Carbon isotope composition of organic seston and sediments in a Georgia salt marsh estuary

The distribution of δ¹³C values for organic seston and sediment was determined in three sounds in the Spartina marsh estuaries along the Georgia coast, which had high, moderate, and low inputs of freshwater. Organic matter in all three sounds had similar carbon isotope compositions, for the most part within the range of marine values (δ¹³C of ?18%. to ?24%.). It appears that river flow does not introduce significant quantities of particulate C₃ plant material (δ¹³C of ?25%. to ?28%.) to Georgia estuaries. Evaluation of δ¹³C values of estuarine seston and three size fractions of sediment indicated that while Spartina carbon (δ¹³C of ?13%.) can be an important component of organic matter in intertidal sediments (mean δ¹³C of ?14.3%. to ?20.0%.), it is less so in subtidal sediments (mean δ¹³C of ?18.8%. to ?21.2%.), and it is hardly present at all in the seston (mean δ¹³C of ?24.5%.). δ¹³C values of dissolved inorganic carbon (DIC) in several water samples ranged between ?2.5%. and ?5.6%., suggesting that the isotope composition of estuarine DIC is influenced by respiratory CO₂ derived from metabolism of ¹³C-depleted plant carbon. Phytoplankton production utilizing this comparatively light DIC could be a source of relatively negative δ¹³C carbon in the estuary. Additional origins of estuarine organic matter greatly depleted in ¹³C compared to Spartina carbon remain to be identified.     

Ein Beitrag zur Isotopengeochemie des Kohlenstoffs in magmatischen Gesteinen

Several arguments indicate that the mean carbon isotopic composition of the earth's crust and the upper mantle should be around-7‰. This agrees quite well with a balance calculation (Table 7) and with what we know about the carbon isotope composition of carbonatites and diamonds. Since fractionation factors decrease with increasing temperatures, the differences in isotopic compositions found in igneous rocks might be expected to be relatively slight and not to differ very much from the mean δ-value for the earth's crust. This also applies to the elements oxygen and sulfur, and to a lesser extent even for hydrogen, but not for carbon. Hoefs (1965) has shown that all igneous rocks contain carbon in at least two different forms:

1. an oxidized form mainly as carbonate and/or as CO₂ (in fluid and gaseous inclusions) in variable concentrations between <100 ppm and several thousand ppm CO₂, and
2. a reduced form with a relatively constant concentration around 200 ppm C. To 1). If the carbonate were of primary magmatic origin, we should expect, in analogy to carbonatites or to some hydrothermal carbonates, a δ ¹³C-value around-7 and a δ ¹⁸O-value between ?15 to ?25‰ relative to PDB, but on the contrary, the variable δ ¹³C- and the relatively heavy δ ¹⁸O-values make it seem probable that the carbonate is not of pirmary magmatic origin, but of secondary, maybe groundwater origin. This does not exclude the possibility that in some cases there may also be some carbonate which is of primary magmatic origin. To 2). If the reduced carbon found in igneous rocks is indigenous to these specimens, theoretically it may occur as elemental carbon (graphite), as carbides, and as organic compounds or as all three combined together.

This reduced carbon has a very light and fairly constant isotopic composition between ?24 and ?28‰ relative to PDB in all igneous rock types. There are two very different possible explanations for these values. The first and simplest one is that this carbon is also of secondary origin, or in other words of biogenic origin—some kind of assimilation of sedimentary organic material. But since this carbon is very evenly distributed, this means that all igneous rocks with a very small, but not negligible, porosity and permeability are impregnated by surface waters containing biogenic-derived organic substances in a concentration of around 200 ppm C. Since bore samples have also been analyzed, this also means that these waters penetrate into igneous rocks even at greater depths. Due to certain similarities in carbon isotopic composition found in extraterrestrial material, in meteorites and in lunar rocks (Table 9), I favor the second possibility of explaining the rather light δ ¹³C values: Several mechanisms have been postulated for the formation of organic matter in our solar system (Fischer-Tropsch type synthesis, Miller-Urey reactions etc.). Evidence supporting the hypothesis of inorganically formed organic matter on the earth has accumulated since Miller (1957) first demonstrated the synthesis of organic compounds from methane, ammonia and water. It is postulated that photosynthesis is not the only process leading to isotopically light carbon, but that some of these reactions (perhaps Fischer-Tropsch type synthesis) may also yield to isotopically light carbon. In addition to these data, some gaseous CO₂-samples of probably volcanic origin from Germany have been analyzed. The CO₂ discharged in areas of ancient volcanic activity shows δ ¹³C value between ?2 and ?5‰, typical for geothermal areas (e.g. Yellowstone, New Zealand). The CO₂ found in inclusions in evaporites, some of them near basaltic dikes, shows a strikingly different δ ¹³C composition (between ?15 and ?25%.) comparable to CO₂ sampled over liquid Hawaiian lavas. On the basis of the isotope-exchange reaction CH₄+2H₂O ? CO₂+4H₂, temperature seems to be the most important parameter, being responsible for the observed differences in isotopic composition.     

