Geochemical characterization of secondary microbial gas occurrence in the Songliao Basin, NE China

A suite of natural gases from the northern Songliao Basin in NE China were characterized for their molecular and carbon isotopic composition. Gases from shallow reservoirs display clear geochemical evidence of alteration by biodegradation, with very high dryness (C₁/C₂₊ > 100), high C₂/C₃ and i-C₄/n-C₄ ratios, high nitrogen content and variable carbon dioxide content. Isotopic values show wide range variations (δ¹³C_CH4 from −79.5‰ to −45.0‰, δ¹³C_C2H6 from −53.7‰ to −32.2‰, δ¹³C_C3H8 from −36.5‰ to −20.1‰, δ¹³C_nC4H10 from −32.7‰ to −24.5‰, and δ¹³C_CO2 from −21.6‰ to +10.5‰). A variety of genetic types can be recognized on the basis of chemical and isotopic composition together with their geological occurrence. Secondary microbial gas generation was masked by primary microbial gas and the mixing of newly generated methane with thermogenic methane already in place in the reservoir can cause very complicated isotopic signatures. System openness also was considered for shallow biodegraded gas accumulations. Gases from the Daqing Anticline are relatively wet with ¹³C enriched methane and ¹³C depleted CO₂, representing typically thermogenic origin. Gases within the Longhupao-Da’an Terrace have variable dryness, ¹³C enriched methane and variable δ¹³C of CO₂, suggesting dominant thermogenic origin and minor secondary microbial methane augment. The Puqian-Ao’nan Uplift contains relatively dry gas with ¹³C depleted methane and ¹³C enriched CO₂, typical for secondary microbial gas with a minor part of thermogenic methane. Gas accumulations in the Western Slope are very dry with low carbon dioxide concentrations. Some gases contain ¹³C depleted methane, ethane and propane, indicating low maturity/primary microbial origin. Recognition of varying genetic gas types in the Songliao Basin helps explain the observed dominance of gas in the shallow reservoir and could serve as an analogue for other similar shallow gas systems.     

Relationships between carbon isotope evolution and variation of microbes during the Permian–Triassic transition at Meishan Section, South China

This paper investigates kerogen carbon isotopes, the difference between carbonate and kerogen carbon isotopes (Δ¹³C_carb-kero = δ ¹³C_carb − δ ¹³C_kero) and the difference between carbonate and n-C₁₉ alkane compound-specific carbon isotopes (Δ¹³C_carb-n-C19 = δ ¹³C_carb − δ ¹³C _n-C19) during the Permian–Triassic transition at Meishan, South China. The results show that kerogen carbon isotopes underwent both gradual and sharp shifts in beds 23–25 and 26–29, respectively. The differences between carbonate and organic carbon isotopes, both the Δ¹³C_carb-kero and Δ¹³C_carb-n-C19, which are mainly affected by CO₂-fixing enzyme and pCO₂, oscillated frequently during the Permian–Triassic transition. Both the variations of Δ¹³C_carb-n-C19 and Δ¹³C_carb-kero coupled with the alternation between cyanobacteria and green sulfur bacteria indicated by biomarkers. The episodic low values of Δ¹³C_carb-n-C19 corresponded to episodic blooms of green sulfur bacteria, while the episodic high values of Δ¹³C_carb-n-C19 corresponded to episodic blooms of cyanobacteria. The relationships between the variation of carbon isotopes and biota show that the microbes which flourished after the extinction of macroorganism affected the carbon isotope fractionation greatly. Combining the carbon isotope compositions and the pattern of size variation of the conodont Neogondolella, this paper supposes that anoxia of the photic zone at bed 24 was episodic and it would be caused by the degradation of terrigenous organic matters by sulfate reducing bacteria in the upper water column. Considered together with results from previous research, the high resolution variation of the biogeochemistry presents the sequence of the important geo-events during the Permian–Triassic crisis.     

Carbon isotopic composition of individual n-alkanes in asphaltene pyrolysates of biodegraded crude oils from the Liaohe Basin, China

Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C₁₆–C₂₉ range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.     

