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.     

Mantle-derived fluids in the basement of the Deccan Trap: evidence from stable carbon and oxygen isotopes of carbonates from the Killari borehole basement, Maharashtra, India

We report here for the first time geochemical, mineralogical and stable carbon and oxygen isotopic data on the crystalline basement rocks of the 1993 Killari earthquake region of Maharashtra (India), which is covered by a thick suite of Deccan volcanics. Our results revealed the hitherto unknown amphibolite–granulite nature of the 2.5?Ga basement, which contains 2.00–2.28?wt% of CO₂. The stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotopic measurements on carbonates separated from two basement samples KIL-13 (440.5?m depth) and KIL-20 (499.6?m depth) collected from the KLR-1 borehole drilled in the epicentral region showed the respective values of ?6.23 and ?6.22‰ versus PDB for δ¹³C and 7.94 and 8.11‰ versus SMOW for δ¹⁸O. The samples plot in the primary igneous carbonatite field, indicating the mantle origin of the carbonates, derived through the process of mantle metasomatism from the deep mantle carbon reservoir. This would suggest large-scale crust-mantle thermal fluid interaction beneath the Killari seismogenic region, which is characterized by massive upwarping of the high-velocity mafic crust and retrograde metamorphism.     

Fluid inclusion and carbon isotope study from bamble granulites (South Norway)

The carbon isotopic composition of CO₂ from fluid inclusions in granulite facies rocks has been determined. The “primary” carbonic fluid — most probably being of Upper Mantle origin — appears to have δ ¹³C-values around ?15%. or even lighter up to ?20%. During the late stages of retromorphosis an enrichment in the heavy carbon isotope seems to occur resulting in δ-values between ?5 and ?7%. which, on the basis of ¹³C/¹²C ratios of carbonatites, kimberlites and diamonds have been taken up till now as representative for juvenile carbon. The implications of these findings are discussed.     

A reconnaissance study of stable isotope ratios in archaean rocks from the yilgarn block,Western Australia

Isotopic compositions of sulphur, carbon, and oxygen have been determined for constituents from a total of 103 samples of sedimentary rocks, mafic and ultramafic igneous rocks, nickel ores, and gold ores from the Archaean Yilgarn Block.

Sulphides in the bulk of the sedimentary rocks have δ³⁴S values close to 0‰ and appear to have precipitated from solutions which incorporated magmatic sulphur (either juvenile or derived from older rocks). There is no evidence for widespread sulphate reduction.

δ³⁴S values of sulphides in the nickel deposits and associated mafic/ultramafic igneous rocks are within the magmatic range. The small, high‐grade deposits of the Kambalda‐Nepean‐Scotia type have small positive δ³⁴S values, and the large, low‐to‐medium grade dunite‐associated deposits of the Mount Keith‐Perseverance type have small negative δ³⁴S values.

Sulphides in the Kalgoorlie gold ores are enriched in ³²S relative to those in their host dolerite, supporting an epigenetic origin for the gold, under moderately high fO₂ conditions.

The δ¹³C values do not provide unequivocal evidence for the source(s) of the reduced carbon (kerogen) in the sedimentary rocks. Whilst they are compatible with biogenic derivation, it is not possible to rule out contributions from pre‐biotic organic ‘soup’ or from hydrothermal solutions of deep‐seated origin.

Carbonate in the sedimentary rocks are predominantly in epigenetic, sulphide‐bearing veinlets. In many cases, their δ¹³C values suggest precipitation from hydro‐thermal solutions containing magmatically derived CO₂. In only two samples are the petrographic features and δ¹³C values compatible with marine carbonates. Talc‐carbonate altered ultramafic igneous rocks have δ¹³C values consistent with their incorporation of magmatically derived CO₂.

The ?δ¹³C (carbonate‐kerogen) values for most of the sedimentary rock studied fall in a narrow range around +10‰, suggesting isotopic exchange between oxidized and reduced carbon species at moderately high temperatures (>250°C).

δ¹⁸O values of carbonate from both sedimentary rocks and igneous rocks are mainly within the range +7.2‰ to +18.0‰. If the values are primary they are consistent with the formation of carbonate from hydrothermal solutions of magmatic and/or metamorphic origin. However, it is also possible the δ¹⁸O values are the result of post‐depositional equilibration with meteoric waters.     

