Carbon isotopic characteristics and their genetic relationships for individual lipids in plants and sediments from a marsh sedimentary environment

The carbon isotopic compositions of individual lip-ids can provide the genetic information about sedi-mentary lipids so that it has extensively applied pros-pects in geochemically studied field[1―8]. However, this applied research relies heavily on the accumula-tion of studied data in the genetic relationships between carbon isotopic compositions of individual lipids and their biological precursors in different sedi-mentary environments. Recently, the useful δ 13C data of individual lipids f…     

Carbon isotopic studies of individual lipids in organisms from the Nansha sea area, China

Sediments contain abundant lipid compounds in general, which are used as biomarker compounds to study organic matter sources and reconstruct the pa-laeoenvironments[1—7]. However, lipid compounds in sediments are generally a mixture of various genetic components so that it is difficult to correctly decouple their biological sources only by the results of bio-chemical researches. Carbon isotopic studies of indi-vidual sedimentary lipid compounds can discover their genetic information, which pr…     

Nitrogen isotopic geochemical characteristics of crude oils in several basins of China

Nitrogen occupies a high content in crust and in atmospheric circle. It is one of the main elements in organism and an important element in sedimentary circle. Although nitrogen is little in crude oil, to a cer-tain degree, it influences the physical and chemical properties of oil, such as viscosity and density[1]. In reservoir the nitrogen-bearing compounds can form ion bonds or hydrogen bonds with substances on rock and form van der Vaals’ force among moleculae so they affect and alter the …     

Distribution and significance of C~_(40) alkanes in the extracts of Cretaceous source rocks from the Songliao Basin

Source rock extracts and crude oils from the Songliao Basin were analyzed by high-temperature gas chromatography (HTGC), gas chromatography-mass spectrometry (HTGC-MS) and gas chromatography-isotope ratio-mass spectrometry (GC-IRMS), for high molecular-weight alkanes. The distributions of n-alkanes in the Nenjiang Formation extracts are in the C14―C63 range; a bimodal distribution occurs in the C-21 and C21―40 regions. The C30―C37 n-alkanes are accompanied by C29―C35 hopanes, whereas the high molecular-weight C45―C47 n-alkanes co-occur with abundant isoalkanes, alkylcyclohexanes and alkylcyclopentanes. The high δ 13C values of the n-alkanes and the microscopic maceral compositions indicate a highly diversified organic source input for the Nenjiang Formation source rocks, ranging from aquatic plants, blue alge-bacteria, to land plant material. In contrast, n-alkanes in the rock extracts of the Qingshankou Formation are characterized by a single modal distribution, with relatively low abundances of C29―C35 hopanes, but high molecular-weight isoalkanes, alkylcyclohexanes and alkylcyclopentanes. The relatively low δ 13C values of C22―C44 n-alkanes and organic material compositions indicate that the source rocks in the Qingshankou Formation contain dominantly type I algal organic matter. The relative abundance of C 40 compounds in source rocks changes little at low maturity stage, but decreases drastically at higher maturity levels, with a concurrent reduction in the odd/even carbon predominance. In crude oils, in contrast, the relative abundance of C 40 compounds appears to relate closely with the oil source and oil viscosity.     

Carbon and hydrogen isotopic characteristics of natural gases from the Luliang and Baoshan basins in Yunnan Province, China

The Luliang and Baoshan basins are two small ba- sins in Yunnan Province. In the recent ten years or so, there have been found a number of natural gas pools of commercial importance in the two basins. Although the gas pools are small in size, the natural …     

Carbon isotopic compositions of 1,2,3,4-tetramethylbenzene in marine oil asphaltenes from the Tarim Basin: Evidence for the source formed in a strongly reducing environment

