Mineralogical and chemical distribution of the Es3L oil shale in the Jiyang Depression,Bohai Bay Basin (E China): Implications for paleoenvironmental reconstruction and organic matter accumulation

The Es₃^L (lower sub-member of the third member of the Eocene Shahejie Formation) shale in the Jiyang Depression is a set of relatively thick and widely deposited lacustrine sediments with elevated organic carbon, and is considered to be one of the most important source rocks in East China. We can determine the mineralogy, organic and inorganic geochemistry of the Es₃^L shale and calculate paleoclimate indexes by using multiple geochemical proxies based on organic chemistry (total organic carbon [TOC] and Rock-Eval pyrolysis), major and trace elements, X-Ray diffraction, and carbon and oxygen isotope data from key wells alongside ECS (Elemental Capture Spectroscopy) well log data. These indicators can be used to analyze the evolution of the paleoenvironment and provide a mechanism of organic matter (OM) accumulation. The Es₃^L oil shale has high TOC abundance (most samples >3.0%) and is dominated by Type I kerogens. Additionally, the organic-rich shale is rich in CaO and enrichment in some trace metals is present, such as Sr, Ba and U. The positive δ¹³C and negative δ¹⁸O values, high Sr/Ba, B/Ga and Ca/Ca + Fe ratios and low C/S ratios indicate that the Es₃^L shales were mainly deposited in a semi-closed freshwater-brackish water lacustrine environment. The consistently low Ti/Al and Si/Al ratios reflect a restricted but rather homogeneous nature for the detrital supply. Many redox indicators, including the Th/U, V/(V + Ni), and δU ratios, pyrite morphology and TOC-TS-Fe diagrams suggest deposition under dysoxic to suboxic conditions. Subsequently, the brackish saline bottom water evolved into an anoxic water body under a relatively arid environment, during which organic-lean marls were deposited in the early stage. Later, an enhanced warm-humid climate provided an abundant mineral nutrient supply and promoted the accumulation of algal material. OM input from algal blooms reached a maximum during the deposition of the organic-rich calcareous shale with seasonal laminations. High P/Ti ratios and a strongly positive relationship between the P and TOC contents indicate that OM accumulation in the oil shale was mainly controlled by the high primary productivity of surface waters with help from a less stratified water column. Factors such as the physical protection of clay minerals and the dilution of detrital influx show less influence on OM enrichment.     

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.     

Stable carbon isotopic ratios of CH4-CO2-bearing fluid inclusions in fracture-fill mineralization from the Lower Saxony Basin (Germany) - A tool for tracing gas sources and maturity

The stable carbon isotopic ratios (δ¹³C) of methane (CH₄) and carbon dioxide (CO₂) of gas-rich fluid inclusions hosted in fracture-fill mineralization from the southern part of the Lower Saxony Basin, Germany have been measured online using a crushing device interfaced to an isotopic ratio mass spectrometer (IRMS). The data reveal that CH₄ trapped in inclusions seems to be derived from different source rocks with different organic matter types. The δ¹³C values of CH₄ in inclusions in quartz hosted by Carboniferous rocks range between −25 and −19‰, suggesting high-maturity coals as the source of methane. Methane in fluid inclusions in minerals hosted by Mesozoic strata has more negative carbon isotope ratios (−45 to −31‰) and appears to represent primary cracking products from type II kerogens, i.e., marine shales. There is a positive correlation between increasing homogenization temperatures of aqueous fluid inclusions and less negative δ¹³C(CH₄) values of in co-genetic gas inclusions probably indicating different mtaturity of the potential source rocks at the time the fluids were released. The CO₂ isotopic composition of CH₄-CO₂-bearing inclusions shows slight negative or even positive δ¹³C values indicating an inorganic source (e.g., water-rock interaction and dissolution of detrital, marine calcite) for CO₂ in inclusions. We conclude that the δ¹³C isotopic ratios of CH₄-CO₂-bearing fluid inclusions can be used to trace migration pathways, sources of gases, and alteration processes. Furthermore, the δ¹³C values of methane can be used to estimate the maturity of the rocks from which it was sourced. Results presented here are further supported by organic geochemical analysis of surface bitumens which coexist with the gas inclusion-rich fracture-fill mineralization and confirm the isotopic interpretations with respect to fluid source, type and maturity.     

