Geochemistry on mantle-derived volatiles in natural gases from eastern China oil/gas provinces (II)

Rescarches on helium, argon, carbon dioxide and methane are very significant in studies of mantle substance characteristics and mantle evolution. A < -shaped pattern of the isotope composition distribution of helium and argon sourced from the mantle and the crust, abundance distribution, isotopic composition and reservoir formation of carbon dioxide, and mantle-sourced methane are discussed.     

Carbon isotopic composition and genetic types of natural gas in the Sichuan Basin,China

The origin and genetic types of natural gas in the Sichuan Basin are still disputed.To classify the origin and genetic types in different areas,the paper analyzes the carbon isotopic composition of gases and geologic features in the Sichuan Basin.The results showed that the gas sourced from terrestrial layers is typically characterized by terrestrial origin and was mainly accumulated nearby to form reservoir.The carbon isotopic composition of gas showed a normal combination sequence distribution,suggesting that natural gas in continental strata is not affected by secondary alteration or that this deformation is very weak.The gas source is singular,and only gas from the southern and northern Sichuan Basin shows the characteristic of mixed sources.However,marine gas presents the characteristics of an oil-formed gas.The carbon isotopic composition of natural gas in the western and central part of the basin mostly distributes in a normal combination sequence,and few of them showed an inversion,indicating that the gas perhaps had not experienced secondary alteration.The carbon isotopic composition of marine-origin gas in the southern,northern and eastern Sichuan Basin displays a completely different distribution pattern,which is probably caused by different mixing ratio of gas with multi-source and multi-period.     

Primary migration and secondary alteration of the Upper Paleozoic gas reservoir in Ordos Basin,China — Application of fluid inclusion gases

The composition of fluid inclusions (FI) often represents the initial geochemical characteristics of palaeo-fluid in reservoir rock. Influence on composition and carbon isotopic composition of gas during primary migration, reservoir-forming and subsequent secondary alterations are discussed through comparing fluid inclusion gas with coal-formed gas and natural gas in present gas reservoirs in the Ordos Basin. The results show that primary migration of gas has significant effect on the molecular but not on the carbon isotopic composition of methane. Migration and diffusion fractionation took place during the secondary migration of gas in Upper Paleozoic gas reservoir according to carbon isotopic composition of methane in Fls. Composition and carbon isotopic composition of natural gas were nearly unchanged after the gas reservoir forming through comparing the FI gases with the natural gas in present gas reservoir.

     

Carbon isotopic composition of modern soil and paleosol as a response to vegetation change on the Chinese Loess Plateau

The relationship between the carbon isotopic composition of paleosols and pale-ovegetation on the Loess Plateau is still unclear. One of the main reasons is that we are short of knowledge about the characteristics of the carbon isotopic composition of modern soil in this area. A preliminary investigation of the carbon isotopic compositions of the modern soil and the loess/paleosol sequence on the Loess Plateau shows that the carbon isotopic composition of modern soil is consistent with the distribution of modern plants on the Loess Plateau, where the ecosystem is dominated by a mixture of C4 and C3 plants. Comparing the δ13C values of modern soil and loess-paleosol sequences from the Xunyi profile, we conclude that C3 plants dominated the landscape during loess sediment stages, while C4 plants expanded during paleosol stages.     

Ni isotopic compositions in Allende and other meteorites

A new technique for high-precision isotopic analyses of Ni was developed and applied to terrestrial samples, Allende inclusions and materials from other meteorites. Most of the Allende inclusions analysed here were previously reported to contain isotopically anomalous Ti. In contrast, the Ni isotopic abundances are indistinguishable from normal within presently obtainable precision with only one possible exception. The latter inclusion was shown by others to contain a significantly fractionated magnesium isotopic pattern of 9‰/amu. A normal Ni isotopic pattern has also been observed for the chromite/carbon fraction of an Allende acid residue which is known to contain heavy noble gases of highly anomalous isotopic composition. All other meteoritic samples analysed (Khohar matrix and chondrules, Murray matrix, a Tieschitz chondrule and an Orgueil magnetic fraction) also show normal isotopic compositions of Ni; no evidence for effects from now extinct⁶⁰Fe could be detected. In spite of ubiquitous isotopic anomalies in Ti from normal Allende inclusions, there is no signature of isotopic variations in Ni from the same samples. Possible constraints for the nucleosynthesis of iron peak elements and for astrophysical and cosmochemical conditions during formation of the solar system are discussed.     

