Characteristics of carbon isotopic composition of alkane gas in large gas fields in China

Exploration and development of large gas fields is an important way for a country to rapidly develop its natural gas industry.From 1991 to 2020,China discovered 68 new large gas fields,boosting its annual gas output to 1925×108m3in 2020,making it the fourth largest gas-producing country in the world.Based on 1696 molecular components and carbon isotopic composition data of alkane gas in 70 large gas fields in China,the characteristics of carbon isotopic composition of alkane gas in large gas fields in China were obtained.The lightest and average values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become heavier with increasing carbon number,while the heaviest values ofδ^(13)C_(1),δ13C2,δ13C3andδ13C4become lighter with increasing carbon number.Theδ^(13)C_(1)values of large gas fields in China range from-71.2‰to-11.4‰(specifically,from-71.2‰to-56.4‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-18.9‰for coal-derived gas,and from-35.6‰to-11.4‰for abiogenic gas).Based on these data,theδ^(13)C_(1)chart of large gas fields in China was plotted.Moreover,theδ^(13)C_(1)values of natural gas in China range from-107.1‰to-8.9‰,specifically,from-1071%o to-55.1‰for bacterial gas,from-54.4‰to-21.6‰for oil-related gas,from-49.3‰to-13.3‰for coal-derived gas,and from-36.2‰to-8.9‰for abiogenic gas.Based on these data,theδ^(13)C_(1)chart of natural gas in China was plotted.

Geochemistry and origins of hydrogen-containing natural gases in deep Songliao Basin,China:Insights from continental scientific drilling

The different reservoirs in deep Songliao Basin have non-homogeneous lithologies and include multiple layers with a high content of hydrogen gas.The gas composition and stable isotope characteristics vary significantly,but the origin analysis of different gas types has previously been weak.Based on the geochemical parameters of gas samples from different depths and the analysis of geological settings,this research covers the diverse origins of natural gas in different strata.The gas components are mainly methane with a small amount of C_(2+),and non-hydrocarbon gases,including nitrogen(N_(2)),hydrogen(H_(2)),carbon dioxide(CO_(2)),and helium(He).At greater depth,the carbon isotope of methane becomes heavier,and the hydrogen isotope points to a lacustrine sedimentary environment.With increasing depth,the origins of N_(2)and CO_(2)change gradually from a mixture of organic and inorganic to inorganic.The origins of hydrogen gas are complex and include organic sources,water radiolysis,water-rock(Fe^(2+)-containing minerals)reactions,and mantle-derived.The shales of Denglouku and Shahezi Formations,as source rocks,provide the premise for generation and occurrence of organic gas.Furthermore,the deep faults and fluid activities in Basement Formation control the generation and migration of mantle-derived gas.The discovery of a high content of H_(2)in study area not only reveals the organic and inorganic association of natural-gas generation,but also provides a scientific basis for the exploration of deep hydrogen-rich gas.

Carbon and Noble Gas Isotopes in the Tengchong Volcanic Geothermal Area, Yunnan, Southwestern China

Carbon and noble gas isotope analyses are reported for bubbling gas samples from the Tengchong volcanic geothermal area near the Indo-Eurasian suture zone. All samples contain a resolvable component of mantle-derived 3He. Occurrence of mantle-derived 3He coincides with surface volcanism. However, 3He occurs over a larger geographic areathan do surface volcanics. δ13C values for CO2 and CH4 vary from -33.4‰ to 1.6 ‰ and from -52.8‰ to -2.8‰, respectively. He and C isotope systematics indicate that CO2 and CH4 in the CO2-rich gases originated predominantly from magmatic component mixed with crustal CO2 produced from carbonate. However, breakdown of organic matter and near-surface processes accounts for the CH4 and CO2 in N2-rich gases. 3He/4He ratio distribution pattern suggests that mantle-derived He and heat sources of high-temperature system in central Tengchong originate from a hidden magma reservoir at subsurface. CO2-rich gases with the highest 3He/4He ratio (5.2 Ra) may be representative of the Tengchong magmatic component. Compared with MORB, this relative low 3He/4He ratio could be fully attributed to either deep crustal contamination, or radioactive aging, or past contamination of the local mantle by U- and Th-rich subducted crustal material. However, a combination of low 3He/4He, high radiogenic 4He/40Ar ratio and identical CO2/3He and δ13Cco2 relative to MORB may suggest addition of prior subductedd crsustal material (ca 1 %-2%) to the MORB reservoir around 1.3 Ga ago, which is essentially compatible with the LIL-elements, and Sr-Nd-Pb isotopes of volcanic rocks.