Etude pedogenetique et isotopique des neoformations de calcite dans un sol sur craie: Caracteristiques et origines

Cryoturbated facies are found at the boundary between soil horizons and Cretaceous chalk. Several types of secondary calcite appear in soil horizons: orange coloured and rounded (partially dissolved) nodules, deeply coloured angular aggregates, transparent isolated rhombs and polycrystalline nodules, needles. The carbon and oxygen isotope compositions of these calcites are correlated: δ¹³C = 4.9δ¹⁸O_PDB + 15.9End members of this correlation are the orange rounded nodules (δ¹³C ? + 8%., $\text{δ}{}^{18}\text{O ? ?1.5‰}$) and the transparent angular polycrystalline nodules (δ¹³C ? ?13; δ¹⁸O ? ?6).Partially dissolved nodules have formed under periglacial climatic conditions. Crystallisation would have occurred under the following (equilibrium) environmental conditions: δ¹⁸O_SMOW (soil solution) ?7, δ¹³C (gaseousCO₂) ? ?5.2, t ? ?2°C. Soil solution was enriched in ¹⁸O by evaporation and atmospheric CO₂ was enriched in ¹³C as compared to present day. Transparent polycrystalline nodules are compatible with present day environmental conditions: δ¹⁸O (soil solution) ranging from ?9 to ?4 and δ¹³C (soil CO₂) ranging from ?24.5 to ?23. These nodules crystallize between May and October at soil temperatures ranging from 10 to 25°C, from evaporated soil solutions. Angular coloured aggregates may form under present day winter conditions for temperatures between 0 and 10°C. However they may also result from present accretion of fragments of periglacial nodules.All recent secondary calcite results from CO₂ degassing and evaporation of soil solutions. Degassing is controlled by the gradient of CO₂ partial pressure within the soil profile. During winter this gradient is low and the resulting calcite precipitation is not significant. During summer a large difference in pCO₂ appears between the root zone and deep soil horizons. The degassing accounts for an increase of about 2‰ in δ¹³C of the total dissolved inorganic carbon and of the related solid carbonate. Evaporation is the main driving force for secondary calcite precipitation.     

Origin of CO2 and carbonate veins in mantle-derived xenoliths in the Pannonian Basin

The origin and evolution of CO₂ inclusions and calcite veins in peridotite xenoliths of the Pannonian Basin, Hungary, were investigated by means of petrographic investigation and stable isotope analyses. The fluid inclusions recovered in paragenetic olivine and clinopyroxene belong to distinct populations: type A (texturally early) inclusions with regular shapes (often with negative crystal forms) forming intragranular trails; type B (texturally late) inclusions defining randomly oriented trails that reach grain boundaries. Type B inclusions are often associated with silicate melt (type C) inclusions. Stable carbon isotope compositions in inclusion-hosted CO₂ were obtained by vacuum crushing followed by conventional dual inlet as well as continuous flow mass spectrometry in order to eliminate possible lab artifacts. Olivines, clino- and orthopyroxenes of the host peridotite have oxygen isotope compositions from 5.3 to 6.0‰ (relative to V-SMOW), without any relationship with xenolith texture. Some of the xenoliths contained calcite in various forms: veins and infillings in silicate globules in veins, secondary carbonate veins filling cracks and metasomatic veins with diffuse margins. The former two carbonate types have δ¹³C values around –13‰ (relative to V-PDB) and low Sr contents (< 0.5 wt.%), whereas the third type,veins with high-temperature metasomatic features have a δ¹³C value of –5.0‰ and high Sr contents up to 3.4 wt.%. In spite of the mantle-like δ¹³C value and the unusually high Sr content typical for mantle-derived carbonate, trace element compositions have proven a crustal origin. This observation supports the conclusions of earlier studies that the carbonate melt droplets found on peridotite xenoliths in the alkaline basalts represent mobilized sedimentary carbonate. The large δ¹³C range and the ¹²C-enrichment in the carbonates can be attributed to devolatilization of the migrating carbonate or infiltration of surficial fluids containing ¹²C-rich dissolved carbon.Carbon isotope compositions of inclusion-hosted CO₂ range from –17.8 to –4.8‰ (relative to V-PDB) with no relation to the amount of CO₂ released by vacuum crushing. Low-δ¹³C values measured by stepwise heating under vacuum suggest that the carbon component is pristine and not related to surficial contamination, and that primary mantle fluids with δ¹³C values around –5‰ were at least partly preserved in the xenoliths. Tectonic reworking and heating by the basaltic magma resulted in partial CO₂ release and local ¹³C-depletion.     

