The Kalatongke Cu-Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt （CAOB）. The chemical and carbo...The Kalatongke Cu-Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt （CAOB）. The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200-400°C, 400-900°C and 900-1200°C. The released volatiles from silicate mineral separates at 400-900°C and 900-1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O （av. ~92 mol%） with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values （from -20.86‰ to -12.85‰） of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantlederived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200-400°C are dominated by H2O with minor CO2, N2＋CO and SO2, with δ13CCO2 values （-25.66‰ to -22.98‰） within the crustal ranges, and are considered to be related to secondary tectonic-hydrothermal activities.展开更多
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 fro...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) for thermogenic gases. Controlled by the kinetic isotope fractionation, both microbial and thermogenic gases have δ 13C and δ D values characterized by normal distribution, i.e. δ 13C1< δ 13C2< δ 13C3< δ 13C4 and δ DCH4< δ DC2H6< δ DC3H8<δ DC4H10, and by a positive correlation between the δ 13C and δ D values. Simple carbonbearing molecules (CH4, CO and CO2) can form abiogenic alkane gases via polymerization in the abiological chemical process in nature, with δ 13C1 heavier than -30‰. Moreover, controlled by the kinetic isotope fractionation, abiogenic alkane gases are characterized by a reverse distribution of δ 13C values and a normal trend of δ D values, namely δ 13C1> δ 13C2> δ 13C3> δ 13C4 and δ DCH4<δ DC2H6< δ DC3H8< δ DC4H10. The δ 13C values and δ D values are negatively correlated. Natural gases from 26 commercial gas wells distributed in the Xujiaweizi and Yingshan-Miaotaizi faulted depressions in the Songliao Basin, China, show δ13C1 values ranging from -30.5‰ to -16.7‰ with a very narrow δ D range between -203‰―-196‰. These gases are characterized by a reverse distribution of δ 13C values but a normal distribution of δ D values, and a negative correlation between their δ 13C and δ D values, indicating an abiological origin. The present study has revealed that abiogenic hydrocarbons not only exist in nature but also can make significant contribution to commercial gas reserviors. It is estimated that the reserve volume of alkane gases with abiogenic characteristics in these 26 gas wells in the Songliao Basin is over 500×108 m3. The prospecting practice in the Songliao Basin has demonstrated that abiogenic alkane gases are of a promising resource, and it provides an example for the investigation of and search for abiogenic commercial natural gases worldwide.展开更多
The mechanism of hydrogen sulfide(H_2S) generation plays a key role in the exploration and development of marine high-sulfur natural gas, of which the major targets are the composition and isotope characteristics of s...The mechanism of hydrogen sulfide(H_2S) generation plays a key role in the exploration and development of marine high-sulfur natural gas, of which the major targets are the composition and isotope characteristics of sulfur-containing compounds.Hydrocarbon source rocks, reservoir rocks, natural gases and water-soluble gases from Sichuan Basin have been analyzed with an online method for the content of H_2S and isotopic composition of different sulfur-containing compounds. The results of comparative analysis show that the sulfur-containing compounds in the source rocks are mainly formed by bacterial sulfate reduction(BSR), and the sulfur compounds in natural gas, water and reservoir are mainly formed by thermal sulfate reduction(TSR). Moreover, it has been shown that the isotopically reversion for methane and ethane in high sulfur content gas is caused by TSR. The sulfur isotopic composition of H_2S in natural gas is inherited from the gypsum or brine of the same or adjacent layer,indicating that the generation and accumulation of H_2S have the characteristics of either a self-generated source or a near-source.展开更多
基金financially supported by NSF of China(Grant 41072056, 40772058, 91014003, 40534020 and40772062)Key Projects of China Geological Survey(1212011121092)MOE (311010)
