea responsible for the anaerobic oxidation of methane. The biomarker patterns obtained from the Black Sea samples were further compared to those from a Oligocene seep carbonate (Lincoln Creek Formation, WA, USA) in order to evaluate their biomarker potential for ancient settings. The prominent occurrence of isotopically light crocetane (−112‰) and PMI (−120‰) meets the findings for the contemporary materials. Thus, isotopically depleted isoprenoids provide diagenetically stable fingerprints for the reconstruction of carbon cycling in both, modern and ancient methane seep systems.     

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.     

Mineral-forming and diagenetic processes related to Tertiary hydrocarbon seepage at the Bohemian Massif/Outer Western Carpathians interface: Evidence from the Hrabůvka quarry,Moravia, Czech Republic

Ancient hydrocarbon seepage occurred in the Hrabůvka quarry at the boundary between the basement of the Bohemian Massif (represented by folded Lower Carboniferous siliciclastics of the Culm facies) and Tertiary sedimentary cover of the Carpathian Foredeep (formed by Lower Badenian siliciclastics and calcareous clays). The unconsolidated Lower Badenian sediments contain lithified domains composed of limestone and breccias with limestone cement, whereas the basement rocks are cut by subvertical neptunic dykes filled up by limestone and calcite-marcasite-pyrite veinlets representing sealed fluid conduits. The deeply negative δ¹³C values of both vein calcite and limestone (down to −38.1‰ V-PDB) indicate that oxidation of hydrocarbons was the major source of carbon for authigenic mineralization. A fluid inclusion study suggests low fluid temperatures (<50 °C) and low and variable salinities of aqueous fluids associated with hydrocarbons (0.7–6.7 wt. % NaCl eq.). The variability of δ¹⁸O values of authigenic carbonates (−1.7 to −8.2‰ V-PDB) could reflect either slight changes in temperature of escaping fluids (mostly within 15 °C), and/or some mixing with meteoric waters. The low δ³⁴S values of vein marcasite (∼–20‰ V-CDT) are consistent with bacterial reduction of sulfate in the hydrothermal system. Low C₁/(C₂+C₃) ratios in hydrocarbon gas extracted from authigenic carbonates (9.9 and 5.8) as well as the high δ¹³C values of methane (−31.8 and −32.4‰ V-PDB) are compatible with a thermogenic source of hydrocarbons. REE data indicate sequestration of REE from finely dispersed detrital material in the apical part of the hydrothermal system. The available data are compatible with two possible scenarios of fluid origin. The hydrocarbons could have been leached from underlying Paleozoic sedimentary sequence by aqueous fluids that infiltrated into the basement after Tertiary tectonic reactivation. Alternatively, an external source of hydrocarbon-bearing fluids can be found in the adjacent Outer Western Carpathians flysch nappes containing petroleum-producing lithologies. Nevertheless, a regional flow of hydrocarbon-bearing fluids is evidenced by the occurrence of very similar hydrocarbon-bearing vein mineralizations in a wider area.     

The impact of organic fluids on the carbon isotopic compositions of carbonate-rich reservoirs: Case study of the Lucaogou Formation in the Jimusaer Sag,Junggar Basin,NW China