Characteristics and origin of carbon isotopes of n-alkanes in crude oils from the western Pearl River Mouth Basin,South China sea

The quantitative characterization of carbon isotopes of n-alkanes is commonly carried out in organic geochemical studies. Possible controls on carbon isotopes include source organic matter, maturity, fractionation during oil expulsion and migration, and the mixing of different oils. In this study of the origin of crude oils in the western Pearl River Mouth Basin, the influences of all of these factors have been considered in reaching a conclusion. Carbon isotopes of n-alkanes in the crude oils, and the extracts of the two effective source rocks (the Wenchang and Enping formations) in the basin, exhibit clear differences. The Wenchang source rocks have heavy δ¹³C values that remain almost constant or become slightly heavier with increasing carbon number. The Enping source rocks have light δ¹³C values that become lighter with increasing carbon number. Two groups of oils in this area were identified based on the carbon isotopes of the n-alkanes; groupIoils are similar to extracts of the Wenchang source rocks. However, the groupIIoils are different from both the Wenchang and Enping source rocks and the carbon isotopic profiles of their n-alkanes exhibit a “V” feature with increasing carbon number. The results of artificial thermal maturation experiments indicate that, from the early stage to the peak stage of oil generation (with EasyRo between 0.64% and 1.02%), the δ¹³C values of n-alkanes in the pyrolysis oils become heavier by about 3‰ with increasing thermal maturity, but the shape of the carbon isotopic profiles are not significantly changed. Calculated δ¹³C values of n-alkanes in “mixed” artificial pyrolysis oils indicate that the mixture of oils generated from the same source rocks with different maturities could not change the carbon isotopic profile of the n-alkanes, however, a mixing of the Wenchang and Enping oils could give the “V” feature in the profiles, similar to the groupIIoils in this area. The groupIIoils appear to be mixed Wenchang and Enping oils, the latter being the dominant component in the mixture. We conclude that the source organic matter and the degree of mixing are the main factors controlling the carbon isotopic characteristics of n-alkanes in crude oils in the western Pearl River Mouth Basin.     

Late-Quaternary supply of terrigenous organic matter to the Congo deep-sea fan (ODP site 1075): implications for equatorial African paleoclimate

Late-Quaternary sections (about 1 Ma) from the Congo deep-sea fan (ODP Leg 175, site 1075) were used to reconstruct the terrigenous organic matter supply to the easternmost equatorial Atlantic Ocean. Variations in quantity and quality of the riverine organic matter reflect the interaction between the paleoclimatic development within the continental catchment area and the paleoceanographic conditions in the Congo river plume. To characterize the delivery of organic matter from terrigenous and marine sources, we used elemental and bulk carbon isotopic analyses, Rock-Eval pyrolysis, lignin chemistry, and organic petrology. High-amplitude fluctuations occurring about every 15-25 ka reveal a mainly precessional control on organic sedimentation. Results from Rock-Eval pyrolysis indicate a mixed kerogen type III/II, as would be anticipated in front of a major river. Fluctuations in T_max from Rock-Eval pyrolysis demonstrate pronounced cyclic changes in the delivery of low- and high-mature organic matter. Contribution of the low-mature organic fraction was strongest during warm climates supporting enhanced marine production offshore of the Congo. Organic petrological observations confirm the existence of abundant terrigenous plant tissues, both non-oxidized (vitrinite) and oxidized (inertinite). Charcoal-like organic matter (fusinite) is attributed to periods of increased bush fires in the continental hinterland, and implies more arid climatic conditions. Results from ratios of specific phenolic lignin components suggest that terrigenous organic matter in Late-Quaternary sections of site 1075 mainly derives from non-woody angiosperm tissue, i.e., grasses and leaves. Correlation between the amount of specific lignin phenols and the bulk '¹³C_org signature fosters the conclusion that an appreciable amount of the terrigenous organic fraction derives from C4 plant matter. This may cause an underestimation of the terrigenous proportion of bulk organic matter when assessments are based on bulk carbon isotopic signatures alone.     