S, C, O, H Isotope Data and Noble Gas Studies of the Maoniuping LREE Deposit, Sichuan Province, China: A Mantle Connection for Mineralization

The Maoniuping REE deposit, located about 22 km to the southwest of Mianning, Sichuan Province, is the second largest light REE deposit in China, subsequent to the Bayan Obo Fe-Nb-REE deposit in the Inner Mongolia Autonomous Region. Tectonically, it is located in the transitional zone between the Panxi rift and the Longmenshan-Jinpingshan orogenic zone. It is a carbonatite vein-type deposit hosted in alkaline complex rocks. The bastnaesite-barite, bastnaesite-calcite, and bastnaesite- microcline lodes are the main three types of REE ore lodes. Among these, the first lode is distributed most extensively and its REE mineralization is the strongest. The δ^34Sv.cDT values of the barites in the ore of the deposit vary in a narrow range of ＋5.0 to ＋5.1‰ in the bastnaesite-calcite lode and ＋3.3 to ＋5.9‰ in the bastnaesite-barite lode, showing the isotopic characteristics of magma-derived sulfur. The δ^13Cv-PDB values and the δ^Ov.SMOW values in the bastnaesite-calcite lode range from -3.9 to -6.9‰ and from ＋7.3 to ＋9.7 ‰, respectively, which fall into the range of ＂primary carbonatltes＂, showing that carbon and oxygen in the ores of the Maoniuping deposit were derived mainly from a deep source. The δ^13Cv.PDB values of fluid inclusions vary from -3.0 to -5.6‰, with -3.0 to -4.0‰ in the bastnaesitecalcite lode and -3.0 to -5.6‰ in the bastnaesite-barite lode, which show characteristics of mantle- derived carbon. The δDv-SMOW values of fluid inclusions range from -57 to -88‰, with -63 to -86‰ in the bastnaesite-calcite lode and -57 to -88‰ in the bastnaesite-barite lode, which show characteristics of mantle-derived hydrogen. The δ^18OH2OV.SMOW values vary from ＋7.4 to ＋8.6‰ in the bastnaesitecalcite lode, and ＋6.7 to ＋7.8‰ in the bastnaesite-barite lode, almost overlapping the range of ＋5.5 to ＋9.5‰ for magmatic water. The 4He content, R/Ra ratios are （13.95 to 119.58）×10^-6 （cm^3/g）STP and 0.02 to 0.11, respectively, and ^40Ar/^36Ar is 313± 1 to 437 ± 2. Considering the 4He increase caused by high contents of radioactive elements, a mantle-derived fluid probably exists in the inclusions in the fluorite, calcite and bastnaesite samples. The Maoniuping deposit and its associated carbonatite-alkaline complex were formed in 40.3 to 12.2 Ma according to K-Ar and U-Pb data. All these data suggest that large quantities of mantle fluids were involved in the metallogenic process of the Maoniuping REE deposit through a fault system.

The Impact of Aqueous Medium on Gas Yields and Kinetic Behaviors of Hydrogen Isotope Fractionation during Organic Matter Thermal Degradation