The stable isotopic composition of modern soil carbonate and its relationship to climate

The oxygen isotopic composition of modern soil carbonate is well correlated with the isotopic composition of local meteoric water. The carbon isotopic cycle for CO₂ in soils can be described in terms of the proportion of biomass using the C₄ photosynthetic pathway and the CO₂ respiration rate of the soil; at low soil respiration rates significant atmospheric CO₂ mixing can occur. In general, the carbon isotopic composition of soil carbonate is related to the proportion of C₄ biomass present in soil, but soils that freeze to the depth of carbonate formation often have a significant atmospheric component. This suggests that freezing of the soil solution should be considered as another important mechanism for soil carbonate formation. Because of these relationships, the isotopic composition of soil carbonate may be a paleoclimatic and paleoecologic indicator in cases in which diagenetic alteration has not occurred.     

Primary migration and secondary alteration of the Upper Paleozoic gas reservoir in Ordos Basin,China — Application of fluid inclusion gases

The composition of fluid inclusions (FI) often represents the initial geochemical characteristics of palaeo-fluid in reservoir rock. Influence on composition and carbon isotopic composition of gas during primary migration, reservoir-forming and subsequent secondary alterations are discussed through comparing fluid inclusion gas with coal-formed gas and natural gas in present gas reservoirs in the Ordos Basin. The results show that primary migration of gas has significant effect on the molecular but not on the carbon isotopic composition of methane. Migration and diffusion fractionation took place during the secondary migration of gas in Upper Paleozoic gas reservoir according to carbon isotopic composition of methane in Fls. Composition and carbon isotopic composition of natural gas were nearly unchanged after the gas reservoir forming through comparing the FI gases with the natural gas in present gas reservoir.     

Primary migration and secondary alteration of the Upper Paleozoic gas reservoir in Ordos Basin,China―Application of fluid inclusion gases

The composition of fluid inclusions(FI)often represents the initial geochemical characteristics of palaeo-fluid in reservoir rock.Influence on composition and carbon isotopic composition of gas during primary migration,reservoir-forming and subsequent secondary alterations are discussed through comparing fluid inclusion gas with coal-formed gas and natural gas in present gas reservoirs in the Ordos Basin.The results show that primary migration of gas has significant effect on the molecular but not on the carbon isotopic composition of methane.Migration and diffusion fractionation took place during the secondary migration of gas in Upper Paleozoic gas reservoir according to carbon isotopic composition of methane in FIs.Composition and carbon isotopic composition of natural gas were nearly unchanged after the gas reservoir forming through comparing the FI gases with the natural gas in present gas reservoir.     

Molecular and stable carbon isotopic characterization of PAH contaminants at McMurdo Station, Antarctica

The molecular and stable carbon isotopic compositions of contaminant polycyclic aromatic hydrocarbons (PAHs) at McMurdo Station, Antarctica were analyzed in samples collected from land and sub-tidal area. PAHs in the study areas were characterized by high amounts of naphthalene and alkylated naphthalenes from petroleum products introduced by human activities in the area. Principal component analysis (PCA) of PAH composition data identified multiple sources of PAH contamination in the study area. Compositional assignments of origins were confirmed using compound specific stable carbon isotopic analysis.     

Variations in chemical compositions of the eolian dust in Chinese Loess Plateau over the past 2.5 Ma and chemical weathering in the Asian inland

Major and trace elements as well as strontium isotopic composition have been analyzed on the acid-insoluble (AI) phase of the loess-paleosol sequence from Luochuan, Shaanxi Province, China. Results show that the chemical composition of AI phase of loess and paleosols is distinctive to the average composition of upper continental crust (UCC), characterized by depletion of mobile elements Na, Ca and Sr. The distribution pattern of elements in AI phase reveals that initial dust, derived from a vast area of Asian inland, has suffered from Na- and Ca-removed chemical weathering compared to UCC. Some geochemical parameters (such as CIA values, Na/K, Rb/Sr and⁸⁷Sr/⁸⁶Sr ratios) display a regular variation and evolution, reflecting that the chemical weathering in the source region of loess deposits has decreased gradually since 2.5 Ma with the general increase of global ice volume. This coincidence reflects that the aridity of Asian inland since the Quaternary is a possible regional response to the global climate change.     

