In this study, biomarkers, together with stable carbon(δ13 C) and hydrogen(δD) isotopic compositions of n-alkanes have been examined in a suite of condensates collected from the East China Sea Shelf Basin(ECSSB) in ...In this study, biomarkers, together with stable carbon(δ13 C) and hydrogen(δD) isotopic compositions of n-alkanes have been examined in a suite of condensates collected from the East China Sea Shelf Basin(ECSSB) in order to delineate their source organic matter input, depositional conditions and evaluate their thermal maturity. Previously, GC-MS analyses have shown that all the condensates are formed in oxidizing environment with terrestrial plants as their main source input. No significant differences were apparent for biomarker parameters, likely due to the low biomarker content and high maturity of these condensates. Conventional GC-MS analysis however, may provides limited information on the sources and thermal maturity of complex mixtures due to insufficient component resolution. In the current study, we used comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry(GC×GC-TOFMS) to increase the chromatographic resolution. Compounds such as alkyl cyclohexanes, alkyl cyclopentanes and diamondoids, which can be difficult to identify using conventional GC-MS analysis, were successfully identified using GC×GC-TOFMS. From our analyses we propose two possibly unreported indicators, including one maturity indicator(C5--cyclohexane/C5+-cyclohexane) and one oxidation-reduction environment indicator(alkyl-cyclohexane/alkyl-cyclopentane). Multiple petroleum charging events were proposed as an explanation for the maturity indicators indexes discrepancy between methyl-phenanthrene index(MPI) and methyl-adamantane index(MDI). In addition, the stable isotopic results show that condensates from the Paleogene have significantly higher positive δ13 C values of individual n-alkanes than the Neogene samples. Based on δD values, the samples can be divided into two groups, the differences between which are likely to be attributed to different biosynthetic precursors. Variation within each group can likely be attributed to vaporization.展开更多
The carbon isotopic composition of individual light hydrocarbons generated from source rocks that had been pyrolysed in vacuum glass tube were determined by using the GC-IRMS techniques. The results indicate that abun...The carbon isotopic composition of individual light hydrocarbons generated from source rocks that had been pyrolysed in vacuum glass tube were determined by using the GC-IRMS techniques. The results indicate that abundant CO2 in the pyrolysates has a remarkable effect on the determination of CH4δ13C. Running cryogenically with an initial temperature of -40℃ can effectively eliminate the effect. In addition, it conduces to measuring the δ13C of C2+ hydrocarbons by increasing the injection volume and/or absorbing CO2 with the solution of sodium hydroxide. The above measures will help to get the carbon isotopic composition of C1-C7 components, which is of great significance for gas/source rock correlation and for study on the genesis of natural gas.展开更多
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 spectro...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.展开更多
The molecular compositions and com- pound-specific carbon isotope compositions of indi- vidual long-chain n-alkanes of atmospheric aerosols collected during two severe Asian dust episodes in Qingdao in spring of 2002 ...The molecular compositions and com- pound-specific carbon isotope compositions of indi- vidual long-chain n-alkanes of atmospheric aerosols collected during two severe Asian dust episodes in Qingdao in spring of 2002 were analyzed using gas chromatography/mass spectrometry (GC/MS) and gas chromatography/isotope ratio mass spectrometry (GC/IRMS). Typical plant wax n-alkanes (C29 and C31) had lower δ 13C values than those from anthropo- genic (engine exhaust) sources (C21―C23). The av- erage δ 13C value of plant wax n-alkane C29 in non-dust episode periods was -30.5‰ (?30.3‰― ?31.9‰), while -31.3‰ (?31.1‰―?31.5‰) in dust episode periods; for C31, it was ?31.4‰ (?31.1‰― ?33.0‰) in non-dust episode periods, and ?31.7‰ (?31.3‰―?32.6‰) in dust episode periods. Plant wax in the dust episode samples was mainly from herbaceous plants via long-range transport, while local plant wax was mainly from deciduous plants and woody plants. In North China coast, 83.3% of the plant wax in the severe dust episode samples was from C3 plants while 80.0% for the non-dust samples, indicating that plant wax transported to the north- western Pacific Ocean by airborne dust from East Asia was mainly from C3 plants. The results suggestthat the molecular and molecular-isotopic composi- tions of individual long-chain n-alkanes can, as an effective indicator, identify the terrestrial organic components in the dust from East Asia and sedi- ments in the northwest Pacific Ocean.展开更多
The carbon isotopic compositions of individual terpenoids in the heavy oils from the Karamay oilfield were determined by using the method of enrichment of terpanes with molecular sieve 13X and GC-IRMS technique. The t...The carbon isotopic compositions of individual terpenoids in the heavy oils from the Karamay oilfield were determined by using the method of enrichment of terpanes with molecular sieve 13X and GC-IRMS technique. The terpanes, selectively enriched from the biodegraded oils with molecular sieve 13X, can meet the demand of GO-IRMS analysis. The carbon isotopic compositions of the hopanoids (δ<sup>13</sup>C-31.7‰—-37.8‰) infer that their main source is probably non-methanotrophic bacteria,and that the depositional environment of source rocks is a strongly reductive, rapidly depositional, and closed-semi-closed saline lagoon.展开更多