In order to recognize the impact of aqueous medium on gas yields and the kinetic behaviors of hydrogen isotope fractionation during organic matter thermal degradation, the gold tube apparatus was used to conduct thermal simulation experiments by mixing the nC18 with the water of different properties and proportions. The yields of natural gas components, the relation among hydrogen isotope composition of each component and the experimental temperatures vs. heating rates have been obtained, and the results indicate that under the higher temperature conditions, the hydrous experiment has obvious impact on gas yields, such as when more water is added, higher amounts of hydrocarbon gas and H2 are yielded, and the existence of water obviously prolongs the temperature interval with the existence of heavy hydrocarbon gas. It also shows that the hydrogen isotope of hydrocarbon gas generated by the hydrous experiment is obviously lighter than that generated by the anhydrous experiment, and with the increasing amount of added water, the δD value of hydrocarbon gas gradually decreases. Compared with gas yields, the variation of δD value is more sensitive to aqueous medium in the thermal simulation experiment. However, compared with the amount of the added water, the aqueous medium property has smaller impact on the gas yields, which still shows the inherit effect on hydrogen isotope composition of aqueous medium. Through the model simulation and the isotope fractionation behavior analysis, it is validated that the hydrogen isotope fractionation process can be well described by the chemical kinetic model. The difference of reaction fraction of normal methane and D-containing methane is large, corresponding to the same activation energy. The content of normal methane is obviously higher in the part with lower activation energy, while the content of D-containing methane is higher in the part with higher activation energy. Therefore, it will result in larger hydrogen isotope fractionation amplitude, and the δD values will be more sensitive to the variation of maturity. Meanwhile, the average activation energy of methane generation from nC18 in the hydrous experiment is higher than that in the anhydrous experiment, and the greater amount of added water, the larger the average activation energy of methane generation reaction. This has laid foundation for its exploratory application in the study of gas reservoir forming history and the gassource correlation, which indicates the research and application prospects in this orientation.

The Openness Degree Study of the Jiaoshiba Shale Gas, Sichuan Basin, China–Potential Factor Responsible for Reversed Isotope Series

Objective Reversed alkane δ;C and δ;H values in many prolific shale plays all over the world have aroused much attention in the study of the formation mechanism of reversed isotope series in alkanes in the past few years（Zou Caineng et al., 2016）. Although many researchers have put forward different hypotheses, the mechanism has not been well understood yet. The openness degree of oil and gas system

Origin of the Gas Hydrate and Free Gas in the Qilian Permafrost,Northwest China:Evidence from Molecular Composition and Carbon Isotopes

The Qilian permafrost of the South Qilian Basin(SQB)has become a research focus since gas hydrates were discovered in 2009.Although many works from different perspectives have been conducted in this area,the origin of gas from gas hydrate is still controversial.Molecular composition and carbon isotope of 190 samples related to gas hydrates collected from 11 boreholes allowed exploration of genetic type,thermal maturity,biodegradation,as well as gas-source correlation of alkane gases from gas hydrates and free gases.Results indicate that alkane gases biodegraded after the formation of natural gas.According to differences in carbon isotopes of methane and their congeners(CH4,C2H6,C3H8),the thermal maturity(vitrinite reflectance,VRo)of most alkane gases ranges from 0.6%to 1.5%,indicating a mature to high mature stage.The thermal maturity VRo of a small part of alkane gas(in boreholes DK5 and DK6)is higher than 1.3%,indicating a high mature stage.Alkane gases were mainly produced by secondary cracking,consisting of crude oilcracking gases and wet gases cracking to dry gases.Genetic types of alkane gases are primarily oil-type gases generated from shales and mudstones in the upper Yaojie Formation of Jurassic,with less coal-type gases originated from the mudstones in the Triassic Galedesi Formation and the lower Yaojie Formation of Jurassic.Carbon dioxides associated with alkanes from gas hydrates and free gases indicate the thermal decomposition and biodegradation of organic matter.The origins of natural gases from gas hydrates and free gases shed light on the evaluation of petroleum resource potential,deeply buried sediments,and petroleum resource exploration in the SQB.