Heavy carbon in individual oxide grains from the Murchison meteorite

The carbon isotopic composition of individual oxide grains from Murchison HF—HCl acid residue CFOc has been measured in the ion microprobe. Many grains (Mg-spinel, Cr-spinel, and Fe-oxide) contain carbon with large¹³C excesses ranging to 7000‰ (corresponding to¹²C/¹³C= 11). In most cases the carbon is present as micron-sized subgrains. The association of silicon with the anomalous carbon points towards SiC as carrier. If this tentative identification is correct then the SiC grains most likely originated in the circumstellar atmospheres of red giants. Oxide grains in which the ¹⁸O/¹⁶O ratio has also been measured show variable¹⁶O excesses which are not correlated with the¹³C excesses. This indicates that the sources of the anomalous carbon and oxygen isotopic compositions of the oxide grains are unrelated.     

High precision in-situ Pb isotopic analysis of sulfide minerals by femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry

An in-situ microanalysis of Pb isotopic compositions in sulfide minerals is carried out by using femtosecond laser-ablation multi-collector inductively coupled plasma mass spectrometry(fs LA-MC-ICP-MS).High-temperature-activated carbon was used to filter Hg contained in the carrier gas,which reduced the Hg background signal by 48%and also lowered the detection limit of the analysis.Fractionation and mass discrimination effects existing in the ICP-MS analytical processes were corrected using an internal reference Tl in conjunction with an external reference NIST SRM 610.The proposed method was used to analyze the Pb isotopic compositions of chalcopyrite,pyrite,and sphalerite from the Dulong Sn-Zn-In polymetallic ore district.The results showed that in this ore district,the sulfide minerals and different grains of the same sulfide mineral show a large variation in Pb content up to 1000-fold.The studied pyrites show relatively higher Pb contents and homogeneous Pb isotopic compositions,whereas the sphalerites have low Pb contents but most variable Pb isotopic compositions.It is suggested that the large variation of Pb isotopic composition may reflect a late hydrothermal superimposition on the primary sulfide formation.In addition,radiogenic Pb accumulated by radioactive decay of trace amounts of U over time in the host minerals may also be one of the causes for the large variation range of Pb content and Pb isotopic composition of those low-Pb sphalerites.Chalcopyrite and sphalerite grains with Pb content greater than 10 ppm presented a consistent Pb isotopic distribution,whereas all the sulfide grains with Pb content greater than 100 ppm had consistent Pb isotopic composition within 2s measurement uncertainties.The in-situ analysis of Pb isotopic composition agreed well with the results obtained by conventional chemical methods within2s measurement uncertainties,indicating that the data obtained by fs LA-MC-ICP-MS are reliable.Additionally,this study indicates that the Pb isotopic composition could truthfully record the source of ore-forming minerals only for sulfide minerals with high Pb content.On the contrary,the Pb isotopic composition of low-Pb sulfide minerals may be affected by trace amounts of U in the host minerals that may lead to a highly radiogenic Pb isotope ratio.Alternatively,it is also possible that late fluid metasomatic overprinting may alter the Pb isotopic compositions.     

Paleoclimate implication of oxygen and carbon isotopic composition from diagenesis coral

Oxygen and carbon isotopic compositions of diagenesis? coral samples from NY-1 core at the depth of 22 to 50 m, together with mineral compositions of transitive coral samples of 17 to 18 m at the depth, were meas ured. The data exhibited that when aragonite changed to calcite, its oxygen and carbon isotopic compositions dropped roughly on a linear trend. The linear trend implies that the oscillation pattern of the origin oxygen and carbon isotopic ratios of the aragonite could probably be retained after they diageneticly changed into calcite. Oxygen isotopic stratigraphy for the NY-1 core at the depth between 22 and 50 m was determined according to the δ⁸O ratios of the calcite coral. The oxygen stratigraphy provided an age of about 289 ka for 45 m of the NY-1 core, which agreed with that by paleomagnetic stratigraphy.     