Metabolic effects on stable carbon isotopic composition of freshwater bivalve shell Corbicula fluminea

The stable isotopic composition of the bivalve shell has been widely used to reconstruct the pa-laeo-climate and palaeo-environment. The climatic and environmental significance of carbon isotopic composition of the bivalve shell is still in dispute, and incorporation of metabolic carbon can obscure carbon isotope records of dis-solved inorganic carbon. This study deals with freshwater bivalve, Corbicula fluminea aragonite shell. The results indicated that the δ13C values of bivalve shells deposited out of equilibrium with the host water and showed an onto-genic decrease, indicating that there are metabolic effects and more metabolic carbon is incorporated into larger shells. The proportion of metabolic carbon of shells varies between 19.8% and 26.8%. However, δ13CS can still be used as qualitative indicators of δ13CDIC and environmental processes that occurred during shell growth.     

Genetic identification of natural gases from shallow reservoirs in some oil- and gas-bearing basins of China

Natural gases of shallow reservoirs with the carbon isotopic compositions of methane ranging from -50‰ to -60‰ (PDB) were considered as mixed gases of biogenic and thermogenic origins previously and some of them were considered as low-mature (or low temperature thermogenic) gases lately. In this paper natural gases with the carbon isotopic compositions of methane in the above range were identified using the molecular and stable carbon isotopic compositions of methane, ethane and propane. The mixed gases of biogenic and mature thermogenic origins display the characteristics of δ 13 C1 ranging from -50‰to -60‰,δ13C2 ＞ -35‰,Δvalues (δ13C3 -δ13C2) ＜ 5‰ and C1/∑C2 ratios ＜ 40. Immature to low-mature gases display the characteristics of δ 13 C1 ranging from - 50‰ to - 60‰, δ13 C2 ＜- 40‰,Δ values (δ13C3 -δ13C2) ＞7‰, and C1/∑C 2 ratios ＞60.     

Stable carbon isotope characteristics of different plant species and surface soil in arid regions

The stable carbon isotope composition in surface soil organic matter (δ¹³Csoil) contains integrative information on the carbon isotope composition of the standing terrestrial plants (δ¹³Cleaf). In order to obtain valuable vegetation information from the δ¹³C of terrestrial sediment, it is necessary to understand the relationship between the δ¹³C value in modern surface soil and the standing vegetation. In this paper, we studied the δ¹³C value in modern surface soil organic matter and standing vegetation in arid areas in China, Australia and the United States. The isotopic discrepancy between δ¹³Csoil and δ¹³Cleaf of the standing dominant vegetation was examined in those different arid regions. The results show that the δ¹³Csoil values were consistently enriched compared to the δ¹³Cleaf. The δ¹³Cleaf values were positively correlated with δ¹³Csoil, which suggests that the interference of microorganisms and hydrophytes on the isotopic composition of surface soil organic matter during soil organic matter formation could be ignored in arid regions. The averaged discrepancy between δ¹³Csoil and δ¹³Cleaf is about 1.71%in Tamarix L. in the Tarim Basin in China, 1.50% in Eucalytus near Orange in Australia and 1.22% in Artemisia in Saratoga in the United States, which are different from the results of other studies. The results indicate that the discrepancies in the δ¹³C value between surface soil organic matter and standing vegetation were highly influenced by the differences in geophysical location and the dominant species of the studied ecosystems. We suggest that caution should be taken when organic matter δ¹³C in terrestrial sediment is used to extract paleovegetation information (C₃/C₄ vegetation composition), as the δ¹³C in soil organic matter is not only determined by the ratio of C₃/C₄ species, but also profoundly affected by climate change induced variation in the δ¹³C in dominant species.     