2.0 Ga orogenic graphite deposits and associated 13C-enriched meta-carbonate rocks from South China Craton: Implications for global Lomagundi event

The Lomagundi (-Jatuli) event, characterized by extremely high positive global inorganic carbon isotope excursion at about 2.2 billion years ago, is pivotal in investigating the causes and consequences of great oxygenation event, inventory and sequestration of carbon on the Earth’s surface, evolution of life, and more profoundly tectonic control on Earth’s environment. However, the reasons that caused the isotopic excursion are not resolved yet. Herein, we report the discovery of meta-carbonate rocks with distinct positive carbon isotopic excursion from the Paleoproterozoic continental collision zone of the Kongling Complex, South China Craton. The δ¹³C_V-PDB values for meta-carbonate rocks show positive values in the range from +5.5‰ to +11.6‰, whereas the δ¹³C_V-PDB values of associated graphite deposits range from ?25.8‰ to ?9.5‰. Zircon U-Pb-Hf isotopes from zircon-bearing meta-carbonate sample yielded weighted average ²⁰⁷Pb/²⁰⁶Pb age of 2001.3 ± 9.5 Ma, with corresponding ε_Hf(t) range from ?7.05 to ?3.16, comparable to the values of local 2.9–2.6 Ga basement rocks. Geochemical characteristics of meta-carbonate rocks, such as their rare earth element patterns and the trace element parameters of La, Ce, Eu, and Gd anomalies and Y/Ho ratio, suggest that the carbonate deposition took place in passive continental margin in association with large volumes of organic carbon. The extensive graphite deposits from Kongling Complex in South China Craton, their equivalents in the North China Craton and elsewhere across the globe prove that the burial of ¹²C-enriched organic carbon has eventually resulted in the global enrichment of ¹³C in the atmospheric CO₂, which is recorded in the marine carbonate rocks. Isotopic mass balance estimates indicate that more than half of the organic carbon was buried during the oceanic closure. Hence, the observed global shift could be directly related to the continent collision event in greater China, thus resolving the long-standing paradox of the Lomagundi global positive carbon isotope excursion. Moreover, the present results suggest that orogenesis play a significant role in sequestration of carbon into the continental crust.     

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.     

Determining the origin of carbon dioxide and methane in the gaseous emissions of the San Vittorino plain (Central Italy) by means of stable isotopes and noble gas analysis

The chemistry and isotope ratios of He, C (δ¹³C) and H (δD) of free gases collected in the San Vittorino plain, an intramontane depression of tectonic origin, were determined to shed light on mantle degassing in central Italy. The C isotopic composition of CO₂ (δ¹³C–CO₂ −2.0‰ to −3.8‰) and He isotope ratios (R/R_A 0.12–0.27) were used to calculate the fraction of CO₂ originating from mantle degassing vs. sedimentary sources. The results show that CO₂ predominantly (average of 75%) derives from the thermo-metamorphic reaction of limestone. Between 6% and 22% of the CO₂ in the samples derives from organic-rich sedimentary sources. The mantle source accounts for 0–6% of the total CO₂; however, in two samples, located in proximity to the most important faults of the plain, the mantle accounts for 24% and 42%. The presence of faults and fractures allows upward gas migration from a deep source to the Earth’s surface, not only in the peri-Tyrrhenian sector, as generally reported by studies on natural gas emissions in central Italy, but also in the pre-Apennine and Apennine belts. Isotope ratios of CH₄ (δ¹³C–CH₄ −6.1‰ to −22.7‰; δD–CH₄ −9‰ to −129‰) show that CH₄ does not appear to be related to mantle or magma degassing, but it is the product of thermal degradation of organic matter (i.e. thermogenic origin) and/or the reduction of CO₂ (i.e. geothermal origin). Most of the samples appear to be affected by secondary microbial oxidation processes.     