Although 1-alkyl-2,3,6-trimethylbenzenes and a high relative amount of 1,2,3,4-tetramethylbenzene have been detected in marine oils and oil asphaltenes from Tabei uplift in the Tarim Basin, their bio-logical sources are not determined. This paper deals with the molecular characteristics of typical ma-rine oil asphaltenes from Tabei and Tazhong uplift in the Tarim Basin and the stable carbon isotopic signatures of individual compounds in the pyrolysates of these asphaltenes using flash pyrolysis-gas chromatograph-mass spectrometer (PY-GC-MS) and gas chromatograph-stable isotope ratio mass spectrometer (GC-C-IRMS), respectively. Relatively abundant 1,2,3,4-tetramethylbenzene is detected in the pyrolysates of these marine oil asphaltenes from the Tarim Basin. δ 13C values of 1,2,3,4-tetrame-thylbenzene in the pyrolysates of oil asphaltenes vary from-19.6‰ to-24.0‰, while those of n-alkanes in the pyrolysates show a range from-33.2‰ to-35.1‰. The 1,2,3,4-tetramethylbenzene in the pyro-lysates of oil asphaltenes proves to be significantly enriched in 13C relative to n-alkanes in the pyro-lysates and oil asphaltenes by 10.8‰―15.2‰ and 8.4‰―13.4‰, respectively. This result indicates a contribution from photosynthetic green sulfur bacteria Chlorobiaceae to relatively abundant 1,2,3,4-tetramethylbenzene in marine oil asphaltenes from the Tarim Basin. Hence, it can be speculated that the source of most marine oil asphaltenes from the Tarim Basin was formed in a strongly reducing water body enriched in H2S under euxinic conditions.     

Identification and quantification of mixed sources of oil spills based on distributions and isotope profiles of long-chain n-alkanes

Combined with quantitative determination of concentration and isotopic composition of petroleum hydrocarbons, weathering simulation experiments on artificially mixed oils and their two end-member oils are performed for identification and quantification of mixed sources. The >C₁₈n-alkanes show no appreciable losses during a short-term weathering process. An approach based on distribution of long-chain n-alkanes (>C₁₈) is suggested for estimating the contribution proportion of each source in mixed oils. Stable carbon isotope profile of individual n-alkanes is a powerful tool to differentiate sources of oil spills, but unavailable to accurately allocate each contribution due to a relatively large analytical error.     

Stable carbon and nitrogen isotopic composition of gas hydrate-bearing sediment from Hydrate Ridge,Cascadia Margin

Serious interest has been directed toward natural gas hydrate as a potential energy resource; factor in global climate change, and submarine geohazard since naturally occurring gas-hydrate deposits were found in the 1960s. Hydrate Ridge, Cascadia convergent mar- gin, is characterized by abundant methane hydrates at and below the seafloor, active venting of fluids and gases, chemosynthetic communities, and some of the highest methane oxidation rates ever found in the ma-rine environment. All of…     

Influence of aquatic plants on the hydrogen isotope composition of sedimentary long-chain n-alkanes in the Lake Qinghai region,Qinghai-Tibet Plateau

The hydrogen isotopic composition(δD) of leaf wax long-chain n-alkanes(C27, C29, and C31) from lacustrine sediments has been widely applied to reconstruct terrestrial paleoclimatic and paleohydrological changes. However, few studies have addressed whether the aquatic-derived n-alkanes can affect the δD values of lake sedimentary long-chain n-alkanes, which are usually regarded as a recorder of the terrestrial hydrological signals. Here we systematically investigated δD values of long-chain n-alkanes from modern aquatic plants, both near-shore and off-shore surface sediments, surrounding terrestrial plant litters, as well as river water and lake water in Lake Qinghai and its satellite lakes on the northeastern Qinghai-Tibet Plateau. Our data showed that(i) δD values of long-chain n-alkanes from aquatic plants varied from-184‰ to-132‰ for n-C27, from-183‰ to-138‰ for n-C29, and from-189‰ to-130‰ for n-C31, respectively, with no significant differences among the three n-alkanes homologues;(ii) δD values of long-chain n-alkanes from aquatic plants were generally more positive than those from surrounding terrestrial plants, possibly because that they recorded the D-enrichment of lake water in this semi-arid region;(iii) δD values of long-chain n-alkanes from surface sediments showed significant differences among the three n-alkanes homologues, due to the larger aquatic input of n-C27 to the sedimentary lipid pool than that of n-C31, and(iv) n-C27 δD values of near-shore aquatic plants and near-shore sediments are more negative than those from off-shore as a result of lower δD values of near-shore lake water. Our findings indicate that in this region(i) the offset between sedimentary n-C27 and n-C31 δD values(ΔδDC27-C31) could potentially be used to evaluate if sedimentary long-chain n-alkanes are derived from a single source;(ii) while δD values of n-C27 may be influenced by lake water hydrological changes, sedimentary n-C31 is derived predominantly from terrestrial plants and thus its δD can serve as a relatively reliable indicator for terrestrial paleoclimatic and paleohydrological reconstructions.     