Affecting factors and application of the stable hydrogen isotopes of alkane gases

To study the composition, affecting factors of the stable hydrogen isotopes of alkane gases and their application to identification of the natural gas origin and maturities, the chemical and isotopic compositions of 118 gas samples of Carboniferous- Permian in the Ordos Basin, and of Triassic in the Sichuan Basin, combined with 68 gas samples from the Sinian and Cambrian reservoirs in the Sichuan Basin, and Ordovician and Siliurian reservoirs of Tarim Basin, are analyzed comprehensively. The following conclusions are obtained:(1) Natural gases in the study area and strata of the Ordos and Sichuan basins are dominated by alkane gases, and the dryness coefficients and maturities of the Carboniferous-Permian gases in the Ordos Basin are higher than the gases in the Triassic Xujiahe Formation of the Sichuan Basin, while the hydrogen isotopes of the latter ones are much enriched in 2H than the former.(2) The δ2HCH4-C1/C2+3 genetic identification diagram of natural gas was drawn, and the diagrams of hydrogen isotopic differences between the heavy alkane gases and methane vs. hydrogen isotopes of alkane gases can also be used in natural gas genetic identification.(3) The δ2HCH4-Ro formulas of coal-formed gas in different areas of the two basins are given, and the δ2HC2H6-δ2HCH4 is a new index for maturity, and the (δ2HC2H6-δ2HCH4)-Ro formula of the coal-formed gas can be used to calculate the maturity of the natural gas.(4) The stable hydrogen isotopes of alkane gases are affected by parent materials in source rocks, maturity, mixing and the aqueous medium conditions, among which the aqueous paleo-salinity is the key factor. To sum up, the hydrogen isotopes of alkane gases are affected by multiple factors, and they are significant to the identification of the origin, and maturity of natural gas, and the water environment during the deposition of source rocks.

Oxygenic iron clusters in ZSM-5 zeolite promote quantum sieving of gaseous hydrogen isotopes

Isotopic separation is of paramount importance for producing high-purity heavy hydrogen,yet the process remains hugely challenging.Here,we report on an Fe/ZSM-5 zeolite that was able to efficiently separate deuterium from protium via chemical quantum sieving.Structural data showed that four types of Fe species were present in Fe/ZSM-5 and oligomeric Fe-O clusters in the zeolite pores were correlated directly with gas selectivity.Gas adsorption revealed that Fe-O species served as the main adsorption sites and interacted with D_(2) more strongly than with H_(2).D_(2)/H_(2)separation was exemplified using thermal desorption spectroscopy.D_(2)/H_(2) selectivity increased with Fe loading in Fe/ZSM-5 and a selectivity of 32.1 was obtained with an optimal loading of 7 wt%.The shift of desorption temperature supports the chemical affinity-based quantum sieving of D_(2)over H_(2).This study demonstrates an effective strategy for enhancing D_(2)/H_(2) separation and the high selectivity means that Fe/ZSM-5 has strong potential in hydrogen isotope separation.

Helium,Argon and Carbon Isotopic Compositions of Spring Gases in the Hainan Island,China

Chemical and isotopic compositions have been measured for N2-He-rich bubbling gases discharging from hot springs in the Hainan Island, Southern China. Observed 3He/4He ratios （0.1-1.3 RA） indicate the occurrence of a mantle component throughout the island, which has been highly diluted by a crustal radiogenic 4He component. The occurrence of mantle-derived helium is high in the northern island （12%-16% of total He） and gradually decreases towards southern coast （1%-3% of total He）. Such a distribution pattern is most likely controlled by the Pleocene-Quaternary volcanic activities in the northern island and groundwater circulation along the deep major faults. The 4~Ar/36Ar and N2/Ar ratios suggest that N2 and Ar of the hot spring gases are mostly meteoric. Although 13C values of CO2 （-20%0 to -27%0） with low concentrations are consistent with the biogenic origin, the combination of SHe/4He and 51SCco2 suggests a two end-member mixing of mantle and crustal components with CO2/3He ratios of 2x 109 and 8 1011, respectively. However, the low CO2/3He ratios （1- 22106） can not be ascribed in terms of the simple mixing but has to be explained by the addition of radiogenic 4He and loss of CO2 by calcite precipitation in the hydrothermal system, which is most likely controlled by the degree of gas-water-rock interaction.