Sedimentary and residual gas geochemical characteristics of the Lower Cambrian organic-rich shales in Southeastern Chongqing,China

To study the sedimentary environment of the Lower Cambrian organic-rich shales and isotopic geochemical characteristics of the residual shale gas, 20 black shale samples from the Niutitang Formation were collected from the Youyang section, located in southeastern Chongqing, China. A combination of geochemical, mineralogical, and trace element studies has been performed on the shale samples from the Lower Cambrian Niutitang Formation, and the results were used to determine the paleoceanic sedimentary environment of this organic-rich shale. The relationships between total organic carbon (TOC) and total sulfur (TS) content, carbon isotope value (δ¹³C_org), trace element enrichment, and mineral composition suggest that the high-TOC Niutitang shale was deposited in an anoxic environment and that the organic matter was well preserved after burial. Stable carbon isotopes and biomarkers both indicate that the organic matter in the Niutitang black shales was mainly derived from both lower aquatic organisms and algaes and belong to type I kerogen. The oil-prone Niutitang black shales have limited residual hydrocarbons, with low values of S₂, I_H, and bitumen A. The carbon isotopic distribution of the residual gas indicate that the shale gas stored in the Niutitang black shale was mostly generated from the cracking of residual bitumen and wet gas during a stage of significantly high maturity. One of the more significant observations in this work involves the carbon isotope compositions of the residual gas (C₁, C₂, and C₃) released by rock crushing. A conventional δ¹³C₁–δ¹³C₂ trend was observed, and most δ¹³C₂ values of the residual gases are heavier than those of the organic matter (OM) in the corresponding samples, indicating the splitting of ethane bonds and the release of smaller molecules, leading to ¹³C enrichment in the residual ethane.     

Biogeochemical studies on the transport of organic matter along the Otsuchi River watershed,Japan

The distributions and stable isotope ratios of biogenic nitrogen and carbon were investigated in detail along a small watershed in order to establish a biogeochemical framework for assessing the fate of organic matter. Forest ecosystems supply soluble and particulate materials to river systems which are depleted in ¹⁵N and ¹³C. The number of suspended particles and the concentrations of δ¹⁵N and δ¹³C in the river sediments increased along the watershed, indicating a change from river to marine ecosystems. Dramatic variation of δ¹⁵N and δ¹³C were observed in the intertidal sediments, where the progress of denitrification, discharge of domestic sewage, and the accumulation and the decomposition of macroalgae and seagrasses took place.The contribution of land-derived organic matter to estuarine sediments has been estimated from δ¹³C and from δ¹⁵N data. The contribution the landderived organo-silty-clay mineral was 70–100% in the inner bay sediments and 34–42% at the open bay. Possible factors that influence the variation of stable isotope ratios along the watershed are discussed. The relationship between the sizes of particles and isotope ratios clearly demonstrated that organo-silty-clay minerals with diameter smaller than 64 μm were the major source of land-derived refractory organics.     