Geochemical characteristics and possible origin of natural gas in the Taibei Depression,Turpan-Hami Basin,China

292 chemical composition data and 82 isotopic composition data of gas samples collected from the Taibei Depression of the Turpan-Hami Basin, West China, were used in the study of their origin. Non-hydrocarbon gas is poor in most samples whereas abundant nitrogen in some samples is positively correlated with δ13C1. Although methane is the main constituent, higher molecular gaseous hydrocarbons, from ethane to pentane, are detected in most samples, in accordance with the distribution of oil reservoirs. The stable carbon isotope ratios of methane, eth-ane and propane are defined as d13C1: -45.5‰ to -33.5‰, d13C2: -30.2‰ to -10.5‰, and d13C3: 27.6‰ to -11.2‰, respectively. According to the distribution of carbon isotope ratios, 2 families of gas can be grouped, most showing normal distribution of carbon isotopes, and others having obvious heavier carbon isotopes and being of abnormal distribution. Based on the isotopic composition, the disagreement between the relationship of Δ(d13C1-d13C2) and d13C2 and that of Δ(d13C1-d13C2) and d13C2, and the calculated Ro, there are oil-associated gas, coal-derived gas and mixture of them. Other samples with obviously heavier isotopic compositions from the Yanmuxi oilfield of the Taibei Depression have been degraded by organisms.     

Use of biomarker distributions and compound specific isotopes of carbon and hydrogen to delineate hydrocarbon characteristics in the East Sirte Basin (Libya)

Biomarker ratios, together with stable carbon (δ¹³C) and hydrogen (δD) isotopic compositions of individual hydrocarbons have been determined in a suite of crude oils (n = 24) from the East Sirte Basin to delineate their sources and respective thermal maturity. The crude oil samples are divided into two main families (A and B) based on differences in source inputs and thermal maturity. Using source specific parameters including pristane/phytane (Pr/Ph), hopane/sterane, dibenzothiophene/phenanthrene (DBT/P), Pr/n-C₁₇ and Ph/n-C_l8 ratios and the distributions of tricyclic and tetracyclic terpanes, family B oils are ascribed a marine source rock deposited under sub-oxic conditions, while family A oils have a more terrigenous source affinity. This genetic classification is supported by the stable carbon isotopic compositions (δ¹³C) of the n-alkanes. Using biomarker maturity parameters such as the abundance of Pr and Ph relative to n-alkanes and the distribution of sterane and hopane isomers, family A oils are shown to be more thermally mature than family B oils. The contrasting maturity of the two families is supported by differences between the stable hydrogen isotopic compositions (δD) of Pr and Ph and the n-alkanes, as well as the δ¹³C values of n-alkanes in their respective oils.     

n-alkane distribution coupled with organic carbon isotope composition in the shell bar section, Qarhan paleolake, Qaidam basin, NE Tibetan Plateau

Lipids extracted from lacustrine deposits in the paleolake Qarhan of the Qaidam basin in the northeastern Tibetan Plateau were determined by conventional gas chromatography-mass spectrometry. Several series of biomarkers were identified, mainly including n-alkanes, n-alkan-2-ones, n-alkanoic acids, branched alkanes, triterpenoids and steroids, indicative of various biogenic contributions. On the basis of cluster analysis, the n-C₁₅, n-C₁₇, n-C₁₉ alkanes were proposed to be derived from algae and/or photosynthetic bacteria, the n-C₂₁, n-C₂₃, n-C₂₅ homologues from aquatic plants, and the n-C₂₉, n-C₃₁ homologues from vascular plants. In contrast, the n-C₂₇ alkane is not categorized in the n-C₂₉ and n-C₃₁ group of alkanes, probably due to more complex origins including both aquatic and vascular plants, and/or differential biodegradation. Stratigraphically, layers-2, 4 and 5 were found to show a close relationship in n-alkane distribution, associated with a positive shift in carbon isotope composition of bulk organic matter (δ¹³C_org), inferring a cold/dry period. Layers-1 and 6 were clustered together in association with a negative δ¹³C_org, excursion, probably indicating a relatively warm/humid climate. The potential coupling between the n-alkane distributions and δ¹³C_org, suggests a consequence of vegetation change in response to climate change, with the late MIS3 being shown to be unstable, thought to be the climatic optimum in the Tibetan Plateau. Our results suggest that the cluster analysis used in this study probably provides an effective and authentic method to investigate the n-alkane distribution in paleolake sediments.     