Water Role and Its Influence on Hydrogen Isotopic Composition of Natural Gas during Gas Generation

In order to discuss the role and influence of water during the generation of natural gas,the participation mechanism of water during the evolution of organic matter and its influences were summarized.In addition,we carried out an anhydrous cracking experiment of oil extracted from the Feixianguan Formation source rock in a closed system,which led to the establishment of the kinetic models for describing carbon and hydrogen isotopic fractionation during gas generation from organic matter.The models were calibrated and then applied to the northeastern Sichuan Basin.By combining a series of gas generation experiments from octadecane pyrolysis without water or with distilled water in varying mass proportions,several results were proved:(1) the hydrogen isotopic composition of natural gas becomes lighter with the participation of formation water;(2) we can quantitatively study the hydrogen isotopic fractionation with the kinetic model for describing carbon isotopic fractionation; (3) more abundant and reliable geological information can be obtained through the combined application of carbon and hydrogen isotopic indices.

Noble Gas Isotopic Compositions of Cobalt-rich Ferromanganese Crusts from the Western Pacific Ocean and Their Geological Implications

Noble gas isotopic compositions of various layers in three-layered （outer, porous and compact layers） cobalt-rich ferromanganese crusts and their basaltic and phosphorite substrates from the western Pacific Ocean were analyzed by using a high vacuum gas mass spectrum. The analytical results show that the noble gases in the Co-rich crusts have derived mainly from the ambient seawater, extraterrestrial grains such as interplanetary dust particles （IDPs） and wind-borne continental dust grains, and locally formation water in the submarine sediments, but different noble gases have different sources. He in the crusts derives predominantly from the extraterrestrial grains, with a negligible amount of radiogenic He from the eolian dust grains. Ar is sourced mainly from the dissolved air in the seawater and insignificantly from radiogenic Ar in the eolian continental dust grains or the formation water. Xe and Ne derive mainly from the seawater, with minor amounts of extraterrestrial Xe and Ne in the IDPs. Compared with the porous and outer layers, the compact layer has a relatively high 4He content and lower 3He/4He ratios, suggesting that marine phosphatization might have greatly modified the noble gas isotopic compositions of the crusts. Besides, the 3He/4He values of the basaltic substrates of the cobalt-rich crusts are very low and their R/R. ratios are mostly 〈0.1 R., which are similar to that of phosphorite substrates （0.087 R.）, but much lower than that of fresh submarine MORB （8.75±14 Ra） or seamount basalts （3-43 Ra）, implying that the basaltic substrates have suffered strong water/rock interaction and reacted with radiogenic ^4He and P-rich upwelling marine currents during phosphatization. The trace elements released in the basalt/seawater interaction might favor the growth of cobalt-rich crusts. The relatively low ^3He/^4He values in the seamount basalts may be used as an important exploration criterion for the cobalt-rich ferromanganese crusts.

Comparative Study of Hydrogen and Carbon Isotopic Composition of Gases Generated from the Pyrolysis of a Peat under Saltwater and Freshwater Conditions

To understand the influence of the diagenetic water medium on the isotopic compositions of thermogenic coalbed gas, both hydrous and anhydrous closed-system pyrolyses were performed at temperatures of 250°C to 650°C on an herbaceous marsh peat. Compared to the results of anhydrous pyrolysis, the hydrocarbon gases generated from hydrous pyrolyses have very different hydrogen isotopic compositions. However, the carbon isotopic compositions of the hydrocarbon gases became only slightly heavier in hydrous pyrolysis, compared to that from anhydrous pyrolysis. With the progress of thermal evolution from peat to a more advanced thermal maturity of vitrinite reflectance values（Ro） of 5.5% during the pyrolysis, the difference in the average δD value increased from 52‰ to 64‰ between the hydrous pyrolysis with saltwater and anhydrous pyrolysis and increased from 18‰ to 29‰ between the hydrous pyrolysis with freshwater and anhydrous pyrolysis, respectively. The difference in the average δ^（13）C value was only 1‰–2‰ between the hydrous and anhydrous pyrolysis. The relationships between the δD values of the generated hydrocarbon gases and Ro values as well as among δD values of the hydrocarbon gas species are established. The close relationships among these parameters suggest that the water medium had a significant effect on the hydrogen isotopic composition and a minimal effect on the carbon isotopic composition of the hydrocarbon gases. The results of these pyrolyses may provide information for the understanding of the genesis of coalbed gas from herbaceous marsh material with the participation of different diagenetic water media.