Hydrological characteristics of karstic groundwater in the northeast Viet Nam as studied by isotopic techniques

The stable water isotopic composition (δ²H and δ¹⁸Ο), tritium (³H) activity, dissolved organic carbon, alkalinity, as well as the composition of carbon 13 (δ¹³C) in dissolved inorganic carbon (DIC) of 36 water samples taken from 16 resurgences in the northeast provinces of Viet Nam in the dry (Mar 2008) and rainy (June 2008) seasons were analyzed to elucidate hydrological characteristics of the karstic aquifers in the area. The stable water isotopic composition of the water samples collected clearly demonstrated that the karstic groundwater in the region was recharged from the local meteorological water. The tritium activity in the samples was found to be in between 3 and 4 TU, falling in the range of the ³H activity in the local precipitation and thus meaning that the traveling of recharge water to the resurgences was very short. Concentrated and diffuse allogenic recharges seem to be important sources of karstic groundwater in the study region. Water in the karstic aquifers could be classified into three types as: (a) water from karstic areas with dense vegetation cover that causes DIC be depleted in carbon 13 (¹³δ<?12‰ vs. Pee Dee Belemnite standard of Vienna, VPDB); (b) water from karstic areas with poor vegetation cover that originates DIC with carbon 13 composition ranging from ?11 to ?12‰; and (c) surface water from lakes, springs and rivers that has DIC with enriched carbon 13 (δ¹³C >?10‰). This implies that there are several sources of carbon dioxide contributing to the DIC in water of the karstic aquifers in the study region. Among other potential sources, the atmospheric CO₂, CO₂ from carbonate rock dissolution, biomineralization of soil organic matters and plant roots respiration seem to be important sources of the DIC in the waters of this region. The results show high vulnerability towards anthropogenic contaminants of karstic groundwater in the study region.     

Carbon and oxygen isotopic compositions of Newania Dolomite Carbonatites, Rajasthan, India: implications for source of carbonatites

The Newania carbonatite complex of Rajasthan, India is one of the few dolomite carbonatites of the world, and oddly, does not contain alkaline silicate rocks thus providing a unique opportunity to study the origin and evolution of a primary carbonatite magma. In an attempt to characterize the mantle source, the source of carbon, and the magmatic and post-magmatic evolution of Newania carbonatites, we have carried out a detailed stable carbon and oxygen isotopic study of the complex. Our results reveal that, in spite of being located in a metamorphic terrain, these rocks remarkably have preserved their magmatic signatures in stable C and O isotopic compositions. The δ¹³C and δ¹⁸O variations in the complex are found to be results of fractional crystallization and low temperature post-magmatic alteration suggesting that like other carbonatites, dolomite carbonatites too fractionate isotopes of both elements in a similar fashion. The major difference is that the fractional crystallization of dolomite carbonatites fractionates oxygen isotopes to a larger extent. The modes of δ¹³C and δ¹⁸O variations in the complex, ?4.5?±?1‰ and 7?±?1‰, respectively, clearly indicate its mantle origin. Application of a multi-component Rayleigh isotopic fractionation model to the correlated δ¹³C versus δ¹⁸O variations in unaltered carbonatites suggests that these rocks have crystallized from a CO₂ + H₂O fluid rich magma, and that the primary magma comes from a mantle source that had isotopic compositions of δ¹³C ~ ?4.6‰ and δ¹⁸O ~ 6.3‰. Such a mantle source appears to be a common peridotite mantle (δ¹³C = ?5.0?±?1‰) whose carbon reservoir has insignificant contribution from recycled crustal carbon. Other Indian carbonatites, except for Amba Dongar and Sung Valley that are genetically linked to Reunion and Kerguelen plumes respectively, also appear to have been derived from similar mantle sources. Through this study we establish that dolomite carbonatites are generated from similar mantle source like other carbonatites, have comparable evolutionary history irrespective of their association with alkaline silicate rocks, and may remain resistant to metamorphism.     

Fluid composition and origin in the hydrothermal system of the Nezhdaninsky gold deposit,Sakha (Yakutia), Russia