基金sponsored by the National Science and Technology Major Project of China (Nos. 2016ZX05024-002003, 2016ZX05027-001-005)
文摘In this study, biomarkers, together with stable carbon(δ13 C) and hydrogen(δD) isotopic compositions of n-alkanes have been examined in a suite of condensates collected from the East China Sea Shelf Basin(ECSSB) in order to delineate their source organic matter input, depositional conditions and evaluate their thermal maturity. Previously, GC-MS analyses have shown that all the condensates are formed in oxidizing environment with terrestrial plants as their main source input. No significant differences were apparent for biomarker parameters, likely due to the low biomarker content and high maturity of these condensates. Conventional GC-MS analysis however, may provides limited information on the sources and thermal maturity of complex mixtures due to insufficient component resolution. In the current study, we used comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry(GC×GC-TOFMS) to increase the chromatographic resolution. Compounds such as alkyl cyclohexanes, alkyl cyclopentanes and diamondoids, which can be difficult to identify using conventional GC-MS analysis, were successfully identified using GC×GC-TOFMS. From our analyses we propose two possibly unreported indicators, including one maturity indicator(C5--cyclohexane/C5+-cyclohexane) and one oxidation-reduction environment indicator(alkyl-cyclohexane/alkyl-cyclopentane). Multiple petroleum charging events were proposed as an explanation for the maturity indicators indexes discrepancy between methyl-phenanthrene index(MPI) and methyl-adamantane index(MDI). In addition, the stable isotopic results show that condensates from the Paleogene have significantly higher positive δ13 C values of individual n-alkanes than the Neogene samples. Based on δD values, the samples can be divided into two groups, the differences between which are likely to be attributed to different biosynthetic precursors. Variation within each group can likely be attributed to vaporization.
文摘The carbon isotopic composition of individual light hydrocarbons generated from source rocks that had been pyrolysed in vacuum glass tube were determined by using the GC-IRMS techniques. The results indicate that abundant CO2 in the pyrolysates has a remarkable effect on the determination of CH4δ13C. Running cryogenically with an initial temperature of -40℃ can effectively eliminate the effect. In addition, it conduces to measuring the δ13C of C2+ hydrocarbons by increasing the injection volume and/or absorbing CO2 with the solution of sodium hydroxide. The above measures will help to get the carbon isotopic composition of C1-C7 components, which is of great significance for gas/source rock correlation and for study on the genesis of natural gas.
基金Chinese National 973 Key ResearchDevelopment Program (Grant No. 2006CB701404)Daqing Oilfield Company Limited
文摘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.
基金This work was supported by the National Natural Science Foundation of China （Grant Nos： 40276016, 90211022）.
文摘The molecular compositions and com- pound-specific carbon isotope compositions of indi- vidual long-chain n-alkanes of atmospheric aerosols collected during two severe Asian dust episodes in Qingdao in spring of 2002 were analyzed using gas chromatography/mass spectrometry (GC/MS) and gas chromatography/isotope ratio mass spectrometry (GC/IRMS). Typical plant wax n-alkanes (C29 and C31) had lower δ 13C values than those from anthropo- genic (engine exhaust) sources (C21―C23). The av- erage δ 13C value of plant wax n-alkane C29 in non-dust episode periods was -30.5‰ (?30.3‰― ?31.9‰), while -31.3‰ (?31.1‰―?31.5‰) in dust episode periods; for C31, it was ?31.4‰ (?31.1‰― ?33.0‰) in non-dust episode periods, and ?31.7‰ (?31.3‰―?32.6‰) in dust episode periods. Plant wax in the dust episode samples was mainly from herbaceous plants via long-range transport, while local plant wax was mainly from deciduous plants and woody plants. In North China coast, 83.3% of the plant wax in the severe dust episode samples was from C3 plants while 80.0% for the non-dust samples, indicating that plant wax transported to the north- western Pacific Ocean by airborne dust from East Asia was mainly from C3 plants. The results suggestthat the molecular and molecular-isotopic composi- tions of individual long-chain n-alkanes can, as an effective indicator, identify the terrestrial organic components in the dust from East Asia and sedi- ments in the northwest Pacific Ocean.
文摘The carbon isotopic compositions of individual terpenoids in the heavy oils from the Karamay oilfield were determined by using the method of enrichment of terpanes with molecular sieve 13X and GC-IRMS technique. The terpanes, selectively enriched from the biodegraded oils with molecular sieve 13X, can meet the demand of GO-IRMS analysis. The carbon isotopic compositions of the hopanoids (δ<sup>13</sup>C-31.7‰—-37.8‰) infer that their main source is probably non-methanotrophic bacteria,and that the depositional environment of source rocks is a strongly reductive, rapidly depositional, and closed-semi-closed saline lagoon.