The carbon isotopic composition of diamonds: relationship to diamond shape,color, occurrence and vapor composition

Three hundred and thirty new ¹³C analyses of diamonds are presented, indicating, in conjunction with earlier published work, a range of about 30%. in the carbon isotopic composition of diamonds. The frequency distribution of diamond δ¹³C analyses shows a very pronounced mode at ?5 to ?6%.vs PDB, a large negative skewness, and a sharp boundary at about ?1%.. Analyses of diamonds from the Premier and Dan Carl mines, South Africa, demonstrate that: (1) differences in ¹³C content that can be related to diamond color and shape are smaller than 1%.; (2) the mean ¹³C content of kimberlite carbonates is 1–2%. lower than that of associated diamonds; (3) significant differences in ¹³C content exist between the mean isotopic compositions of diamonds from these two pipes; (4) the variability in δ¹³C differs from one mine to the other.Computations were carried out evaluating the effect on the ¹³C content of diamonds of: (i) various precipitation processes; (ii) the abundance of the species H₂, H₂O, CH₄, CO, CO₂ and O₂ in the vapor; (iii) the initial isotopic composition variability of the source carbon; (iv) variations of the carbon isotope effects resulting from changes in pressure and temperature and (v) reservoir effects (Rayleigh fractionation). Fifty-eight genetic models were investigated for compatibility with the ¹³C distribution in diamonds and associated carbonate. The modeling does not permit an unambiguous answer to the question whether or not a vapor participated in diamond formation, although the presence of methane during diamond formation is compatible with the carbon isotopic composition data, possible oxygen fugacities in the mantle and with the composition of gases liberated from diamonds. In all probability carbon isotope effects in the diamond formation process were small, and the very large range in δ¹³C observed was inherited from the source carbon.     

A large epeiric methanogenic Bambuí sea in the core of Gondwana supercontinent?

Carbon isotope compositions of both sedimentary carbonate and organic matter can be used as key proxies of the global carbon cycle and of its evolution through time,as long as they are acquired from waters where the dissolved inorganic carbon(DIC)is in isotope equilibrium with the atmospheric CO2.However,in shallow water platforms and epeiric settings,the influence of local to regional parameters on carbon cycling may lead to DIG isotope variations unrelated to the global carbon cycle.This may be especially true for the terminal Neoproterozoic,when Gondwana assembly isolated waters masses from the global ocean,and extreme positive and negative carbon isotope excursions are recorded,potentially decoupled from global signals.To improve our understanding on the type of information recorded by these excursions,we investigate the pairedδ^13Ccarb andδ^13Corg evolution for an increasingly restricted late Ediacaran-Cambrian foreland system in the West Gondwana interior:the basal Bambui Group.This succession represents a 1~(st)-order sedimentary sequence and records two majorδ^13Ccarb excursions in its two lowermost lower-rank sequences.The basal cap carbonate interval at the base of the first sequence,deposited when the basin was connected to the ocean,hosts antithetical negative and positive excursions forδ^13Ccarb andδ^13Corg,respectively,resulting inΔ^13C values lower than 25‰.From the top of the basal sequence upwards,an extremely positiveδ^13Ccarb excursion is coupled toδ^13Corg,reaching values of+14‰and-14‰,respectively.This positive excursion represents a remarkable basin-wide carbon isotope feature of the Bambui Group that occurs with only minor changes inΔ^13C values,suggesting change in the DIC isotope composition.We argue that this regional isotopic excursion is related to a disconnection between the intrabasinal and the global carbon cycles.This extreme carbon isotope excursion may have been a product of a disequilibria between the basin DIC and atmospheric CO2 induced by an active methanogenesis,favored by the basin restriction.The drawdown of sulfate reservoir by microbial sulfate reduction in a poorly ventilated and dominantly anoxic basin would have triggered methanogenesis and ultimately methane escape to the atmosphere,resulting in a^13C-enriched DIC influenced by methanogenic CO2.Isolated basins in the interior of the Gondwana supercontinent may have represented a significant source of methane inputs to the atmosphere,potentially affecting both the global carbon cycle and the climate.     