Petrochemical characteristics of igneous, sedimentary, and metasomatic rocks; chemical and isotopic compositions of minerals and fluids; and PT parameters of mineral formation at the Nezhdaninsky deposit are reported. A model of hydrothermal system formation is developed on this basis. In addition to decreasing Ba/Rb and Li/Mg ratios in the course of the hydrothermal process, resulting in the formation of ore-bearing metasomatic rocks, increasing K/Ba and diminishing K/Cs ratios indicate the probable participation of magmatic fluid in the ore deposition. The agreement of the K/Rb and K/Ba ratios with the values typical of the main trend of igneous rocks (MT) implies that the K, Rb, and Ba contents were distributed in the ore-forming hydrothermal fluid according to the ratios in the source magmatic chamber. The K/Rb ratios in metasomatic rocks correspond to the MT and approach the pegmatitic-hydrothermal trend and the composition of orthomagmatic fluid of Mo-W greisen. Similar REE patterns of igneous and terrigenous rocks do not allow the REE source to be constrained unequivocally. The lithological control of lithophile element distribution testifies to the supply of host rock components to the hydrothermal system. All studied rocks and minerals are enriched in LREE. The REE total and the contribution of HREE decrease from preore to synore metasomatic rocks, from preore to regenerated carbonates, and from older to younger scheelite. A similar tendency is noted in granitoids of the Kurum pluton. The δ¹⁸O values of quartz range from +10.3 to +12.6‰ in Au-Mo-W zones, from +15.9 to +16.4‰ in metasomatic rocks, from +14.8 to +16.6‰ in gold-ore veins, and from +13.5 to +16.9‰ in silver-base-metal ore mineralization. The estimates of \(\delta ^{18} O_{H_2 O} \) suggest that water was supplied from a magmatic source (δ¹⁸O = +(5.5?9.0‰)) and as a product of sedimentary rock dehydration. High-temperature (up to 390°C) and highly concentrated (up to 31 wt % NaCl equiv) fluids participated in the mineral formation. The phase separation of the fluid into H₂O-CO₂ liquid and predominantly carbon dioxide gas was combined with mixing of a high-temperature and relatively highly concentrated chloride solution with a low-temperature and poorly mineralized fluid. The redox conditions varied from equilibrium with CH₄-bearing fluid at the gold-molybdenum-tungsten stage to equilibrium with CO₂-bearing fluid during the gold-ore stage.     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

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.     

Fluid infiltration effects on stable isotope systematics of the Susurluk skarn deposit,NW Turkey

A calcic skarn deposit occurs along the contact zone between Oligo-Miocene Çatalda? Granitoid and Mesozoic limestones in Susurluk, northwestern Turkey. The skarn zone with little or no retrograde stage is represented by fluid inclusions with high homogenization temperatures (up to >600 °C) and a wide range of salinity (12 to >70 wt.% NaCl). Pluton-derived fluids facilitated occurrence of continuous prograde reactions in the country rocks (particularly in the proximal zone) and oxygen isotopic depletion in calc-silicate and calcite minerals. δ¹⁸O of anhydrous minerals within proximal and distal zones indicate that skarn-forming fluids had a magmatic origin. The δ¹⁸O values are 5.93–9.08‰ (mean 6.8‰) for garnet, 4.08–9.94‰ (mean 6.4‰) for pyroxene, 4.89–7.92‰ (mean 6.4‰) for wollastonite and 6.65–8.28‰ (mean 7.5‰) for vesuvianite. Temperatures estimated by isotopic compositions of mineral pairs are significantly lower than those measured from the fluid inclusions, indicating that isotopic equilibrium is not preserved between the skarn minerals. δ¹⁸O and δ¹³C values are systematically depleted from marbles to skarn carbonates. Calc-silicate forming reactions and permeability increase triggered by volatilization and consequent strong infiltration of H₂O-rich siliceous fluids into the system promoted fluid–rock interaction causing isotopic resetting and isotopic depletion of silicates (e.g. pyroxene and wollastonite) and skarn calcites.     

Isotopic composition (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genesis of carbonates from the famennian manganiferous formation of Pai-Khoi

The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ¹³C values from–6.6 to 1.3‰ and δ¹⁸O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ¹³C from–5.2 to–2.9 and δ¹⁸O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ¹³C from–16.4 to–13.1 and δ¹⁸O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ¹³C from–13.0 to–10.4‰ and δ¹⁸O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ¹⁸O from 18.7 to 17.6‰ and δ¹³C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO₂. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions.     

Fractionation of hydrogen,oxygen and carbon isotopes in n-alkanes and cellulose of three Sphagnum species

Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were determined in a greenhouse study. Three Sphagnum species were grown under controlled climate conditions. Stable isotope ratios of cellulose, bulk organic matter (OM) and C₂₁–C₂₅ n-alkanes were measured to explore whether fractionation in Sphagnum is species-specific, as a result of either environmental conditions or genetic variation. The oxygen isotopic composition (δ¹⁸O) of cellulose was equal for all species and all treatments. The hydrogen isotopic composition (δD) of the n-alkanes displayed an unexpected variation among the species, with values between −154‰ for Sphagnum rubellum and −184‰ for Sphagnum fallax for the C₂₃ n-alkane, irrespective of groundwater level. The stable carbon isotopic composition (δ¹³C) of the latter also showed a species-specific pattern. The pattern was similar for the carbon isotope fractionation of bulk OM, although the C₂₃ n-alkane was >10‰ more depleted than the bulk OM. The variation in H fractionation may originate in the lipid biosynthesis, whereas C fractionation is also related to humidity conditions. Our findings clearly emphasize the importance of species identification in palaeoclimate studies based on stable isotopes from peat cores.     