Genetic features of gas-condensate reservoirs in the Kekeya Field,southwest depression in the Tarim Basin,China

Oils, condensates and natural gases in the Kekeya Field, southeast depression of the Tarim Basin were studied for their geochemical characteristics. According to the distribution analysis of the C₂/C₃ values with C₁/C₂ values, C₂/C₃ values with C₁/C₃ values, as well as C₂/C₃ values with dryness index, there are two different types of natural gases in the studied field, which are spatially regularly distributed. One is the oil cracking gas, located on shallow reservoirs over X ²₅ reservoir, namely Upper oil legs; the other is kerogen cracking gas, located on X ²₇ reservoirs, X₈ reservoirs and E₂ k reservoirs, namely Lower oil legs. In addition, the distribution patterns of molar concentration of oils and condensates with different carbon numbers of the n-alkanes in the Kekeya Field indicate that the crude oils have experienced several kinds of secondary alterations, which were closely related to the charging of gaseous hydrocarbons after petroleum accumulation. These results indicate that, based on the research of δ ¹³C values of individual hydrocarbons, heptane values and isoheptane values of light hydrocarbons and aromatic maturity parameters for oils, condensates and natural gases, oils and gases were charged at different geological time in the Kekeya Field.

     

Temporal and spatial variations of <Emphasis Type="Italic">δ</Emphasis><Superscript>15</Superscript>N and <Emphasis Type="Italic">δ</Emphasis><Superscript>18</Superscript>O for atmospheric N<Subscript>2</Subscript>O above the oceanic surface from Shanghai to Antarctica

During the 22nd Chinese Antarctic Research Expedition (CHINARE-22), the atmospheric gas samples above the oceanic surface and near the surface were collected on the track for the scientific ship “Xuelong” and on Millor Peninsula of eastern Antarctica, respectively, using the Tedlar gas bags. Every day the sampling times were 10:00 and 22:00 (local time), respectively. In the laboratory, high-precision measurement of the isotopic compositions for N₂O in these gas samples was conducted using Thermo Finnigan MAT-253 Isotopic Mass Spectrometer with a fully automated interface for the pre-GC concentration (PreCon) of trace gases. The temporal and spatial variations of δ ¹⁵N and δ ¹⁸O in atmospheric N₂O were analyzed. The mean δ ¹⁵N and δ ¹⁸O-N₂O values above the oceanic surface were (7.21±0.50)‰ and (44.52±0.52)‰, respectively. From 30°N to Antarctica, the δ ¹⁵N (6.05‰–7.88‰) linearly increased with the rate of about 0.01‰ with the latitude while the δ ¹⁸O (43.05‰–48.78‰) showed a large fluctuation. The δ ¹⁵N negatively correlated with air temperature and N₂O concentration, and slightly positively correlated with δ ¹⁸O. The summertime variations of δ ¹⁵N and δ ¹⁸O-N₂O appeared the same trend on Millor Peninsula of eastern Antarctica. They significantly positively correlated with each other and negatively with N₂O concentration. The δ ¹⁵N and δ ¹⁸O-N₂O at different sites averaged (7.42±0.35)‰ and (44.69±0.49)‰, respectively, slightly higher than those above the oceanic surface, significantly higher than those of atmospheric N₂O in the low-latitude regions of Northern Hemisphere. The predominant factors affecting the spatial variations of δ ¹⁵N and δ ¹⁸O values were also discussed. The isotopic data given in this study can help to investigate the global and regional N₂O budgets. Supported by the National Natural Science Foundation of China (Grant Nos. 40676005 and 40406001)     