Carbon and oxygen isotope constraints on fluid sources and fluid–wallrock interaction in regional alteration and iron-oxide–copper–gold mineralisation, eastern Mt Isa Block, Australia

The source of metasomatic fluids in iron-oxide–copper–gold districts is contentious with models for magmatic and other fluid sources having been proposed. For this study, δ ¹⁸O and δ ¹³C ratios were measured from carbonate mineral separates in the Proterozoic eastern Mt Isa Block of Northwest Queensland, Australia. Isotopic analyses are supported by petrography, mineral chemistry and cathodoluminescence imagery. Marine meta-carbonate rocks (ca. 20.5‰ δ ¹⁸O and 0.5‰ δ ¹³C calcite) and graphitic meta-sedimentary rocks (ca. 14‰ δ ¹⁸O and −18‰ δ ¹³C calcite) are the main supracrustal reservoirs of carbon and oxygen in the district. The isotopic ratios for calcite from the cores of Na–(Ca) alteration systems strongly cluster around 11‰ δ ¹⁸O and −7‰ δ ¹³C, with shifts towards higher δ ¹⁸O values and higher and lower δ ¹³C values, reflecting interaction with different hostrocks. Na–(Ca)-rich assemblages are out of isotopic equilibrium with their metamorphic hostrocks, and isotopic values are consistent with fluids derived from or equilibrated with igneous rocks. However, igneous rocks in the eastern Mt Isa Block contain negligible carbon and are incapable of buffering the δ ¹³C signatures of CO₂-rich metasomatic fluids associated with Na–(Ca) alteration. In contrast, plutons in the eastern Mt Isa Block have been documented as having exsolved saline CO₂-rich fluids and represent the most probable fluid source for Na–(Ca) alteration. Intrusion-proximal, skarn-like Cu–Au orebodies that lack significant K and Fe enrichment (e.g. Mt Elliott) display isotopic ratios that cluster around values of 11‰ δ ¹⁸O and −7‰ δ ¹³C (calcite), indicating an isotopically similar fluid source as for Na–(Ca) alteration and that significant fluid–wallrock interaction was not required in the genesis of these deposits. In contrast, K- and Fe-rich, intrusion-distal deposits (e.g. Ernest Henry) record significant shifts in δ ¹⁸O and δ ¹³C towards values characteristic of the broader hostrocks to the deposits, reflecting fluid–wallrock equilibration before mineralisation. Low temperature, low salinity, low δ ¹⁸O (<10‰ calcite) and CO₂-poor fluids are documented in retrograde metasomatic assemblages, but these fluids are paragenetically late and have not contributed significantly to the mass budgets of Cu–Au mineralisation.     

Carbon isotopes of Middle–Lower Jurassic coal-derived alkane gases from the major basins of northwestern China

Coal-derived hydrocarbons from Middle–Lower Jurassic coal-bearing strata in northwestern China are distributed in the Tarim, Junggar, Qaidam, and Turpan-Harmi basins. The former three basins are dominated by coal-derived gas fields, distributed in Cretaceous and Tertiary strata. Turpan-Harmi basin is characterized by coal-derived oil fields which occur in the coal measures. Based on analysis of gas components and carbon isotopic compositions from these basins, three conclusions are drawn in this contribution: 1) Alkane gases with reservoirs of coal measures have no carbon isotopic reversal, whereas alkane gases with reservoirs not of coal measures the extent of carbon isotopic reversal increases with increasing maturity; 2) Coal-derived alkane gases with high δ¹³C values are found in the Tarim and Qaidam basins (δ¹³C₁: − 19.0 to − 29.9‰; δ¹³C₂: − 18.8 to − 27.1‰), and those with lowest δ¹³C values occur in the Turpan-Harmi and Junggar basins (δ¹³C₁: − 40.1 to − 44.0‰; δ¹³C₂: − 24.7 to − 27.9‰); and 3) Individual specific carbon isotopic compositions of light hydrocarbons (C_5–8) in the coal-derived gases are lower than those in the oil-associated gases. The discovered carbon isotopic reversal of coal-derived gases is caused by isotopic fractionation during migration and secondary alteration. The high and low carbon isotopic values of coal-derived gases in China may have some significance on global natural gas research, especially the low carbon isotope value of methane may provide some information for early thermogenic gases. Coal-derived methane typically has much heavier δ¹³C than that of oil-associated methane, and this can be used for gas–source rock correlation. The heavy carbon isotope of coal-derived ethane is a common phenomenon in China and it shed lights on the discrimination of gas origin. Since most giant gas fields are of coal-derived origin, comparative studies on coal-derived and oil-associated gases have great significance on future natural gas exploration in the world.     