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

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

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

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

Source rock characteristics and biostratigraphy of the Lower Silurian (Telychian) organic-rich shales at Akyaka, central Taurus region, Turkey

The Akyaka section in the central Taurus region in the southern part of Turkey includes the organic matter and graptolite-rich black shales which were deposited under dysoxic to anoxic marine conditions in the Early Silurian. A biostratigraphical analysis, based on graptolite assemblages, indicates that the sediments studied may well be referable to the querichi Biozone and early Telychian, Llandovery. A total of 15 samples have been subjected to Leco and Rock-Eval pyrolysis and graptolite reflectance measurements for determination of their source rock characteristics and thermal maturity. The total organic carbon content of the graptolite-bearing shales varies from 1.75 to 3.52 wt% with an average value of 2.86 wt%. The present Rock-Eval pyrolytic yields and calculated values of hydrogen and oxygen indexes imply that the recent organic matter type is inert kerogen. The measured maximum graptolite reflectance (G_Rmax %) values are between 5.04% and 6.75% corresponding to thermally over maturity. This high maturity suggests a deep burial of the Lower Silurian sediments resulting from overburden rocks of Upper Paleozoic to Mesozoic Upper Cretaceous and Middle-Upper Eocene thrusts occurred in the region.     

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

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

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

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

δ13C analyses of oceanic particulate organic matter

Seventy-nine δ¹³C analyses of oceanic particulate matter (> 0·μ) from semi-tropical (Gulf of Mexico, Caribbean and Atlantic) and polar (South Indian Ocean) waters showed that the carbon isotope composition of the particulate matter from the cold polar surface waters was lighter ($\text{?24·7}\text{to}\text{?26·0‰}$) than that from the surface in the semi-tropical regions ($\text{?19·8}\text{to}\text{?22·3 ‰}$), reflecting the temperature effect on the photosynthetic fixation of carbon. δ¹³C for deep samples (> 330 m) were generally more negative than the surface samples, except in some well-mixed polar areas.A difference both in organic carbon isotopic composition and percentage organic carbon in the POM and the tops of sediment cores was also apparent; a loss of approximately 95 % of incoming carbon and an increase in ¹³C of several per mille being observed during deposition of particulate matter. This indicates that after settling on the bottom there is extensive diagenesis of the POM by organisms, indicating the non-refractory nature of the organic matter.     

Spatial variation in organic matter utilization by benthic communities from Yura River–Estuary to offshore of Tango Sea,Japan

We investigated the distribution of δ¹³C and δ¹⁵N of organic matter among benthic communities from the upper estuary of Yura River to offshore of Tango Sea, Japan, to determine spatial variation in utilization of organic matter by benthic communities. The δ¹³C values of benthic animals ranged from −27 to −15‰ in the upper estuary, −21 to −15‰ in the lower estuary, −20 to −16‰ in the shallow coast (5–10 m depths), −18 to −16‰ in the deep coast (30–60 m depths) and −19 to −15‰ in offshore (100–150 m depths) stations. Adapting the dual isotope values to mixing models, we estimated the relative contributions of potential food sources to the benthos diet. Phytoplankton and macroalgae that intruded the estuary in summer were utilized as alternative food aside from the terrestrial-origin organic matter assimilated by the estuarine benthic consumers. Resuspended benthic microalgae were important source of energy in the shallow coastal stations, while abundant supply of phytodetritus fueled the deep coastal and offshore benthic food webs. Spatial difference in the diet of benthic communities depends largely on the shifts in the primary carbon source. Thus, benthic communities are important link of autochthonous/allochthonous production and secondary production in the continuous river–estuary–marine system.     

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.     