Constraints on granite-related uranium mineralization in the Sanjiu uranium ore field,SE China provided by pyrite mineralogy,major and trace elements,S-He-Ar isotopes

The Sanjiu uranium ore field,located in the central of Zhuguangshan granitic batholith,is a newly discovered granite-related uranium ore field in South China.The main sulfide in the ore field is pyrite,which is closely related to uranium mineralization.The textures major and trace elements,S-He-Ar isotopes compositions of pyrites in ores of different grade were observed and/or analyzed by optical microscope,scanning electron microscope,electron microprobe,laser ablation inductively coupled plasma mass spectrometry,and noble gas mass spectrometer(Helix-SFT).It is observed that these U-related pyrites are generally euhedral-subhedral with dissolution textures,anhedral variety with colloform texture veinlet and fine particles,and the color of the associated minerals is mostly dark hue,such as purple-black fluorite dark-red hematite,and dark-green chlorite,etc.The analytical results show that the average compositions of major elements in pyrite are FeS1.944.Pyrites are characterized by S-deficiency,low content of Co and Th,and Co/Ni>1which indicate that these ores are of low-temperature hydrothermal origin.We found that the higher the grade of ore,the more deficient in S,the more obvious negative δ^34S,and the higher REE content(close to U-rich granitic pluton)of pyrite.The S-He-Ar isotopic compositions of various varieties of pyrites indicate that the ore-forming fluids mainly come from crust-derived fluids and mixed with mantle-derived fluids.

Research progress on isotopic fractionation in the process of shale gas/coalbed methane migration

The research progress of isotopic fractionation in the process of shale gas/coalbed methane migration has been reviewed from three aspects: characteristics and influencing factors, mechanism and quantitative characterization model, and geological application. It is found that the isotopic fractionation during the complete production of shale gas/coalbed methane shows a four-stage characteristic of “stable-lighter-heavier-lighter again”, which is related to the complex gas migration modes in the pores of shale/coal. The gas migration mechanisms in shale/coal include seepage, diffusion, and adsorption/desorption. Among them, seepage driven by pressure difference does not induce isotopic fractionation, while diffusion and adsorption/desorption lead to significant isotope fractionation. The existing characterization models of isotopic fractionation include diffusion fractionation model, diffusion-adsorption/desorption coupled model, and multi-scale and multi-mechanism coupled model. Results of model calculations show that the isotopic fractionation during natural gas migration is mainly controlled by pore structure, adsorption capacity, and initial/boundary conditions of the reservoir rock. So far, the isotope fractionation model has been successfully used to evaluate critical parameters, such as gas-in-place content and ratio of adsorbed/free gas in shale/coal etc. Furthermore, it has shown promising application potential in production status identification and decline trend prediction of gas well. Future research should focus on:(1) the co-evolution of carbon and hydrogen isotopes of different components during natural gas migration,(2) the characterization of isotopic fractionation during the whole process of gas generation-expulsion-migration-accumulation-dispersion, and(3) quantitative characterization of isotopic fractionation during natural gas migration in complex pore-fracture systems and its application.

Stable carbon and hydrogen isotopic characteristics of natural gas from Taibei sag, Turpan-Hami Basin, NW China