Stable carbon and oxygen isotopic study of carbonate along a loess/paleosol section in Lantian County, Shaanxi Province, on the southeastern edge of the Chinese Loess Plateau

Studies of carbonate carbon isotope of loess/paleosol (δ¹³C_carb) in the Chinese Loess Plateau (CLP) have shown δ¹³C_carb less negative in loess and more negative in paleosol, which is opposite to that of bulk organic matter. Although some mechanisms have been proposed to explain this inconsistency, few studies have been conducted to investigate how carbonate migration could affect the reliability of utilizing δ¹³C_carb as an effective indicator. Here, a loess/paleosol profile with a nodule horizon intercalated in the loess layer, located on the southeastern edge of the CLP, was investigated to understand the influence of carbonate eluviation and reprecipitation on δ¹³C_carb along the section. The mean grain size and magnetic susceptibility generally conform to the field observed loess/paleosol stratigraphy. However, carbonate content shows distinct differences in the two sides of the nodule horizon, clearly indicating eluviation along the section. The variation of carbon and oxygen isotopic compositions of soil carbonate (δ¹³C_SC and δ¹⁸O_SC) and nodule carbonate (δ¹³C_NC and δ¹⁸O_NC) along the profile does not present a clearly meaningful picture. Generally, δ¹³C_SC and δ¹⁸O_SC have a similar change trend along the profile and are positively correlated, but there is no apparent relationship between δ¹³C_NC and δ¹⁸O_NC. More importantly, δ¹⁸O_NC values fall in the range of δ¹⁸O_SC, whereas δ¹³C_NC values are much more positive than δ¹³C_SC. Detailed analyses of the data indicate migration of carbonate along the profile, which is an important factor that determines that loess/paleosol δ¹³C_carb could not be employed as a high-resolution paleovegetational and paleoenvironmental indicator in the CLP, at least on or below the glacial/interglacial scales.     

Variscan and post-Variscan lead–zinc mineralization, Rhenish Massif, Germany: evidence for sulfide precipitation via thermochemical sulfate reduction

A mechanical decrepitation device coupled with a gas chromatograph has been used to characterize the molecular composition of gaseous and liquid hydrocarbons contained in minerals. Application of this technique allows the identification of low-molecular-weight n-alkanes and some aromatic hydrocarbons in sulfides and gangue minerals from epigenetic Variscan and post-Variscan lead–zinc deposits in the Rhenish Massif, Germany. Based on the analysis of 200 samples, Variscan and post-Variscan mineralization can be distinguished by the composition of associated hydrocarbons. Variscan sulfides and gangue minerals contain high abundancies of methane. In contrast, n-alkanes in the C₂–C₉ range and aromatic hydrocarbons (benzene, toluene) are dominant in post-Variscan mineralization. The absence of high-molecular-weight hydrocarbons in ore minerals suggests highly mature gas associated with hydrothermal activity, during which hydrothermal fluids caused an increase in thermal maturation of organic matter and the generation of low-molecular-weight hydrocarbons in the adjacent organic-rich rocks. The hydrocarbon compositions contained in fluid inclusions of Variscan and post-Variscan minerals are probably governed by the maturation level of the potential source rocks. In Variscan time tectonic brines (T > 175 °C) generated predominantly methane, whereas basement brines (T < 175 °C) expelled higher-molecular-weight hydrocarbons (wet gases, condensates, aromatic hydrocarbons) from adjacent rocks during the Mesozoic event. The specific role of hydrocarbons in sulfide precipitation via thermochemical sulfate reduction is indicated by geochemical characteristics of organic matter associated with the Plombières Pb–Zn deposit, in eastern Belgium. Intense alteration phenomena were observed in near-ore kerogens, compared with unaltered kerogens far from the ore body, as well as by a very high maturity (5.40% R_o), a systematic depletion in ¹²C towards the vein-type mineralization, high atomic S/C ratios (0.49), and by low atomic H/C ratios (0.29). The data suggest that hydrothermal solutions caused a drastic increase in the thermal maturation of organic matter within the adjacent wall rock. Increased thermal maturation resulted in increased δ¹³C-values of organic carbon due to the preferential release of ¹²C. The change in the organic matter to a H-depleted and S-enriched bulk composition in association with sulfide ores strongly suggests that thermochemical sulfate reduction was responsible for organic degradation. Thus, thermochemical sulfate reduction probably triggered base metal sulfide precipitation in Variscan and post-Variscan ore deposits of the Rhenish Massif. Finally, based on data from this study and previous investigations, new genetic models are presented for both Variscan and post-Variscan mineralization in the Rhenish Massif. Received: 15 September 1999 / Accepted: 2 December 1999     

