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 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.     

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.     

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.     

Deuterium content of humic acids from marine and non-marine environments

Deuterium values obtained for humic acids isolated from marine sediments from the NE Pacific are in the range of $\text{δ}\text{D}\text{= (?105 ± 5)‰}$, corresponding to values obtained for marine plankton from the same area. Soil humic acids have a much broader range of δD values (?57 to ?97‰), depending on the isotopic values of the precipitation and the isotopic composition of the parent plant precursor.Data obtained on hydrogen isotope distribution confirms previous hypotheses based on chemical analysis and on carbon isotopes, which indicated the authigenic nature of marine humates.     

Authigenic dolomites in the Eocene–Oligocene organic carbon-rich shales from the Polish Outer Carpathians: Evidence of past gas production and possible gas hydrate formation in the Silesian basin

Eocene–Oligocene dolomite concretions and beds from the Grybów and Dukla units of the Polish Outer Carpathians were studied. These rocks occur in the organic carbon-rich, marine and fine-grained deposits of hemipelagic or turbiditic origin. Mineralogic, elemental and stable C and O isotopic composition of the dolomites was determined. Results indicate that the rocks were formed by precipitation of predominantly Fe-rich dolomite cement close to the sediment-water interface prior to significant compaction. The main source of bicarbonate for dolomite formation was bacterial methanogenesis as evidenced by the high δ¹³C values up to 16.6‰. The main source of alkalinity was probably weathering of silicate minerals which might have also liberated Ca and Mg ions for the dolomites to form. The distribution of these dolomites indicates that microbial methane production was widespread in the Silesian basin. Moreover, formation of some dolomites in the Eastern part of the Dukla unit was probably associated with gas hydrates as suggested by the elemental and oxygen isotopic composition of dolomitic matrix. Therefore, the dolomites may serve as a proxy of areas where biogenic methane was produced, where the rocks had high hydrocarbon potential, and where hydrates could have existed.Detailed mineralogic and petrographic analyses allowed for the reconstruction of the diagenetic sequence and the evolution of pore fluids. Textural relationships between successive cement generations indicate that the central parts of the composite dolomite crystals experienced corrosion and that the latest ankerite cement filled the secondary intragranular cavities within those crystals. This observation shows that reconstructions of pore fluid evolution based on core-to-rim analyses of such composite crystals may lead to wrong interpretations. Septarian cracks developed in the dolomites are often filled with multistage cements. The earliest generations are ferroan dolomite and ankerite cements which precipitated within the cracks simultaneously to the ferroan dolomite and ankerite cements from the matrix of the dolomitic rocks which shows that septarian cracking occurred very early, during the final stages of concretionary formation. These cements were followed by the late-diagenetic precipitates, mainly quartz, kaolinite and blocky calcite. This calcite is commonly associated with bitumen which shows that it precipitated during or after oil migration in the decarboxylation zone.     

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.     

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.     

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.     

苏北浅滩钙结核的特征及其环境指示意义

对采自苏北浅滩的钙结核样品进行了岩石学、矿物学和碳氧同位素的分析。样品富含石英和长石砂屑,碳酸钙胶结,其碳和氧同位素组成分别为-8.38‰~-8.19‰V-PDB及-5.23‰~-5.03‰V-PDB。根据样品的氧同位素组成,利用碳酸盐-水体系氧同位素方程,结合现今底层水温度,并考虑可能存在的温度变化,计算得到古沉淀流体的δ18 O水范围为-4.72‰~-4.52‰VSMOW,较正常海水偏负,认为钙结核的形成可能受到了淡水影响。根据结核中碎屑矿物的成分及其成熟度,判断其包含的碎屑矿物源自古黄河,认为这些结核样品可能形成于海陆交互环境,形成时间约为7~6.5ka BP左右,当时古海平面高度比现今低10m左右,古黄河河道可能位于苏北浅滩附近。     

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.     

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.

Natural abundances of 15N as a source indicator for near-shore marine sedimentary and dissolved nitrogen

Because organic matter originating in the euphotic zone of the ocean may have a distinctive nitrogen isotope composition (¹⁵N/¹⁴N), as compared to organic matter originating in terrestrial soils, it may be used to evaluate the relative nitrogen contribution to marine and estuarine sediment. The nitrogen isotope ratios of 42 sediment samples of total nitrogen and 38 dissolved pore-water ammonium samples from Santa Barbara Basin sediment cores were measured. The range of δ¹⁵N values for total nitrogen was $\text{+2.89 – +9.4‰}$ with a mean of $\text{+6.8‰}$ and for pore water ammonium, $\text{+8.2 – +12.4‰}$ with a mean of 10.2‰.The results suggest that the dissolved ammonium in the pore water is produced from bacterial degradation of marine organic matter. The range of δ¹⁵N values for total nitrogen in the sediment is interpreted as resulting from an admixture of nitrogen derived from marine ($\text{+10‰}$) and terrestrial (+2‰ marines. The marine component of this mixture, composed principally of calcium carbonate with smaller amounts of opal and organic matter, contains ～ 1.0% nitrogen. The terrestrial component, which comprises over 80% of the sediment, contains ～ 0.1% organically bound nitrogen and accounts for > 25% of the total nitrogen in Santa Barbara Basin sediment.     