Abiogenic hydrocarbons in commercial gases from the Songliao Basin, China

This paper discusses the kinetic fractionation, composition and distribution characteristics of carbon and hydrogen isotopes for various alkane gases formed in different environments, by different mecha- nisms and from different sources in nature. It is demonstrated that the biodegradation or thermode- gradation of complex high-molecule sedimentary organic material can form microbial gas or thermogenic gas. The δ 13C1 value ranges from -110‰ to -50‰ for microbial gases but from -50‰ to -35‰ (even heavier) f...     

The distribution characteristic and its significance of compound specific isotopic composition of aromatic hydrocarbon from marine source rock and oil in the Tarim Basin,western China

Aromatic hydrocarbons are generally main distillation of crude oil and organic extract of source rocks. Bicyclic and tricyclic aromatic hydrocarbons can be purified by two-step method of chromatography on alumina. Carbon isotopic composition of individual aromatic hydrocarbons is affected not only by thermal maturity, but also by organic matter input, depositional environment, and hydrocarbon generation process based on the GC-IRMS analysis of Upper Ordovician, Lower Ordovician, and Cambrian source rocks in different areas in the Tarim Basin, western China. The subgroups of aromatic hydrocarbons as well as individual aromatic compound, such as 1-MP, 9-MP, and 2,6-DMP from Cambrian-Lower Ordovician section show more depleted 13 C distribution. The 13 C value difference between Cambrian-Lower Ordovician section and Upper Ordovician source rocks is up to 16.1‰ for subgroups and 14‰ for individual compounds. It can provide strong evidence for oil source correlation by combing the 13 C value and biomarker distribution of different oil and source rocks from different strata in the Tarim Basin. Most oils from Tazhong area have geochemical characteristics such as more negative 13C9-MP value, poor gammacerane, and abundant homohopanes, which indicate that Upper Ordovician source rock is the main source rock. In contrast, oils from Tadong area and some oils from Tazhong area have geochemical characteristics such as high 13C9-MP value, abundant gammacerane, and poor homohopanes, which suggest that the major contributor is Cambrian-Lower Ordovician source rock.     

Stable isotopic studies of dinosaur eggshells from the Nanxiong Basin, South China

Stable carbon and oxygen isotopes have been observed in dinosaur eggshell samples,identified as Macroolithus yaotunensis,collected in two sections of the Nanxiong Basin,Guangdong Province,South China.Multiple positiveδ18O perturbations that occurred during the K/T transition of about 150 ka suggest that there may have been at least three periods of the extreme dry climate with a mean annual air temperature over 27℃.δ13C ranges from -8.37‰ to -11.60‰ of the dinosaur eggshells,added to the metabolic enrichment of 16‰,may indicate that the dinosaurs represented by this type of eggshells probably consumed the plant species of C3 type with the δ13C values of -24.3‰- -27.6‰.Moreover,the trend toward more negative δ13C values of the eggshells during the K/T transition could be an indirect consequence of a lasting increase in atmospheric CO2 concentration.     