Sources of dissolved organic carbon in forest soils: evidences from the differences of organic carbon concentration and isotope composition studies

There is considerable discussion and uncertainty in the literature regarding the importance of fresh litter versus older soil organic matter as sources of soil dissolved organic carbon (DOC) in forest floor. In this study, the differences of organic carbon concentration and stable isotope composition were analyzed under different background conditions to identify the origins of DOC in forest soil. The data show that there is no significant difference in SOC content between these collected soil samples (P > 0.05), but the litter-rich surface soils have relatively higher DOC concentration than the litter-lacking (P < 0.01) ones, and the δ ¹³C values of DOC (δ ¹³C_DOC) are closer to δ ¹³C of litter than δ ¹³C values of SOC (δ ¹³C_SOC). In the litter-lacking surface soil samples, the range of δ ¹³C_DOC is between δ ¹³C_SOC and δ ¹³C of dominant plant leaves. These results suggest that DOC mainly derive from litter in the litter-rich surface soil with, and the main path of DOC sources may change with surrounding conditions. In addition, δ ¹³C_SOC and δ ¹³C_DOC become more positive, and the absolute values of Δ (δ ¹³C_DOC − δ ¹³C_SOC) decrease with depth in the soil profiles, which indicate that the percentage of DOC below 5 cm, derived from degradation of humus, may increase with soil depth.     

A compound-specific n-alkane δC and δD approach for assessing source and delivery processes of terrestrial organic matter within a forested watershed in northern Japan

We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ¹³C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ¹³C values of odd carbon numbered C₂₃-C₃₃n-alkanes ranged from −37.2‰ to −31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from −244‰ to −180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ¹³C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C₂₅-C₃₁n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment.     

Using GC-MS/Combustion/IRMS to determine the C/C ratios of individual hydrocarbons produced from the combustion of biomass materials--application to biomass burning

Simultaneous mass spectral detection and stable carbon isotope analysis was performed on individual indigenous n-alkanes isolated from single C₄ and C³ plant species and on a series of aliphatic and polycyclic aromatic hydrocarbons (PAH) produced from the combustion of these same biomass materials. The analysis technique used a combined gas chromatograph-mass spectrometer/combustion/isotope ratio mass spectrometer (GC-MS/C/IRMS). Precision (2σ) for replicate measurements of individual compounds in standard solutions using this novel configuration ranged between 0.2 and 0.5‰ for n-alkanes and 0.3 and 0.8‰ for PAH. Accuracy of the n-alkane measurements ranged between 0.1 and 0.4‰ and that of the PAH measurements ranged between 0.2 and 0.9‰. Replicate GC-MS/C/IRMS measurements on the combustion-derived n-alkene/alkane pairs were performed to within a precision of between 0.1 and 1.1‰ and the precision for the combustion PAH was similar to the standard PAH solution. No notable isotopic effects were observed when altering the temperature of the combustion process from 900 to 700°C, or as a result of the individual n-alkenes/alkanes partitioning between the gaseous and condensate fractions. Combustion-derived n-alkenes/alkanes ranged from C₁₁ to C₃₁, and the C₄-derived n-alkenes/alkanes were approx. 8‰ more enriched in ¹³C than the C₃-derived compounds. Both the C₄ and C₃-derived n-alkenes/alkanes (C₂₀-C₃₀) were isotopically similar to the indigenous n-alkanes and were 2-3‰ more depleted in ¹³C than the lower mol. wt (C₁₁₁₁-C₁₉) n-alkenes/alkanes, suggesting an independent origin for the lower mol. wt compounds. Combustion-generated C₄ and C₃-derived 2-, 3-, and 4-ring PAH were also isotopically distinct (Δδ = 10‰). Unlike the n-alkenes/alkanes, no compound-to-compound variations were observed between the low and high mol. wt PAH. This study demonstrates that the isotopic composition of original plant biomass material is mainly preserved in the aliphatic hydrocarbons and PAH generated by its combustion. Consequently, analyses of these compounds in sediments impacted by fire occurrences may provide useful information about paleo-fire activity that may help elucidate the impact biomass burning may have had and could have on climate-biosphere interactions.     