The processes involved in the interaction between organic fluids and carbonates, and the resulting effect on reservoir quality during the evolution and maturation of organic matter remain unclear despite the fact that these processes influence the carbon and oxygen isotopic compositions of carbonates. Here, we provide new insights into these processes using data obtained from a detailed analysis of a mixed dolomitic–clastic and organic-rich sedimentary sequence within the middle Permian Lucaogou Formation in the Junggar Basin of NW China. The techniques used during this study include drillcore observations, thin section petrography, scanning electron microscopy (SEM) and electron probe microanalysis, and carbon and oxygen isotope analyses. Oil grades and total organic carbon (TOC) contents represent the amount of oil charging and the abundance of organic fluids within a reservoir, respectively, and both negatively correlate with the whole-rock δ¹³C and δ¹⁸O of the carbonates in the study area, indicating that organic fluids have affected the reservoir rocks. Secondary carbonates, including sparry calcite and dolomite overgrowths and cements, are common within the Lucaogou Formation. Well-developed sparry calcite is present within dark mudstone whereas the other two forms of secondary carbonates are present within the dolomite-rich reservoir rocks in this formation. Comparing thin section petrology with δ¹³C compositions suggests that the carbon isotopic composition of matrix carbonates varies little over small distances within a given horizon but varies significantly with stratigraphic height as a result of the development of secondary carbonates. The net change in whole-rock δ¹³C as a result of these secondary carbonates ranges from 1.8‰ to 4.6‰, with the secondary carbonates having calculated δ¹³C compositions from −18.6‰ to −8.5‰ that are indicative of an organic origin. The positive correlation between the concentration of Fe within matrix and secondary carbonates within one of the samples suggests that the diagenetic system within the Lucaogou Formation was relatively closed. The correlation between δ¹³C and δ¹⁸O in carbonates is commonly thought to be strengthened by the influence of meteoric water as well as organic fluids. However, good initial correlation between δ¹³C and δ¹⁸O of whole rock carbonates within the Lucaogou Formation (resulted from the evaporitic sedimentary environment) was reduced by organic fluids to some extent. Consequently, the δ¹³C–δ¹⁸O covariations within these sediments are not always reliable indicators of diagenetic alteration by organic fluids or meteoric water.The characteristics and δ¹³C compositions of the sparry calcite within the formation is indicative of a genetic relationship with organic acids as a result of the addition of organic CO₂ to the reservoir. Further analysis suggests that both carbonate and feldspar were dissolved by interaction with organic CO₂. However, dissolved carbonate reprecipitated as secondary carbonates, meaning that the interaction between organic fluids and dolomites did not directly improve reservoir quality, although this process did enhance the dissolution of feldspar and increase porosity. This indicates that the δ¹³C and δ¹⁸O of secondary carbonates and their influence on whole-rock carbonate isotopic values can be used to geochemically identify the effect of organic fluids on closed carbonate-rich reservoir systems.     

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.     

南海北部表层沉积物碳酸盐含量和δ18O及δ13C的空间与粒径分布特征及其控制因素

为深入研究南海北部表层沉积物中碳酸盐的来源及其控制因素,采用湿筛法,对南海北部珠江口、陆架、陆坡及海盆表层沉积物中碳酸盐的含量、δ18O和δ13C及其粒度分布特征进行了研究。结果表明,南海北部表层沉积物中的碳酸盐可能主要以海洋自生碳酸盐为主,其含量在空间上以陆坡显著高于海盆、陆架及珠江口为特征。粒度上,陆架(水深80 m)和浅陆坡(水深550 m)处碳酸盐的粒度分布相对平均,但在珠江口及730 m以深,76.9%~84.5%的碳酸盐分布于小于32 μm的粒级中。另外,珠江口和陆架与陆坡和海盆碳酸盐δ18O和δ13C的空间及粒度分布特征显著不同。珠江口陆架区,在空间上从珠江口向陆架,全样碳酸盐的δ18O和δ13C由轻变重。粒度上,碳酸盐的δ18O和δ13C随着粒径的增大而变重,并且δ18O和δ13C之间正相关,主要受珠江淡水的δ18O及其δ13C_DIC控制。陆坡海盆区,空间上,从陆坡向海盆,δ18O略有变轻,δ13C基本不变。粒度上,碳酸盐的δ18O和δ13C随着粒度的增大没有明显的变化趋势,并且δ18O与δ13C之间不相关或负相关。其δ18O可能主要受表层海水的温度控制,其δ13C可能主要受海水δ13C_DIC控制。     

Isotopic composition of gas hydrates in subsurface sediments from offshore Sakhalin Island, Sea of Okhotsk

Hydrate-bearing sediment cores were retrieved from recently discovered seepage sites located offshore Sakhalin Island in the Sea of Okhotsk. We obtained samples of natural gas hydrates and dissolved gas in pore water using a headspace gas method for determining their molecular and isotopic compositions. Molecular composition ratios C₁/_C2+ from all the seepage sites were in the range of 1,500–50,000, while δ¹³C and δD values of methane ranged from ?66.0 to ?63.2‰ VPDB and ?204.6 to ?196.7‰ VSMOW, respectively. These results indicate that the methane was produced by microbial reduction of CO₂. δ¹³C values of ethane and propane (i.e., ?40.8 to ?27.4‰ VPDB and ?41.3 to ?30.6‰ VPDB, respectively) showed that small amounts of thermogenic gas were mixed with microbial methane. We also analyzed the isotopic difference between hydrate-bound and dissolved gases, and discovered that the magnitude by which the δD hydrate gas was smaller than that of dissolved gas was in the range 4.3–16.6‰, while there were no differences in δ¹³C values. Based on isotopic fractionation of guest gas during the formation of gas hydrate, we conclude that the current gas in the pore water is the source of the gas hydrate at the VNIIOkeangeologia and Giselle Flare sites, but not the source of the gas hydrate at the Hieroglyph and KOPRI sites.     

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.     

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.     

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.