Turpan-Hami Basin is a major petroliferous basin in China. To date the natural gas exploration is concentrated in the Taibei sag. The origin and source of natural gas in the Taibei sag has long been controversial. To further investigate the origin and source of the natural gas in the Taibei sag, combined with previous studies and the local geological backgrounds, this study collected 23 gas samples from the Baka, Qiuling, Shanshan and Wenmi oil fields in the Taibei sag and analyzed the sample composition, stable carbon and hydrogen isotopes of all the gas samples. The results show that, gases from the four oil fields in the Taibei sag are dominated by hydrocarbon gas and belong to wet gas. Methane accounts for 65.84% to 97.94%, the content of heavy hydrocarbon (C2-5) can be up to 34.98%, while the content of nonhydrocarbon (CO2, N2) is trace. The δ13C1 value is –44.9‰ to –40.4‰,δ13C2 is –28.2‰ to –24.9‰,δ13C3 is –27.1‰ to –18.0‰ and δ13C4 is –26.7‰ to –22.1;while the variation of δD1 is not significant from –272‰ to –252‰,δD2 is –236‰ to –200‰ and δD3 is –222‰ to –174‰. Methane and its homologues (C2-5) are characterized by normal stable carbon and hydrogen isotopic distribution pattern, i.e., with the increase of carbon number, methane and its homologues become more and more enriched in 13C or D (δ13C1<δ13C2<δ13C3<δ13C4<δ13C5,δD1<δD2<δD3), which is consistent with the carbon and hydrogen isotopic features of typical thermogenic gas. All these results show that the natural gases in the four oil fields are coal-derived gas with low maturity (Ro averaged at 0.7%), and are sourced from the Middle-Lower Jurassic coal measure. The hydrogen isotopic data of natural gas are affected by both thermal maturity and the water medium of the environment where source rocks are formed. The hydrogen isotopic data indicate that the source rocks are formed in terrestrial limnetic facies with freshwater. Natural gases from Well Ba23 and Well Ke19 experienced biodegradation in the late stage.

Using triple oxygen isotopes and oxygen-argon ratio to quantify ecosystem production in the mixed layer of northern South China Sea slope region

Quantifying the gross and net production is an essential component of carbon cycling and marine ecosystem studies.Triple oxygen isotope measurements and the O_(2)/Ar ratio are powerful indices in quantifying the gross primary production and net community production of the mixed layer zone,respectively.Although there is a substantial advantage in refining the gas exchange term and water column vertical mixing calibration,application of mixed layer depth history to the gas exchange term and its contribution to reducing indices error are unclear.Therefore,two cruises were conducted in the slope regions of the northern South China Sea in October 2014(autumn)and June 2015(spring).Discrete water samples at Station L07 in the upper 150 m depth were collected for the determination ofδ^(17)0,δ^(18)O,and the O_(2)/Ar ratio of dissolved gases.Gross oxygen production(GOP)was estimated using the triple oxygen isotopes of the dissolved O_(2),and net oxygen production(NOP)was calculated using O_(2)/Ar ratio and O_(2)concentration.The vertical mixing effect in NOP was calibrated via a N_(2)O based approach.GOP for autumn and spring was(169±23)mmol/(m^(2)·d)(by O_(2))and(189±26)mmol/(m^(2)·d)(by O_(2)),respectively.While NOP was 1.5 mmol/(m^(2)·d)(by O_(2))in autumn and 8.2 mmol/(m^(2)·d)(by O_(2))in spring.Application of mixed layer depth history in the gas flux parametrization reduced up to 9.5%error in the GOP and NOP estimations.A comparison with an independent O_(2)budget calculation in the diel observation indicated a26%overestimation in the current GOP,likely due to the vertical mixing effect.Both GOP and NOP in June were higher than those in October.Potential explanations for this include the occurrence of an eddy process in June,which may have exerted a submesoscale upwelling at the sampling station,and also the markedly higher terrestrial impact in June.

Sensitivity assessment of strontium isotope as indicator of polluted groundwater for hydraulic fracturing flowback fluids produced in the Dameigou Shale of Qaidam Basin