Evaluation of the carbon isotopic effects of NDIR and CRDS analyzers on atmospheric CO2 measurements

Non-dispersive infrared(NDIR) and cavity ring-down spectroscopy(CRDS) CO_2 analyzers use 12CO_2 isotopologue absorption lines and are insensitive to all or part of other CO_2-related isotopologues. This may produce biases in CO_2 mole fraction measurements of a sample if its carbon isotopic composition deviates from that of the standard gases being used. To evaluate and compare the effects of carbon isotopic composition on NDIR and CRDS CO_2 analyzers, we prepared three test sample air cylinders with varying carbon isotopic abundances and calibrated them against five standard cylinders with ambient carbon isotopic composition using CRDS and NDIR systems. We found that the CO_2 mole fractions of the sample cylinders measured by G1301(CRDS) were in good agreement with those measured by Lo Flo(NDIR). The CO_2 values measured by both instruments were higher than that of a CO_2 isotope measured by G2201i(CRDS) analyzer for a test cylinder with depleted carbon isotopic composition δ~(13)C =-36.828‰, whereas no obvious difference was found for other two test cylinders with δ~(13)C=-8.630‰ and δ~(13)C=-15.380‰, respectively. According to the theoretical and experimental results, we concluded that the total CO_2 mole fractions of samples with depleted isotopic compositions can be corrected on the basis of their 12CO_2 values calibrated by standard gases using Lo Flo and G1301 if the δ~(13)C and δ18O values are known.     

Nonlinear relationship between preservation of microstructure and geochemical composition of Pleistocene brachiopod shells from the Ryukyu Islands,southwestern Japan

Stable carbon and oxygen isotope composition of fossilized brachiopod shells serves as an important source to delineate Earth's paleoenvironmental evolution in the Phanerozoic. However, the original isotopic composition is potentially modified by various kinds of diagenesis. To evaluate the extent to which the original isotopic composition of fossilized brachiopod shells is modified by meteoric diagenesis, microstructure, cathodoluminescence (CL) images, and carbon and oxygen isotope composition of fossilized Kikaithyris hanzawai (rhynchonellate brachiopod) shells were examined. The shells were collected from Pleistocene shallow marine carbonates exposed on the Ryukyu Islands, southwestern Japan. The extent of diagenetic alteration is quantitatively evaluated here as both the preservation state of the original shell microstructure and the luminescence/non‐luminescence of shells. Although altered fibers were commonly observed in the brachiopod shells, the original isotopic composition was almost retained. There are no significant differences in the isotopic composition between the luminescent and non‐luminescent shells. There is no direct relationship between the preservation state of the original shell microstructure and the luminescence/non‐luminescence of shells at three of four horizons, indicating that CL images are not necessarily useful for the detection of diagenetic alteration of shells or shell portions. Applying multiple criteria to assessing diagenetic alteration and cross‐checking them are required to distinguish between diagenetically altered and unaltered brachiopod shells.     

Boron Isotopic Composition of Freshwater Lakes from Central Europe and Possible Contamination Sources

The boron isotopic compositions of common synthetic boron products, municipal wastewaters from Switzerland, and three Swiss freshwater lakes were investigated. The δ11B values (δ11B values are normalized to the standard NIST SRM-951) of synthetic Na-borates (–0.4 to 7.6‰) and Ca-Na-borates (–13.4 to –4.9‰) overlap with those of natural borate minerals and hence suggest that the isotopic signal of anthropogenic boron is not modified during the manufacturing process. As a result it is possible to predict the isotopic composition of synthetic boron products and their potential impact upon contamination of water resources. The δ11B values of municipal wastewaters from two locations in northern Switzerland (–7.7 to –4.5‰) reflect utilization of Na/Ca- and/or Ca-borates depleted in 11B. Freshwater lakes from Switzerland (Lake Zürich, Greifensee, Lake Lugano) yielded a δ11B range of –1.7 to 7.1‰ and boron concentrations of 17 to 102 mg L–1. The boron isotopic ratios decrease with increasing boron concentrations, indicating mixing between anthropogenic boron with a low δ11B signature and meteoric boron with a heavier isotopic signal. We suggest that the isotopic composition of meteoric boron over central Europe has δ11B values in the range of ca. 10 to 20‰, whereas in coastal areas the marine component is larger with a higher 11B/10B ratio (δ11B ∼ 30‰).     