Stable isotope(δ~(13)C_(ker),δ~(13)C_(carb),δ~(18)O_(carb)) distribution along a Cambrian outcrop section in the eastern Tarim Basin,NW China and its geochemical significance

This study investigated the geochemical features of the lower Paleozoic strata of Yaerdang Mountain outcrop along with the core samples from well TD2∈ in the eastern Tarim Basin,NW China.The total organic carbon abundance,hydrocarbon-generating precursor biospecies,and stable isotope ratios of organics and carbonate(δ~(13)C_(ker),δ~(13)C_(carb) and δ~(18)O_(carb)) were comprehensively studied for their possible correlative constraints during sedimentary evolution.The results revealed that the δ~(13)C_(ker)(VPDB) of Cambrian kerogens along the outcrop section varied from-34.6‰ to-28.4‰,indicating an increasing tendency from the lower Cambrian to the upper Cambrian.This was on the whole accompanied by the variation in the δ~(13)C_(carb) and δ~(18)O_(carb) along the profile,which might be associated with the changes in the sea level and also in the compositional variation of benthic and planktonic biomass.The large variation in the stable carbon isotope ratios up to 6‰ along the outcrop section reflected the heterogeneity of the Cambrian source rocks from the eastern Tarim Basin.Hence,the ~(13)C-enriched crude oils from well TD2∈might have been derived from a localized stratum of Cambrian source rocks.The results from this study showed the possibility of multiple source kitchens in the Cambrian-lower Ordovician portion of Tarim Basin.     

Carbon and nitrogen pools in Padanian soils (Italy): Origin and dynamics of soil organic matter

Carbon and nitrogen elemental (C-N, wt%) and isotopic (δ¹³C-δ¹⁵N, ‰) investigation has been carried out on alluvial and deltaic soils from the Padanian plain (northern Italy), an area interested by intensive agricultural activities, to refine previous inferences on depositional facies, pedogenetic processes and anthropogenic influences. Soil analysis, carried out by EA-IRMS, have been focused on inorganic and organic fractions properly speciated by a thermally-based method, whereas further insights on the organic matter constituents have been obtained by sequential fractionation. The bulk EA-IRMS analyses reveal a remarkable compositional heterogeneity of the investigated soils (TC 0.89 to 11.93?wt%, TN 0.01 to 0.78?wt%, δ¹³C_TC -1.2 to -28.2‰, δ¹⁵N -1.2 to 10.0‰) that has to be explained as an integration between inorganic and organic pools. The latter have been subdivided in Non-Extractable Organic Matter (NEOM, δ¹³C -16.3 to -28.6‰) and in extractable fractions as Fulvic (FA, δ¹³C -24.7 to -27.5‰, δ¹⁵N 0.6 to 5.7‰) and Humic (HA, δ¹³C -24.6 to -27.0‰, δ¹⁵N 1.0 to 9.7‰) Acids, which have been used to infer soil dynamics and Soil Organic Matter (SOM) stability processes. Results indicate that SOM at depth of 100?cm was generally affected by microbial reworking, with the exception of clayey and peaty deposits in which biological activity seems inhibited. Peaty and clayey soils display an organic fraction loss of ca. 20% toward the surface, suggesting deterioration possibly induced by intensive agricultural activities. These latter may be the cause of the ubiquitous losses of organic fraction throughout the investigated area over the last seventy years, evaluated by the comparison with historical data on corresponding topsoils. The obtained insights are very important because these soils are carbon (and nitrogen) sinks that are vulnerable and can be degraded, loosing agricultural productivity and potentially contributing to greenhouse gases fluxes.     