Carbon, oxygen, strontium, and sulfur isotopic compositions in late Precambrian rocks of the Patom Complex, central Siberia: Communication 2. Nature of carbonates with ultralow and ultrahigh δ13C values

The Patom Complex is characterized by a unique association of carbonate rocks with ultralow (≤8‰) and ultrahigh (>6‰) δ¹³C values. The thickness, stable isotopic composition along the strike, and lithological and geochemical parameters suggest that these rocks could not form as a result of short-term local events or epigenetic processes. Ultralow δ¹³C values (less than ?8‰) in carbonate rocks of the Zhuya Group, which substantially exceed all the known negative C isotope anomalies in thickness (up to 1000 m) and amplitude (δ¹³C = ?10 ± 2‰), point to sedimentation under conditions of extreme “contamination” of water column by oxidized isotopically light organic (hereafter, light) carbon. The decisive role in this contamination belonged to melting and oxidation of huge volumes of methane hydrates accumulated in sediments during the powerful and prolonged Early Vendian glacial epoch. The accumulation of δ¹³C-depleted carbonates was preceded by the deposition of carbonates with anomalously high δ¹³C values. These carbonates formed at high rates of the burial of organic matter and methane in sediments during periods when the sedimentation basin consumed carbon dioxide from the atmosphere and organic carbon was conserved in sediments.     

Geochemical comparison between gas in fluid inclusions and gas produced from the Upper Triassic Xujiahe Formation,Sichuan Basin,SW China

Natural gas in the Xujiahe Formation of the Sichuan Basin is dominated by hydrocarbon (HC) gas, with 78–79% methane and 2–19% C₂₊ HC. Its dryness coefficient (C₁/C_1–5) is mostly < 0.95. The gas in fluid inclusions, which has low contents of CH₄ and heavy hydrocarbons (C₂₊) and higher contents of non-hydrocarbons (e.g. CO₂), is a typical wet gas produced by thermal degradation of kerogen. Gas produced from the Upper Triassic Xujiahe Formation (here denoted field gas) has light carbon isotope values for methane (δ¹³C₁: −45‰ to −36‰) and heavier values for ethane (δ¹³C₂: −30‰ to −25‰). The case is similar for gas in fluid inclusions, but δ¹³C₁ = −36‰ to −45‰ and δ¹³C₂ = −24.8‰ to −28.1‰, suggesting that the gas experienced weak isotopic fractionation due to migration and water washing. The field gas has δ¹³C_CO2 values of −15.6‰ to −5.6‰, while the gas in fluid inclusions has δ¹³C_CO2 values of −16.6‰ to −9‰, indicating its organic origin. Geochemical comparison shows that CO₂ captured in fluid inclusions mainly originated from source rock organic matter, with little contribution from abiogenic CO₂. Fluid inclusions originate in a relatively closed system without fluid exchange with the outside following the gas capture process, so that there is no isotopic fractionation. They thus present the original state of gas generated from the source rocks. These research results can provide a theoretical basis for gas generation, evolution, migration and accumulation in the basin.     

Origin and depositional environments of source rocks and crude oils from Niger Delta Basin: Carbon isotopic evidence