Genetic features of gas-condensate reservoirs in the Kekeya Field,southwest depression in the Tarim Basin,China

Oils, condensates and natural gases in the Kekeya Field, southeast depression of the Tarim Basin were studied for their geochemical characteristics. According to the distribution analysis of the C₂/C₃ values with C₁/C₂ values, C₂/C₃ values with C₁/C₃ values, as well as C₂/C₃ values with dryness index, there are two different types of natural gases in the studied field, which are spatially regularly distributed. One is the oil cracking gas, located on shallow reservoirs over X ₅ ² reservoir, namely Upper oil legs; the other is kerogen cracking gas, located on X ₇ ² reservoirs, X₈ reservoirs and E₂ k reservoirs, namely Lower oil legs. In addition, the distribution patterns of molar concentration of oils and condensates with different carbon numbers of the n-alkanes in the Kekeya Field indicate that the crude oils have experienced several kinds of secondary alterations, which were closely related to the charging of gaseous hydrocarbons after petroleum accumulation. These results indicate that, based on the research of δ ¹³C values of individual hydrocarbons, heptane values and isoheptane values of light hydrocarbons and aromatic maturity parameters for oils, condensates and natural gases, oils and gases were charged at different geological time in the Kekeya Field.     

Discrimination of abiogenic and biogenic alkane gases

We have combined the analytical data of the carbon isotope distribution pattern, R/Ra and CH4/3He values of abiogenic and biogenic (referring to the thermogenic and bacterial or microbial) alkane gases in China with those of alkane gases from USA, Russia, Germany, Australia and other countries. Four discrimination criteria are derived from this comparative study: 1) Carbon isotopic composition is generally greater than -30‰ for abiogenic methane and less than -30‰ for biogenic methane; 2) Abiogenic alkane gases have a carbon isotopic reversal trend (δ 13C1> δ 13C2> δ 13C3> δ 13C4) with δ 13C1>-30‰ in general; 3) Gases with R/Ra >0.5 and δ 13C11 δ 13C2>0 are of abiogenic origin; 4) Gases (meth- ane) with CH4/3He≤106 are of abiogenic origin, whereas gases with CH4/3He≥1011 are of biogenic origin.     

Hydrogen isotope composition of natural gases from the Tarim Basin and its indication of depositional environments of the source rocks

By measuring carbon and hydrogen isotope compositions for C1, C2 and C3 of 74 gas samples, natural gases from the Tarim Basin can be divided into six groups on the basis of their origins: (1) coal-type gas derived from coal measures; (2) coal-type gas generated from the T-J lacustrine mudstones; (3) oil-type gas derived from the Cambrian and low Ordovician marine source rocks; (4) oil-type gas from the source rocks deposited in the marine-transitional facies; (5) mixing gas between gas derived from the Carboniferous transitional source rocks and the Mesozoic humic gas, and (6) mixing gases of thermal genetic gas and little deep gas in the Southwest depression of the Tarim Basin. The δ D values of methane in natural gases originating from different type kerogens are affected by both palaeo-environments of the source rock formation (kerogen types) and thermal maturity, with sedimentary environment (kerogen type) as the main controlling factor. Under the similar thermal maturity, the hydrogen isotope composition of methane is more enriched in deuterium in marine environments than lacustrine one. With the increase of thermal maturity and the increase of carbon atomic numbers of gaseous alkanes, the hydrogen isotopes become enriched in deuterium. The δ D values of ethane and propane (δ D2, δ D3) are controlled mainly by thermal maturity and to a lesser degree by sedimentary environment of the source rock formation. The partial reversal of hydrogen isotopes for gaseous alkanes would be related to the microbial oxidation, mixing of sapropelic and humic gases and / or mixing of gases from similar kerogen sources with various thermal maturities. In the oil-type gas, the sulfate reduction reaction would result in the reversed order of δ D1 and δ D2 (e.g. δ D1>δ D2).     