文摘The Kalatongke Cu-Ni sulfide deposits located in the East Junggar terrane, northern Xinjiang, western China are the largest magmatic sulfide deposits in the Central Asian Orogenic Belt （CAOB）. The chemical and carbon isotopic compositions of the volatiles trapped in olivine, pyroxene and sulfide mineral separates were analyzed by vacuum stepwise-heating mass spectrometry. The results show that the released volatiles are concentrated at three temperature intervals of 200-400°C, 400-900°C and 900-1200°C. The released volatiles from silicate mineral separates at 400-900°C and 900-1200°C have similar chemical and carbon isotopic compositions, which are mainly composed of H2O （av. ~92 mol%） with minor H2, CO2, H2S and SO2, and they are likely associated with the ore-forming magmatic volatiles. Light δ13CCO2 values （from -20.86‰ to -12.85‰） of pyroxene indicate crustal contamination occurred prior to or synchronous with pyroxene crystallization of mantlederived ore-forming magma. The elevated contents of H2 and H2O in the olivine and pyroxene suggest a deep mantle-originated ore-forming volatile mixed with aqueous volatiles from recycled subducted slab. High contents of CO2 in the ore-forming magma volatiles led to an increase in oxygen fugacity, and thereby reduced the solubility of sulfur in the magma, then triggered sulfur saturation followed by sulfide melt segregation; CO2 contents correlated with Cu contents in the whole rocks suggest that a supercritical state of CO2 in the ore-forming magma system under high temperature and pressure conditions might play a key role in the assemblage of huge Cu and Ni elements. The volatiles released from constituent minerals of intrusion 1# have more CO2 and SO2 oxidized gases, higher CO2/CH4 and SO2/H2S ratios and lighter δ13CCO2 than those of intrusions 2# and 3#. This combination suggests that the higher oxidation state of the volatiles in intrusion 1# than intrusions 2# and 3#, which could be one of key ore-forming factors for large amounts of ores and high contents of Cu and Ni in intrusion 1#. The volatiles released at 200-400°C are dominated by H2O with minor CO2, N2＋CO and SO2, with δ13CCO2 values （-25.66‰ to -22.98‰） within the crustal ranges, and are considered to be related to secondary tectonic-hydrothermal activities.
基金Supported by National Natural Science Foundation of China (Grant Nos. 49233060, 40572087)Key Technologies R & D Programme (Grant Nos.96110010602, 2008ZX05008)the Foundation of Chinese Academy of Sciences (Grant No. K2000315)
文摘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) for thermogenic gases. Controlled by the kinetic isotope fractionation, both microbial and thermogenic gases have δ 13C and δ D values characterized by normal distribution, i.e. δ 13C1< δ 13C2< δ 13C3< δ 13C4 and δ DCH4< δ DC2H6< δ DC3H8<δ DC4H10, and by a positive correlation between the δ 13C and δ D values. Simple carbonbearing molecules (CH4, CO and CO2) can form abiogenic alkane gases via polymerization in the abiological chemical process in nature, with δ 13C1 heavier than -30‰. Moreover, controlled by the kinetic isotope fractionation, abiogenic alkane gases are characterized by a reverse distribution of δ 13C values and a normal trend of δ D values, namely δ 13C1> δ 13C2> δ 13C3> δ 13C4 and δ DCH4<δ DC2H6< δ DC3H8< δ DC4H10. The δ 13C values and δ D values are negatively correlated. Natural gases from 26 commercial gas wells distributed in the Xujiaweizi and Yingshan-Miaotaizi faulted depressions in the Songliao Basin, China, show δ13C1 values ranging from -30.5‰ to -16.7‰ with a very narrow δ D range between -203‰―-196‰. These gases are characterized by a reverse distribution of δ 13C values but a normal distribution of δ D values, and a negative correlation between their δ 13C and δ D values, indicating an abiological origin. The present study has revealed that abiogenic hydrocarbons not only exist in nature but also can make significant contribution to commercial gas reserviors. It is estimated that the reserve volume of alkane gases with abiogenic characteristics in these 26 gas wells in the Songliao Basin is over 500×108 m3. The prospecting practice in the Songliao Basin has demonstrated that abiogenic alkane gases are of a promising resource, and it provides an example for the investigation of and search for abiogenic commercial natural gases worldwide.
文摘The mechanism of hydrogen sulfide(H_2S) generation plays a key role in the exploration and development of marine high-sulfur natural gas, of which the major targets are the composition and isotope characteristics of sulfur-containing compounds.Hydrocarbon source rocks, reservoir rocks, natural gases and water-soluble gases from Sichuan Basin have been analyzed with an online method for the content of H_2S and isotopic composition of different sulfur-containing compounds. The results of comparative analysis show that the sulfur-containing compounds in the source rocks are mainly formed by bacterial sulfate reduction(BSR), and the sulfur compounds in natural gas, water and reservoir are mainly formed by thermal sulfate reduction(TSR). Moreover, it has been shown that the isotopically reversion for methane and ethane in high sulfur content gas is caused by TSR. The sulfur isotopic composition of H_2S in natural gas is inherited from the gypsum or brine of the same or adjacent layer,indicating that the generation and accumulation of H_2S have the characteristics of either a self-generated source or a near-source.