Hydrogeochemical processes that would occur in polluted groundwater and aquifer system,may reduce the sensitivity of Sr isotope being the indicator of hydraulic fracturing flowback fluids(HFFF)in groundwater.In this paper,the Dameigou shale gas field in the northern Qaidam Basin was taken as the study area,where the hydrogeochemical processes affecting Sr isotope was analysed.Then,the model for Sr isotope in HFFF-polluted groundwater was constructed to assess the sensitivity of Sr isotope as HFFF indicator.The results show that the dissolution can release little Sr to polluted groundwater and cannot affect the εSr(the deviation of the 87Sr/86Sr ratio)of polluted groundwater.In the meantime,cation exchange can considerably affect Sr composition in the polluted groundwater.The Sr with low εSr is constantly released to groundwater from the solid phase of aquifer media by cation exchange with pollution of Quaternary groundwater by the HFFF and it accounts for 4.6% and 11.0% of Sr in polluted groundwater when the HFFF flux reaches 10% and 30% of the polluted groundwater,respectively.However,the Sr from cation exchange has limited impact on Sr isotope in polluted groundwater.Addition of Sr from cation exchange would only cause a 0.2%and 1.2% decrease in εSr of the polluted groundwater when the HFFF flux reaches 10% and 30% of the polluted groundwater,respectively.These results demonstrate that hydrogeochemical processes have little effect on the sensitivity of Sr isotope being the HFFF indicator in groundwater of the study area.For the scenario of groundwater pollution by HFFF,when the HFFF accounts for 5%(in volume percentage)of the polluted groundwater,the HFFF can result in detectable shifts of εSr(Δ_(εSr)=0.86)in natural groundwater.Therefore,after consideration of hydrogeochemical processes occurred in aquifer with input of the HFFF,Sr isotope is still a sensitive indicator of the Quaternary groundwater pollution by the HFFF produced in the Dameigou shale of Qaidam Basin.

Ultralight Oxygen in Corundum-Bearing Rocks of North Karelia, Russia, as a Result of Isotope Separation by Thermal Diffusion (Soret Effect) in Endogenous Fluid Flow

Helium and argon isotopes in fluid inclusions in minerals of corundum bearing rocks with anomalous light oxygen of the Khitoostrov (North Karelia, Russia) were studied. It was found that atmospheric noble gas component is missing. Therefore, all previously proposed models of participation in the fluid surface ice meltwater are not valid. Proposed and justified endogenous mechanism of isotope fractionation of oxygen and other chemical elements by the mechanism of thermal diffusion. Geologically justified existence of the cascading effect for a number of the separation thermodiffusion cells, which lead to significant isotope effects. Cascading is realized due to the “fluid pump”, in which role are acting amphibolized gabbro in the contact with corundum metasomatites. It is assumed that the mechanism is not specific for the case corundum metasomatic rocks, which are a special case of manifestation of such a scenario in processes involving endogenous fluid flows.

Isotopes (¹³C and ¹⁸O) Geochemistry of Lower Triassic Montney Formation, Northeastern British Columbia, Western Canada

Oxygen isotope (δ18O) serves as paleothermometer, and provides paleotemperature for carbonates. δ18O signature was used to estimate the temperature of fractionation of dolomite and calcite in Montney Formation, empirically calculated to have precipitated, between approximately 13°C to ±33°C during Triassic time in northeastern British Columbia, Western Canada Sedimentary Basin (WCSB). Measurements of stable isotopes (δ13C and δ18O) fractionation, supported by quantitative X-ray diffraction evidence, and whole-rock geochemical characterization of the Triassic Montney Formation indicates the presence of calcite, dolomite, magnesium, carbon and other elements. Results from isotopic signature obtained from bulk calcite and bulk dolomite from this study indicates depleted δ13CPDB (-2.18‰ to -8.46‰) and depleted δ18OPDB (-3.54‰ to -16.15‰), which is interpreted in relation to oxidation of organic matter during diagenesis. Diagenetic modification of dolomitized very fine-grained, silty-sandstone of the Montney Formation may have occurred in stages of progressive oxidation and reduction reactions involving chemical elements such as Fe, which manifest in mineral form as pyrite, particularly, during early burial diagenesis. Such mineralogical changes evident in this study from petrography and SEM, includes cementation, authigenic quartz overgrowth and mineral replacement involving calcite and dolomite, which are typical of diagenesis. High concentration of chemical elements in the Montney Formation?-Ca and Mg indicates dolomitization. It is interpreted herein, that calcite may have been precipitated into the interstitial pore space of the intergranular matrix of very fine-grained silty-sandstone of the Montney Formation as cement by a complex mechanism resulting in the interlocking of grains.