Stable carbon isotope ratios in Astrangia danae: evidence for algal modification of carbon pools used in calcification

Stable carbon isotope ratios have been measured in skeletons of the temperature shallow water scleractinian coral, Astrangia danae. δ¹³C values ranging from ?5.42 to ?7.30%. revealed the expected depletion of ¹³C in skeletal carbonate relative to sea water bicarbonate. Differences among the ratios could not be attributed to collection site and were not correlated to skeletal morphology. Values of δ¹³C were directly related to zooxanthellae density for all colonies, so that as zooxanthellae concentration increased, δ¹³C valued increased. Colonies maintained under high temperature conditions were offset from the normal, exhibiting ratios less enriched in ¹³C than similar colonies from natural conditions. These trends supported the models of Weber and Goreau in which the carbon pools used in calcification are modified by algal photosynthesis. Direct evidence of physiological differences between symbiotic and asymbiotic colonies of A. danae has also been provided.     

A fluid inclusion and light element stable isotope study of the gold-bearing quartz vein system,Falun, Sweden

The Falun gold quartz vein mineralization is located ca 230 km NW of Stockholm, Sweden, within the Early Proterozoic volcano-sedimentary sequence of Bergslagen. The mineralization consists of a system with subparallel quartz veins that crosscut the alteration zone to the Falun massive sulphide deposit. Early barren and late gold-bearing quartz veins follow tectonic structures postdating the formation of the massive sulphide ore. Both generations of veins are epigenetic to the massive sulphide ore and were formed by hydrothermal processes. Fluid inclusion study of the gold-bearing quartz veins indicates a low-moderately saline fluid (0.3 to 17.4 equiv wt% NaCl). Heterogeneous trapping is indicated by coexisting inclusions showing a variable CO₂ content from 100% CO₂ ± CH₄ to 100% aqueous fluid. Temperatures of total homogenization also show a wide spread from 116–350°C with a slightly bimodal distribution with peaks at ca 180°C and 280°C. MeasuredδD values — 69 to — 63%0 (SMOW), of inclusion fluid and calculatedδ ¹⁸O values of hydrothermal fluids — 7.5 to — 1.4%0 (SMOW), strongly suggest a meteoric origin for the fluids. The quite consistentδD values and the range inδ ¹⁸O values indicate that major water-rock interaction led to the evolution inδ18O of the hydrothermal fluids.     

Isotopic fractionation between coexisting organic carbon—carbonate pairs in Precambrian sediments

δ¹³C_org and δ¹³C_carb values of 58 coexisting organic carbon-carbonate pairs covering the whole Precambrian have yielded means of ?24.7 ± 6.0%. [PDB] and +0.9 ± 2.7%. [PDB], respectively. Accordingly, isotopic fractionation between inorganic and organic carbon in Precambrian sediments is about the same as in geologically younger rocks (Δδ ? 25%.), a slight increase displayed by the Early Precambrian pairs (Δδ ? 28%.) being probably biassed by an over-representation in this age group of samples from one single locality (nevertheless, this value still lies within the range permitted for a possible deviation). It is reasonable to assume, therefore, that the overall isotope fractionation factor governing biological fixation of inorganic carbon has been virtually constant since some 3.3 × 10⁹ yr ago.     

The isotopic composition of carbonaceous matter in a metamorphic profile from the Swiss Alps

44 Δ¹³C-values for carbonaceous matter in a metamorphic profile from the Swiss Alps have been determined. The analyzed samples range from unmetamorphosed sediments to staurolite schists. The carbon isotopic composition is more-or-less constant with δ-values around ?25%. in the unmetamorphosed sediments, but shifts towards higher ¹³C-content with increasing grade of metamorphism. δ¹³C values of around ?11%. were measured in the rocks of the highest metamorphic grade.     

Carbon and oxygen isotope study of the active water-carbonate system in a karstic Mediterranean cave: Implications for paleoclimate research in semiarid regions