Preliminary attempt to distinguish the domesticated pigs from wild boars by the methods of carbon and nitrogen stable isotope analysis

Despite great achievements in the origins of domestic pigs made by the methods of zooarchaeology and molecular biology, how to scientifically distinguish the domesticated pigs from wild boars during the early stage of pig domestication is still poorly understood. Compared to wild boar’s diets which come from the natural environment, the diets of domestic pigs are more easily influenced by human feeding activities. Therefore, in principle, exploration of the dietary differences among pigs and under-standing the impact on pig diets fed by humans can have great potential to differentiate between wild boars and domesticated pigs. To reveal dietary differences among pigs and distinguish the domesticated pigs from wild boars based on comparison with the diets of humans and other animals, we analyzed the carbon and nitrogen stable isotopes of human bones from Xiaojingshan Site and animal bones from Yuezhuang Site, both of which belong to Houli Culture in Shandong Province and date to about 8500-7500 years ago. The mean δ¹³C value ((−17.8 ± 0.3)‰) and δ¹⁵N value ((9.0±0.6)‰) in human collagen indicate that although millet agriculture began it was not the main subsistence strategy as millets are typical of C₄ plants and that humans made a living mainly by gathering, hunting or raising some domesticated animals. The δ¹³C value (−16.1‰) and δ¹⁵N value (6.9‰) in the bovine suggest that C₃ plants were dominant in its diet with some C₄ plants complemented. The fish has lower δ¹³C value (−24.9‰) and higher δ¹⁵N value (8.8‰) than the bovine, which is the characteristic of the isotopic values from Eurasian freshwater fish. Based on the differences in carbon and nitrogen isotope values, the pigs can be divided into three groups. A group, composed of two pigs, has low δ¹³C values (−18.1‰, −20.0‰) and low δ¹⁵N values (4.7‰, 6.0‰). B group, only one pig, has the highest δ¹³C value (−10.6‰) and mediate δ¹⁵N value (6.4‰). As for the C group, also only one pig, low δ¹³C value (−19.0‰) and the highest δ¹⁵N value (9.1‰) are observed. Previous studies on the stable isotopes from modern or ancient wild boars’ bones have suggested that C₃ plants are predominated in their diets and that their δ¹⁵N values are close to those in herbivores and far from those in carnivores. Based on the comparison with the isotope values from humans, the wild boars and the domestic pigs from Xipo Site in Henan 6000-5500 years ago and Kangjia Site in Shaanxi 4500-4000 years ago, we conclude that A pig group belongs to wild boars while B and C groups can be attributed to domesticated pigs. Supported by Max-Planck Society and Chinese Academy of Sciences, Knowledge Innovation Program of the Chinese Academy of Sciences (Grant No. KJCX3.SYW.N12), National Natural Science Foundation of China (Grant No. 40702003) and President Funding of Graduate University of Chinese Academy of Sciences     

Carbon isotope ratios of C4 plants in loess areas of North China

Carbon isotope ratios (δ ¹³C) of 89 C₄ plant samples were determined from the loess area in North China. δ ¹³C values vary between −10.5‰ and −14.6‰ with a mean of −12.6‰. Along a precipitation gradient from the semi-moist area to the semiarid area, then to the arid area, the δ ¹³C values of C₄ plants show a slight decreasing trend. The δ ¹³C values of C₄ plants in the dry season are found lower than those in the wet season. These trends are opposite to those observed for C₃ species.     

Metamorphic zircon from Xindian eclogite,Dabie Terrain: U-Pb age and oxygen isotope composition

~~Metamorphic zircon from Xindian eclogite,Dabie Terrain: U-Pb age and oxygen isotope composition@E. Deloule$CRPG-CNRS Nancy,54501,France1. Vavra, G, Gebauer. D., Schmid. R. et al., Multiple zircon growth and recrystallization during polyphase Late Carboniferous to Tri-assic metamorphism in granulites of the Ivrea Zone (Southern Alps): an ion microprobe (SHRIMP) study, Contrib. Mineral Petrol., 1996, 122:337-358 2. Vavra, G, Schmid, R., Gebauer, D., Internal morphology, ha…