Light hydrocarbons geochemistry of surface sediment from petroliferous region of the Mehsana block,North Cambay Basin

A study was carried out to test the usefulness of surface geochemical methods as regional evaluation tools in petroliferous region of the Mehsana block, North Cambay Basin. A suite of 135 soil samples collected from the depth of 2.5 m, were analyzed for adsorbed light gaseous hydrocarbons and carbon isotopes (δ¹³C_methane and δ¹³C_ethane). The light gaseous hydrocarbon analysis show that the concentration ranges 402 ppb, 135 ppb, 70 ppb, 9 ppb and 18 ppb of C₁, C₂, C₃, iC₄ and nC₄, respectively. The value of carbon isotopic ranges of methane −29.5 to −43.0‰ (PDB) and ethane −19.1 to −20.9‰ (PDB). This data, when mapped, indicates patterns coinciding with major known oil and/or gas field of Sobhasan/Linch in this study area. The existence of un-altered petroliferous microseeps of catagenetic origin is observed in the study area. A regional study, such as the one described here, can provide important exploration facts concerning the regional hydrocarbon potential in a block. This method has been confirmed and can be applied successfully in frontier basins.     

Biogeochemistry of the Russian Arctic. Kara Sea: Research results under the SIRRO project, 1995–2003

The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions aboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO₂ were examined throughout the whole sea area at more than 200 sites. The δ¹³C varies from −22 and −24‰ where Atlantic waters enter the Kara Sea and in the North-eastern part of the water area to −27‰ in the Yenisei and Ob estuaries. The value of δ¹³C of the plankton is only weakly correlated with the δ¹³C of the organic matter from the sediments and is lower by as much as 3–4‰. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the riverwaters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the off-shore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from −29 to −35‰ in the riverine part, from −28 to −27‰ in the estuaries, and from −27.0 to −25% in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO₂ concentrations, and long-distance CO₂ supply to the sea with riverwaters. The data obtained on the isotopic composition of CO₂ in the surface waters of the Kara Sea were used to map the distribution of δ¹³C_{CO 2}. The complex of hydrocarbon gases extracted from the waters included methane, C₂–C₅, and unsaturated C₂₌–C₄₌ hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3–5 μl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with δ¹³C from −105 to −90‰ first occurs in the sediments at depths of 40–200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the δ¹³C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (δ¹³C from −25 to −60‰) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea. Original Russian Text ? E.M. Galimov, L.A. Kodina, O.V. Stepanets, G.S. Korobeinik, 2006, published in Geokhimiya, 2006, No. 11, pp. 1139–1191.     