In a semiarid climatic zone, such as the Eastern Mediterranean region, annual rainfall variations and fractionation processes in the epikarst zone exert a profound influence on the isotopic compositions of waters seeping into a cave. Consequently, the isotopic compositions of speleothems depositing from cave waters may show complex variations that need to be understood if they are to be exploited for paleoclimate studies. This is confirmed by a four-year study of the active carbonate-water system in the Soreq cave (Israel). The δ¹⁸O (SMOW) values of cave waters range from −6.3 to −3.5%.. The highest δ¹⁸O values occur at the end of the dry season in waters dripping from stalactites, and reflect evaporation processes in the epikarst zone, whereas the lowest values occur in rapidly dripping (fast-drip) waters at the peak of the rainy seasons. However, even fast-drip waters are about 1.5%. heavier than the rainfall above the cave, which is taken to reflect the mixing of fresh with residual evaporated water in the epikarst zone. δ¹³C (PDB) values of dissolved inorganic carbon (DIC) vary from −15.6 to −5.4%., with fast-drip waters having lower δ¹³C values (mostly −15.6 to −12%.) and higher DIC concentrations relative to pool and stalactite-drip water. The low δ¹³C values of fast-drip waters and their supersaturation with respect to calcium carbonate indicates that the seepage waters have dissolved both soil-CO₂ derived from overlying C₃-type vegetation and marine dolomite host rock.The δ¹⁸O (PDB) values of various types of present-day low-magnesium calcite (LMC) speleothems range from −6.5 to −4.3%. and δ¹³C values from −13 to −5.5%. and are not correlated with speleothem type. An analysis of δ¹⁸O values of present-day calcite rafts and pool waters shows that they form in oxygen isotope equilibrium. Similarly, the measured ranges of δ¹³C and δ¹⁸O values for all types of present-day speleothems are consistent with equilibrium deposition at cave temperatures. The δ¹³C–δ¹⁸O range of contemporary LMC thus reflects the variations in temperatures and isotopic compositions of the presentday cave waters. The 10%. variation in the δ¹³C values in waters can be modeled by a simple Rayleigh calculation of the carbon isotope fractionation accompanying CO₂-degassing and carbonate precipitation. These variations may obscure the differences in the carbon isotopic composition of speleothems that could arise when vegetation cover changes from C₃ to C₄-type plants. This consideration emphasizes that it is necessary to characterize the full range of δ¹³C values associated with contemporaneous speleothems in order to clarify the effects of degassing from those due to differing vegetation types.Isotopic studies of a number of different types of fossil LMC speleothems show many of them to exhibit isotopic trends that are similar to those of present-day LMC, but others show both higher and lower δ¹⁸O ranges. In particular, the higher δ¹⁸O range has been shown by independent age-measurements to be associated with a period of drier conditions. The results of the study thus indicate that it is necessary to work on a well calibrated cave system in semiarid climates and that the fossil speleothem record should be obtained from different types of contemporaneous deposit in order to fully characterize the δ¹⁸O–δ¹³C range representative of any given climatic period.     

The concentration and isotopic composition of hydrogen,carbon and nitrogen in carbonaceous meteorites

Concentrations and isotopic compositions were determined for H₂, N₂ and C extracted by stepwise pyrolysis from powdered meteorites, from residues of meteorites partially dissolved with aqueous HF, and from residues of meteorites reacted with HF-HCl solutions. The meteorites treated were the carbonaceous chondrites, Orgueil, Murray, Murchison, Renazzo and Cold Bokkeveld. Data determined for whole rock samples are in approximate agreement with previously published data. Acidification of the meteorites removed the inorganic sources of H₂, so that H₂ in the HF-HCl acid residues came primarily from insoluble organic matter, which makes up 70–80% fraction of the total carbon in carbonaceous meteorites. The δD in the organic matter differs markedly from previously determined values in organic matter in meteorites. The δD values of organic matter from acid residues of C1 and C2 carbonaceous chondrites range from +650 to + 1150%. The acid residues of the Renazzo meteorite, whose total H₂ has a δD of +930‰, gave a δD value of +2500‰. Oxidation of the HF-HCl residue with H₂O₂ solution removes the high δD and the low δ¹⁵N components. The δ¹³C values range between ?10 and ?21 and δ¹⁵N values range between +40 and ?11. The δ¹⁵N of Renazzo is unusual; its values range between +150 and ?190.There is good correlation between δD and the concentration of H₂ in the acid residues, but no correlation exists between δD, δ¹³C and δ¹⁵N in them. A simple model is proposed to explain the high δD values, and the relationships between δD values and the concentration of H₂. This model depends on the irradiation of gaseous molecules facilitating reaction between ionic molecules, and indicates that an increase in the rate of polymerization and accumulation of organic matter on grains would produce an increase in the deuterium concentration in organic matter.     