Thirty-nine crude oils and twenty-one rock samples from Niger Delta Basin, Nigeria have been characterized based on their isotope compositions by elemental analysis-isotope ratio mass spectrometry and gas chromatography-isotope ratio mass spectrometry. The bulk carbon isotopic values of the whole rock extracts, saturate and aromatic fractions range from –28.7‰ to –26.8‰, –29.2‰ to –27.2 ‰ and –28.5 ‰ to –26.7 ‰, respectively while the bulk carbon isotopic values of the whole oils, saturate and aromatic fractions range from –25.4 ‰ to –27.8 ‰, –25.9 ‰ to –28.4 ‰ and –23.5 ‰ to –26.9 ‰, respectively. The average carbon isotopic compositions of individual alkanes (nC₁₂-nC₃₃) in the rock samples range from –34.9‰ to –28.2‰ whereas the average isotopic values of individual n-alkanes in the oils range from –31.1‰ to –23.8‰. The δ¹³C isotope ratios of pristane and phytane in the rock samples range from –29.2 ‰ to –28.2 ‰ and –30.2 ‰ to –27.4 ‰ respectively while the pristane and phytane isotopic values range from –32.1‰ to –21.9‰ and –30.5‰ to –26.9‰, respectively. The isotopic values recorded for the samples indicated that the crude oils were formed from the mixed input of terrigenous and marine organic matter and deposited under oxic to sub-oxic condition in lacustrine-fluvial/deltaic environments. The stable carbon isotopic compositions were found to be effective in assessing the origin and depositional environments of crude oils in the Niger Delta Basin.     

Isotope and chemical composition of gases from mud volcanoes in the Taman Peninsula and problem of their genesis

Variations in the carbon isotope composition in gases and waters of mud volcanoes in the Taman Peninsula are studied. The δ¹³C values in CH₄ and CO₂ vary from ?59.5 to ?44.0‰ (δ¹³C_av = ?52.4 ± 5.4‰) and from ?17.8 to +22.8‰ (δ¹³C_av = +6.9 ± 9.3‰), respectively. In waters from most mud volcanoes of the peninsula, this parameter ranges from +3.3 to +33.1‰, although locally lower values are also recorded (up to ?12‰. Fractionation of carbon isotopes in the CO₂-HCO₃ system corresponds to the isotope equilibrium under Earth’s surface temperatures. The growth of carbon dioxide concentration in the gaseous phase and increase in the HCO₃ ion concentration in their water phase is accompanied by the enrichment of the latter with the heavy ¹³C isotope. The δ¹³C_TDIC value in the water-soluble carbon depends on the occurrence time of water on the Earth’s surface (exchange with atmospheric CO₂, methane oxidation, precipitation of carbonates, and other processes), in addition to its primary composition. In this connection, fluctuations in δ¹³C_TDIC values in mud volcanoes with stagnant waters may amount to 10–20‰. In the clayey pulp, concentrations of carbonate matter recalculated to CaCO₃ varies from 1–4 to 36–50 wt %. The δ¹³C value in the latter ranges from ?3.6 to +8.4‰. Carbonate matter of the clayey pulp represents a mixture of sedimentogenic and authigenic carbonates. Therefore, it is usually unbalanced in terms of the carbon isotope composition with the water-soluble CO₂ forms.     

An experimental set-up for carbon isotopic analysis of atmospheric CO 2 and an example of ecosystem response during solar eclipse 2010

We present here, an experimental set-up developed for the first time in India for the determination of mixing ratio and carbon isotopic ratio of air-CO₂. The set-up includes traps for collection and extraction of CO₂ from air samples using cryogenic procedures, followed by the measurement of CO₂ mixing ratio using an MKS Baratron gauge and analysis of isotopic ratios using the dual inlet peripheral of a high sensitivity isotope ratio mass spectrometer (IRMS) MAT 253. The internal reproducibility (precision) for the δ ¹³C measurement is established based on repeat analyses of CO₂±0.03‰. The set-up is calibrated with international carbonate and air-CO₂ standards. An in-house air-CO₂ mixture, ‘OASIS AIRMIX’ is prepared mixing CO₂ from a high purity cylinder with O₂ and N₂ and an aliquot of this mixture is routinely analyzed together with the air samples. The external reproducibility for the measurement of the CO₂ mixing ratio and carbon isotopic ratios are ±7 (n?=?169) $\upmu $ mol·mol^???1 and ±0.05 (n?=?169) ‰ based on the mean of the difference between two aliquots of reference air mixture analyzed during daily operation carried out during November 2009–December 2011. The correction due to the isobaric interference of N₂O on air-CO₂ samples is determined separately by analyzing mixture of CO₂ (of known isotopic composition) and N₂O in varying proportions. A +0.2‰ correction in the δ ¹³C value for a N₂O concentration of 329 ppb is determined. As an application, we present results from an experiment conducted during solar eclipse of 2010. The isotopic ratio in CO₂ and the carbon dioxide mixing ratio in the air samples collected during the event are different from neighbouring samples, suggesting the role of atmospheric inversion in trapping the emitted CO₂ from the urban atmosphere during the eclipse.