The supply and preservation of ancient and modern components of organic carbon in the Canadian Beaufort Shelf of the Arctic Ocean

The provenance of organic matter in sediments from the Mackenzie River and Beaufort Shelf was investigated using the stable carbon and radiocarbon isotopic compositions of bulk organic matter and the stable carbon isotopic compositions of individual organic compounds, including lignin-derived phenols and lipid-derived fatty acids. Most river suspended sediments and shelf surface sediments contained organic carbon characterized by highly depleted Δ¹⁴C values that were consistent with average radiocarbon ages exceeding 7000 years. The stable carbon isotopic signatures of lignin phenols were uniformly depleted (−25≥δ¹³C≥−32‰), indicating the predominant contributions of C₃ vascular plant sources. The isotopic compositions of C₁₄ and C₁₆ fatty acids exhibited important contrasts between the river (−36‰ to −40‰) and shelf (−25‰ to −29‰) sediments that were consistent with contributions from freshwater algae and/or vascular plants in the former and marine phytoplankton in the latter. Using ¹⁴C isotopic mass balance, the abundances of modern and ancient organic matter were quantitatively constrained. The fate of organic matter in the Beaufort Shelf was explored by normalizing these abundances to the specific surface area of sediments. Ancient organic carbon, which may include old pre-aged soil material as well as fossil bitumen or kerogen, accounted for the majority (∼70%) of the particulate organic matter exported by the Mackenzie River and deposited in surface sediments of the Beaufort Shelf. Modern organic carbon accounted for ∼30% in both river and shelf sediments, with significant contributions from vascular plant-derived materials in both river and shelf samples and from marine algae in the shelf sediments. Respiration (and/or leaching) of particle-bound marine organic matter dominates the carbon metabolism in the Mackenzie Delta/Beaufort Shelf region. However, land-derived pools, including modern carbon derived from vascular plants as well as ancient carbon also appeared to undergo a degree of post-depositional degradation prior to burial in the shelf. These novel source apportionments are reflected in an updated carbon budget for the study area.     

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.     

Characteristics,genesis and parameters controlling the development of a large stratabound HTD body at Matienzo (Ramales Platform,Basque–Cantabrian Basin,northern Spain)

At Matienzo (Basque–Cantabrian Basin, northern Spain), a large stratabound HTD body (4 by 2 km² and 80–400 m thick) delimited by two parallel sinistral strike-slip faults is exposed in Aptian carbonates. The margins of the HTD body are characterised by dolomite “tongues” indicating that some limestone beds were more prone to dolomitisation. However, no clear relationship between HTD occurrence and precursor limestone facies can be established. Massive limestone beds, as found at the top of the HTD body, act as barriers to hydrothermal processes, since no dolomite is present in or above these beds. Three types of dolomites have been differentiated, i.e. 1) matrix, 2) coarse crystalline and 3) zebra dolomite. The distribution of the dolomite types is attributed to ascending fluid flow and changing degree of dolomite oversaturation.The dolomite body was formed by two dolomitisation phases under burial conditions. No indications for a synsedimentary/early diagenetic dolomitisation have been observed. The first dolomitisation phase is characterized by ferroan dolomite and the second by non-ferroan dolomite. The two HTD phases are characterised by depleted δ¹⁸O-values (ranging between −10‰ and −16‰ V-PDB), δ¹³C-values similar to the Aptian–Albian marine signature and homogenisation temperatures of primary fluid inclusions between 120 °C and 150 °C. The dolomitising fluid was enriched in ⁸⁷Sr compared to Aptian seawater, excluding the latter as an unmodified fluid source for dolomitisation. Microthermometry of primary fluid inclusions indicates that the dolomitising fluid evolved from a moderate saline (9.7 – 14.0 wt% NaCl) to a more saline (10.9 – 21.0 wt% NaCl) H₂O–NaCl brine. The dolomitising fluid likely originated from evaporated seawater. Fluid circulation through the dolomitised strata is inferred to have taken place during the tectonically active period of the late Albian throughout which important sinistral-strike slip movements along basement faults occurred.     

Organic carbon stable isotope ratios of continental margin sediments

Stable isotope ratios (δ¹³C) of total organic carbon were measured in surface sediments from the continental margins of the northern and western Gulf of Mexico, the north coast of Alaska and the Niger Delta. Gulf of Mexico outer-shelf isotope ratios were in the same range as has been reported for Atlantic coastal shelf sediments, ?21.5 to ?20‰. Off large rivers including the Mississippi, Niger and Atchafalaya (Louisiana), δ¹³C values increased from terrigenous-influenced (around ?24‰) to typically marine ($\text{～?20‰}$) within a few tens of kilometers from shore. This change was accompanied by a decrease in the amount of woody terrigenous plant remains in the sediment. Alaskan continental margin samples from the cold Beaufort Sea had isotopically more negative carbon (?25.5 to ?22.6‰) than did warmer-water sediments. The data indicate that the bulk of organic carbon in Recent sediments from nearshore to outer continental shelves is marine derived.