Formation of carbonate concretions in surface sediments of two mud mounds,offshore Costa Rica: a stable isotope study

The surface sediments of two mud mounds (“Mound 11” and “Mound 12”) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO₃). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded δ¹⁸O_carbonate values ranging between 34.0 and 37.7 ‰ Vienna standard mean ocean water (VSMOW) and δ¹³C_carbonate values from ?52.2 to ?14.2 ‰ Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The δ¹⁸O_carbonate values suggest mineral formation from seawater-derived pore fluid (δ¹⁸O_porefluid = 0 ‰ VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (δ¹⁸O_porefluid ≈5 ‰) in Mound 11. A positive correlation between δ¹³C_carbonate and δ¹⁸O_carbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (δ¹³C_porefluid ≈0 ‰) and (2) bicarbonate which formed during the AOM (δ¹³C_porefluid ≈?70 ‰). Furthermore, the δ¹⁸O_porefluid composition, with values up to +4.7 ‰ Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boron-enriched fluids. Earlier, it has been shown that the origin of ¹⁸O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (δ¹³C_CH4 = ?38 ‰). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).     

A model of the diagenetic evolution of coaly sedimentary organic matter

Elemental composition was used to calculate the amounts of compounds produced during the diagenetic evolution of a coal series from the Mahakam delta (Kalimantan, Indonesia). These calculations were based on the following hypotheses: organic nitrogen does not take part in reactions and remains unchanged in the residual organic matter, the only compounds produced are water, carbon dioxide and hydrocarbons.This approach shows that carbon loss during diagenesis is mainly as CO₂, and hydrogen loss is mainly as H₂O. Hydrocarbon production is negligible, in accordance with absence of bacterial methane accumulations in the Mahakam delta.The δ¹³C of coals in the sequence becomes about 2 per mil more positive over the diagenetic depth range of coal evolution. Accounting for the coal δ¹³C change in terms of CO₂ loss requires that the CO₂ given off have δ¹³C of about ?40%.. Such negative CO₂ has not been observed in natural systems, except when CH₄ is undergoing oxidation. Several plausible causes for this effect are discussed.     

Geochemical Characteristics of the Upper Triassic Xujiahe Formation in Sichuan Basin, China and its Significance for Hydrocarbon Accumulation

The alternative development of coal-bearing hydrocarbon source rocks and low-porosity and low-permeability tight sandstone reservoirs of the Triassic Xujiahe Formation in the Sichuan Basin is favorable for near-source hydrocarbon accumulation. The natural gas composition of the Xujiahe Formation in the Sichuan Basin is dominated by hydrocarbon gases, of which the methane content is80.16%-98.67%. Typically, the C_2~+ content is larger than 5% in main wet gas. The dry gas is mainly distributed in the western and northern regions of the basin. The non-hydrocarbon gases mainly contain nitrogen, carbon dioxide, hydrogen, and helium, with a total content of 2%. The carbon isotope ranges of methane and its homologues in natural gas are: δ~(13)C_1 of-43.8‰ to-29.6‰, δ~(13)C_2 of-35.4‰ to-21.5‰, δ~(13)C_3 of-27.6‰ to-19.8‰,and δ~(13)C_4 of-27.7‰ to-18.8‰. δ~(13)C_3δ~(13)C_4 occurs in some natural gas with a low evolution degree; such gas is mainly coal-related gas from humic-type source rocks of the Xujiahe Formation. As for the natural gas, δ~2 H_(CH4) values ranged from-195‰ to-161‰,δ~2 H_(C2H6) values ranged from-154‰ to-120‰, and δ~2 H_(C3H8) values ranged from-151‰ to-108‰. The dry coefficient,δ~(13)C and δ~2 H_(CH4) are all positively correlated with the maturity of source rocks. The higher the maturity of source rocks is, the larger the natural gas dry coefficient is and the larger the δ~(13)C and δ~2 H_(CH_4) values are, indicative of the characteristic of near-source accumulation. The δ~2 H_(C2H6) value of natural gas is influenced by paleosalinity to a relatively large extent; the higher the paleosalinity is, the larger the δ~2 H_(C2H6) value is. The Pr/Ph value of the condensate oil ranged from 1.60 to 3.43, illustrating light oxidization-light reduction and partial-oxidization characteristics of the depositional environment of coal-bearing source rocks of the Xujiahe Formation. The natural gas light hydrocarbon(C_5-C_7) from the Xujiahe Formation presented two characteristics: the first was the relatively high aromatic hydrocarbon content(19%-32.1%), which reveals the characteristic of natural gas with humic substances of high-maturity; the second was the low content of aromatic hydrocarbon(0.4%-9.3%),reflecting water-washing during the accumulation of the natural gas. The reported research outcomes indicate a potential mechanism for natural gas accumulation in the Xujiahe Formation, which will further guide natural gas exploration in this region.     