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

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

北极拉普捷夫海夏、秋季颗粒有机碳的分布与来源

随着全球变暖的加剧,北极陆架边缘海碳的源汇过程对全球碳循环的影响及其气候环境效应日益显著。拉普捷夫海作为北冰洋典型的陆架边缘海,在大河、海冰、海洋初级生产力及海岸侵蚀的影响下,该区沉积有机碳的来源、输运和埋藏等过程独具特色。本文基于2018年中俄第二次北极联合科考获得的悬浮颗粒物样品和水文资料,研究了夏末秋初拉普捷夫海颗粒有机碳的分布特征、来源及其影响因素。结果表明,颗粒有机碳（POC）的浓度位于35.27～1 185.58 μg/L之间,平均为172.65 μg/L。受河流输入、海岸侵蚀和海洋初级生产力的影响,表层POC浓度分布呈现近岸高、远岸低趋势;底层POC浓度分布主要受控于沉积再悬浮作用,高浓度POC出现在勒拿河三角洲的东部区域。总悬浮颗粒物浓度与POC浓度总体呈显著正相关,显示出其对POC空间分布的直接影响,且两者在底层中的相关性要高于表层,表明不同层位的POC可能存在来源差异。研究区POC的δ13C值处于?31.03‰～?25.79‰之间,表层δ13C值较底层明显偏负,且部分站位的δ13C值甚至低于周边陆源有机碳的端元,这反映了可能除陆源输入的贡献外,近海浮游植物直接利用大量陆源有机质降解产生的溶解无机碳的过程也对该区域POC的供应和来源解析具有重要的影响。     

Carbon cycle and sea-water palaeotemperature evolution at the Middle–Late Jurassic transition,eastern Paris Basin (France)

A very high-resolution carbon and oxygen stable isotope analysis (bulk-carbonate) of a biostratigraphically well-constrained Callovian–Oxfordian series is provided here for the first time. The homogeneity of the clayey series and the weak diagenetic alteration allow the isotopic signal variations to be considered as primary in origin. A prominent and brief negative excursion in the δ¹³C curve (−2‰), occurring at the start of the Middle Callovian (Jason Zone – Obductum Subzone) and correlated regionally, suggests a possible methane release. The increasing δ¹³C values thereafter up to the Early Oxfordian, concomitant with a warming episode, highlight the burial of carbon in organic-rich layers which, in return, may have triggered a decrease in atmospheric pCO₂. At higher frequencies, observed fluctuations of the δ¹³C and δ¹⁸O values are orbitally driven (405-kyr and 100-kyr eccentricity cycles) and may correspond to the salinity and temperature variability recorded in sea water. The δ¹⁸O isotopic measurements from well-preserved diagenetically screened belemnites and bivalves along the series, compared to available data from Tethyan domains, agree with the scenario of a global cooling at the Middle-Late Jurassic transition. The well-dated δ¹⁸O isotopic curve suggests that the onset of this cooling event occurred at the end of the Coronatum Zone (Middle Callovian).     

Stable isotopes in deep-sea living (stained) foraminifera from the Mozambique Channel (eastern Africa): multispecies signatures and paleoenvironmental application

Oxygen and carbon isotopes (δ¹⁸O and δ¹³C) have been investigated in carbonate tests of deep-sea foraminifera living in the Mozambique Channel (eastern Africa) to understand how environmental constraints (e.g., organic matter, oxygenation) control the intra- and interspecific variability of isotopic signatures. 197 living individuals, including eight different species, from various microhabitats within the sediment were sorted from sediment samples gathered at two stations on the Malagasy upper slope. Results show that the δ¹⁸O values of foraminiferal taxa were not controlled by microhabitat pattern. They presented tremendous and intriguing intraspecific variability that is not explained by the classical ontogenetic effect. The δ¹³C values of infaunal foraminiferal taxa do not show a 1:1 relationship with the bottom water δ¹³C DIC and do not present a constant offset from it; instead, they appear to be mainly controlled by a microhabitat effect. The lower δ¹³C values of shallow, intermediate, and deep infaunal taxa at the deeper station compared to those seen at the shallower station reflect the enhanced exportation of sedimentary organic matter at the sediment–water interface, and its related mineralization within the upper sediments. The ?δ¹³C between shallow/very shallow infaunal species (i.e., Hoeglundina elegans, Uvigerina hispida) and intermediate/deep infaunal species (i.e., Melonis barleeanus, Globobulimina barbata) permits insight into (1) the exportation of organic matter to the seafloor and (2) the various degradation pathways for organic detritus in the benthic environments off NW Madagascar.