Compound‐Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis‐DCE compound‐specific isotope analysis of carbon and chlorine collected over a 16‐month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis‐DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ³⁷Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis‐DCE. Carbon isotopic values range between ?28.9 and ?20.7‰ VPDB for TCE, and ?26.5 and ?11.8‰ VPDB for cis‐DCE. In most wells, isotopic values remained steady over the 15‐month study. Isotopic enrichment from TCE to cis‐DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine‐carbon isotopic enrichment ratios (?_Cl/?_C) were 0.18 for TCE and 0.69 for cis‐DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume.     

Pb isotopic variability in melt inclusions from the EMI–EMII–HIMU mantle end-members and the role of the oceanic lithosphere

Melt inclusions from four individual lava samples representing the HIMU (Mangaia Island), EMI (Pitcairn Island) and EMII (Tahaa Island) end member components, have heterogeneous Pb isotopic composition larger than that defined by the erupted lavas in each island. The broad linear trend in ²⁰⁷Pb/²⁰⁶Pb–²⁰⁸Pb/²⁰⁶Pb space produced by the melt inclusions from Mangaia, Tahaa and fPitcairn samples reproduces the entire trend defined by the Austral chain, the Society islands and the Pitcairn island and seamount groups. The inclusions preserve a record of melt composition of far greater isotopic diversity than that sampled in whole rock basalts. These results can be explained by mixing of a common depleted component with the HIMU, EMI and EMII lavas, respectively. We favor a model that considers the oceanic lithosphere to be that common component. We suggest that the Pb isotopic compositions of the melt inclusions reflect wall rock reaction of HIMU, EMI and EMII melts during their percolation through the oceanic lithosphere. Under these conditions, the localized rapid crystallization of olivine from primitive basalt near the reaction zone would allow the entrapment of melt inclusions with different isotopic composition.     

Land-air boundary environment as recorded by the18O/16O and13C/12C isotope ratios in the shells of land snails

A yearly cycle of carbon and oxygen isotope composition of shells of the Israeli land snailXeropicta vestalis is presented. The¹⁸O/¹⁶O values indicate that the snails use water from the land-air boundary zone. The¹⁸O/¹⁶O ratio of the shells is in isotopic equilibrium with the water condensate from the vapour during the winter months. During the summer months a contribution to the above water from soil water migrating upwards due to evaporation is noticeable. The δ¹³C values indicate that as in marine molluscs, the carbon isotopic composition in land snails is controlled mainly by the aqueous carbonate compound which is in equilibrium with the land-air boundary CO₂.     

A high resolution palaeoclimatic record for the last 27,500 years in tropical West Africa from the carbon and nitrogen isotopic composition of lacustrine organic matter

Variations in the carbon and nitrogen isotopic composition of bulk organic matter in the sediments of Lake Bosumtwi, Ghana reflect climatically induced changes to the lake and the catchment flora. Cores spanning the last 27.5 kyr of sedimentation in the lake show large oscillations inδ¹³C_org PDB andδ¹⁵N_org Air. The late Pleistocene record is particularly detailed, showing changes of ca. 20‰ in carbon and ca. 10‰ in nitrogen isotopic compositions. These variations are of complex origin. Although different in magnitude, major isotopic excursions in the two records are generally in phase and reveal the occurrence of two major dry intervals at and immediately following the Last Glacial Maximum. The Allerød-Younger Dryas period also seems to have been marked by generally dry conditions in this part of tropical West Africa. Nitrogen isotopic evidence suggests that during the period 9.2–3.2 kyr the lake had an extremely stable water column, probably due to the absence of a windy or cool, dry season, or both. Regular circulation of the water column recommenced during the late Holocene and has persisted until the present day.