Evaluation of petroleum hydrocarbon biodegradation in shallow groundwater by hydrogeochemical indicators and C, S-isotopes

Biodegradation is one of the main natural attenuation processes in groundwater contaminated with petroleum hydrocarbons. In this work, preliminary studies have been carried out by analyzing the concentrations of total petroleum hydrocarbons (TPH), dissolved inorganic carbon (DIC), dominant terminal electron accepters or donors, as well as δ ¹³C_DIC and δ ³⁴S_SO4, to reveal the biodegradation mechanism of petroleum hydrocarbons in a contaminated site. The results show that along groundwater flow in the central line of the plume, the concentrations of electron acceptors, pH, and E _h increased but TPH and DIC decreased. The δ ¹³C_DIC values of the contaminated groundwater were in the range of ?14.02 to ?22.28 ‰_PDB and ?7.71 to 8.36 ‰_PDB, which reflected a significant depletion and enrichment of ¹³C, respectively. The increase of DIC is believed to result from the non-methanogenic and methanogenic biodegradation of petroleum hydrocarbon in groundwater. Meanwhile, from the contaminated source to the downgradient of the plume, the ³⁴S in the contaminated groundwater became more depleted. The Rayleigh model calculation confirmed the occurrence of bacterial sulfate reduction as a biodegradation pathway of the petroleum hydrocarbon in the contaminated aquifers. It was concluded that stable isotope measurements, combined with other biogeochemical measurements, can be a useful tool to prove the occurrence of the biodegradation process and to identify the dominant terminal electron-accepting process in contaminated aquifers.     

Stable carbon isotopes of alkane gases from the Xujiahe coal measures and implication for gas-source correlation in the Sichuan Basin,SW China

The Upper Triassic Xujiahe Formation in the Sichuan Basin, SW China consists of a series of coal measures. The first, third and fifth members of this formation are dominated by gas prone dark mudstones and coals. The mudstones contain Type II and III kerogens with average organic carbon contents around 1.96%. These source rocks are mature in the central Sichuan and highly mature in the western Sichuan Basin, characterized by gas generation with subordinate amounts of light oil or condensate oils. The source rocks are intercalated with the sandstone dominated second, fourth and sixth members of the Xujiahe Formation, thus leading to three separate self contained petroleum systems in the region. The proven gas reserves in the Xujiahe Formation are only less than that of the Triassic Feixianguan Formation and the Xujiahe Formation has the second largest gas field (Guang’an gas field) in the basin. Gases derived from the Xujiahe Formation coals generally show a normal stable carbon isotopic trend for C₁–C₄ n-alkanes, with the highest δ¹³C₂ values among the nine gas pay zones in the basin (?20.7‰ to ?28.3‰), and δ¹³C₁ values as low as ?43.0‰ in the central Sichuan. Gas accumulations with an oil leg have also been found in the eastern and southern Sichuan where the thickness of the Xujiahe Formation is significantly reduced. Gases in these accumulations tend to show low δ¹³C₂ values (?30.0‰ to ?36.3‰), characteristic of oil prone source rocks.     

Carbon isotope composition of sedimentary rocks in the southern Siberian Platform and surrounding fold systems

Organic carbon isotope composition was studied in the sedimentary cover of the southern Siberian Platform and its surrounding fold systems. The rocks experienced catagenesis, metamorphism, and metasomatism. The chloroform bitumoid (CB) has a stable carbon isotope composition within a wide range of postsedimentation transformations. The average values of δ¹³C in CB of the sedimentary cover are ?29.5‰. Metamorphism and, especially, ore metasomatism, at the Sukhoi Log deposit caused a 2‰ increase in the heavy carbon isotope concentration of CB as compared to that of the platform deposits. The narrow variations in carbon isotope composition of the bitumoid are defined by their derivation from lipids, whose components are almost insusceptible to changes in the PT conditions. Kerogen from platform deposits is more strongly depleted than CB in the heavy carbon isotope (δ¹³C_av ? 32.2‰). The insoluble carbonaceous matter (ICM) of the metamorphic shales is significantly enriched in the heavy carbon isotope (δ¹³C_av ? 21.9‰). The highest changes in carbon isotope composition were found in concentrates of ICM from metasomatically altered rocks of the Sukhoi Log deposit (δ¹³C_av ? 17.5‰). The heavier carbon isotope composition caused by metamorphism and metasomatism is evidently defined by isotopic exchange between the carbonate carbon and CO₂ of metasomatic solutions, on one hand, and ICM of shales, on the other.