Sulfur isotopic composition of hydrothermal precipitates from the Lau back-arc: implications for magmatic contributions to seafloor hydrothermal systems

The sulfur isotopic composition of sulfides and barite from hydrothermal deposits at the Valu Fa Ridge back-arc spreading center in the southern Lau Basin has been investigated. Sulfide samples from the White Church area at the northern Valu Fa Ridge have δ³⁴S values averaging +3.8‰ (n= 10) for bulk sphalerite-chalcopyrite mineralization and +4.8‰ for pyrite (n= 10). Barite associated with the massive sulfides exhibits an average of +20.7‰ (n= 10). Massive sulfides from the active Vai Lili hydrothermal field at the central Valu Fa Ridge have much higher δ³⁴S ratios averaging +8.0‰ for bulk sphalerite-chalcopyrite mineralization (n= 5), +9.3‰ for pyrite samples (n= 5), and +8.0‰ and +10.9‰ for a chalcopyrite and a sphalerite separate, respectively. The isotopic composition of barite from the Vai Lili field is similar to that of barite from the White Church area and averages +21.0‰ (n= 8). Sulfide and barite samples from the Hine Hina area at the southern Valu Fa Ridge have δ³⁴S values that are considerably lighter than those observed for samples from the other areas and average −4.9‰ for pyrite (n= 9), −4.0 and −5.7‰ for two samples of sphalerite-chalcopyrite intergrowth, and −3.4‰ for a single chalcopyrite separate. The total spread in the isotopic composition of sulfides from Vai Lili and Hine Hina is more than 20‰ over a distance of less than 30 km. The δ³⁴S values of sulfides at Hine Hina are the lowest values so far reported for volcanic-hosted polymetallic massive sulfides from the modern seafloor. Barite from the Hine Hina field also has unusually light sulfur with δ³⁴S values of +16.1 to +16.7‰ (n= 5). Isotopic compositions of the sulfides at Hine Hina indicate a dramatic decrease in δ³⁴S from ordinary magmatic values and, in the absence of biogenic sulfur and/or boiling, imply a unique ³⁴S-depleted source of probable magmatic origin. Sulfide-barite mineralization in the Hine Hina area is associated with a distinctive alteration assemblage consisting of cristobalite, pyrophyllite, kaolinite, opal-CT, talc, pyrite, native sulfur, and alunite. Similar styles of alteration are typically known from high-sulfidation epithermal systems on land. Alunite-bearing, advanced argillic alteration in the Hine Hina field confirms the role of acidic, volatile-rich fluids, and a δ³⁴S value of +10.4‰ for the sulfur in the alunite is consistent with established kinetic isotope effects which accompany the disproportionation of magmatic SO₂ into H₂S and H₂SO₄. The Hine Hina field occurs near the propagating tip of the Valu Fa back-arc spreading center (i.e., dominated by dike injections and seafloor eruptions) and therefore may have experienced the largest contribution of magmatic volatiles of the three fields. The sulfur isotopic ratios of the hydrothermal precipitates and the presence of a distinctive epithermal-like argillic alteration in the Hine Hina field suggest a direct contribution of magmatic vapor to the hydrothermal system and support the concept that magmatic volatiles may be an important component of some volcanogenic massive sulfide-forming hydrothermal systems. Received: 16 January 1997 / Accepted: 28 October 1997     

Transformation of particulate organic matter at the water-bottom boundary in the Russian Arctic seas: Evidence from isotope and radioisotope data

Complex biogeochemical studies including the determination of isotopic composition of C_org in both suspended particulate matter and surface horizon (0–1 cm) of sediments (more than 260 determinations of δ¹³C-C_org) were carried out for five Arctic shelf seas: White, Barents, Kara, East Siberian, and Chukchi. The aim of this study is to elucidate causes that change the isotopic composition of particulate organic carbon at the water-sediment boundary. It is shown that the isotopic composition of C_org in sediments from seas with a high river runoff (White, Kara, and East Siberian) does not inherit the isotopic composition of C_org in particles precipitating from the water column, but is enriched in heavy ¹³C. Seas with a low river runoff (Barents and Chukchi) show insignificant difference between the value of δ¹³C-C_org in both suspended load and sediment because of a low content of the isotopically light allochthonous organic matter (OM) in particulates. Complex biogeochemical studies with radioisotope tracers (¹⁴CO₂, ³⁵S, and ¹⁴CH₄) revealed the existence of specific microbial filter formed from heterotrophic and autotrophic organisms at the water-sediment boundary. This filter prevents the mass influx of products of OM decomposition into water column, as well as reduces the influx of a part of OM contained in the suspended particulate matter from water into sediment.