Molecular biomarkers are the important maturity parameters for sedimentary organic matter. They have also been widely used for determining the maturity of organic matter in ore deposits. However, during the study of o...Molecular biomarkers are the important maturity parameters for sedimentary organic matter. They have also been widely used for determining the maturity of organic matter in ore deposits. However, during the study of organic matter in the Kupferschiefer from the Lubin mine, it had been found that the biomarkers were influenced by sulfide formation. In order to probe into the degree of influence on biomarkers, seven samples collected from a Kupferschiefer section from the Lubin mine were analyzed by various geochemical methods. The results indicated that in the samples with higher copper contents, the values of biomarkers are lower than in the samples with lower copper contents. In highly mineralized samples, hydrogen donation for thermochemical sulfate reduction (TSR) occurred in alkylated phenanthrenes and naphthalenes, leading to the decrease of 12 biomarker parameters during the Kupferschiefer mineralization.展开更多
The Fankou Pb-Zn deposit is a very important and famous deposit in China. The time of Pb-Zn enrichment has been debated for a long time in this deposit. A total of seventeen samples of three sections were taken from t...The Fankou Pb-Zn deposit is a very important and famous deposit in China. The time of Pb-Zn enrichment has been debated for a long time in this deposit. A total of seventeen samples of three sections were taken from the Fankou mine for the study of mineralization time and the mechanism of ore formation. The samples were analyzed by microscope, Soxhlet-extract, GC, and GC/MS methods. The results indicated that organic bulk parameters vary with the Pb-Zn contents in different samples and clearly were influenced by ore sulfide formation. Organically geochemical parameters (MPI 1, CPI) indicate that the paleotemperatures in the Fankou deposit are lower than 80℃ in all three sections. Sulfides in the wall rocks might occur mainly during synsedimentation or early diagenesis by BSR or partly by PR, rather than by TSR at such low temperatures, this stage may be the first mineralization stage. Sulfides near the faults might be formed by TSR after sedimentation, this stage may be the second mineralization stage.展开更多
MoS2 was used as an efficient catalyst for hydropyrolysis (Hypy) of three samples of sedimentary organic matter with different maturities. Through comparison with Soxhlet extraction (SE), it was found that MoS2 ca...MoS2 was used as an efficient catalyst for hydropyrolysis (Hypy) of three samples of sedimentary organic matter with different maturities. Through comparison with Soxhlet extraction (SE), it was found that MoS2 catalytic Hypy can remarkably promote the yields of total chloroform extracts, saturates, aromatics, hopanes and steranes. In addition, the difference of biomarker parameters indicated that isomerization of covalently-bound biomarkers is much more difficult than their free counterparts. Meanwhile, the high conversion of total organic carbon (TOC) in MoS2 catalytic Hypy of organic matter proved that the presence of dispersed molybdenum sulfide accelerated the breaking of C-C bonds and the release of hydrocarbons. To address the catalytic mechanism, a series of control experiments based on free Hypy and catalytic Hypy were conducted. The results showed that the calculated atomic ratio of carbon conversion/hydrogen conversion for catalytic Hypy was much larger than the presumed value of 1/2, indicating that intensive hydrogenation took place and significantly influenced the distribution of liquid products. Analysis of stable hydrogen isotope data, infrared spectra and m/z 83 ion chromatograph of the saturate fraction further confirmed this hypothesis. The difference of S content changing (AS) between catalyst-free Hypy and catalytic Hypy, and the thermal characteristics of the catalyst, indicated that active H2S was definitely generated and it probably initiated free radical reactions in the early stage of hydropyrolysis of organic matter.展开更多
The contents of polycyclic aromatic sulfur compounds (PASCs) in the Kupferschiefer varied from sample to sample. Twenty PASCs were determined in the Kupferschiefer from Poland and Germany. Gold enrichment was only obs...The contents of polycyclic aromatic sulfur compounds (PASCs) in the Kupferschiefer varied from sample to sample. Twenty PASCs were determined in the Kupferschiefer from Poland and Germany. Gold enrichment was only observed in samples with higher PASC contents. At the same time, all the samples with gold enrichment originated from areas close to the redox boundary (the front section of Rote Fule) that was formed by oxidizing brines in contact with the reducing Kupferschiefer. It is proposed that the gold-bearing solutions encountered PASCs in the Kupferschiefer. PASCs could easily displace chloride ions from aurous chloride complexes to form stable gold S-chelates. Subsequent oxidation of these gold organic compounds could destroy the organic components and lead to the formation of metallic gold.展开更多
A suit of oil shales, predominated by black argillaceous silicalite and finely laminated black-brown shale, has been discovered in a set of carbonaceous-siliceous mudstone formations (350 m in thickness) in the third ...A suit of oil shales, predominated by black argillaceous silicalite and finely laminated black-brown shale, has been discovered in a set of carbonaceous-siliceous mudstone formations (350 m in thickness) in the third member of Xiamaling Formation of the Upper Proterozoic Qingbaikou Series (900―873 MaBP), Xiahuayuan, Hebei Province, China. The oil shale, combustible with strong bitumen odour, has su- per-high TOC contents ranging from 21.4% to 22.9%, bitumen “A” contents from 0.58% to 0.88% and oil length from 5.29% to 10.57%. The ultrathin section observation of the shale and the identification of its kerogen demonstrate that its hydrocarbon-generative parent material is mainly benthonic Rhodophyta whose specific tetrasporangia are legible and abundant. It is rarely reported in the literature that such a hydrocarbon-generative parent material, composed mainly of Rhodophyta and with extraordinarily high contents of TOC and bitumen “A”, developed into a set of high-quality source rocks. The extracts of the oil shale are characteristic of richness in 17α(H)-diahopanes and n-alkyl tricyclic terpenoids but low in steranes. Such a biomarker feature is obviously different from that of the extracts from other Proterozoic marine carbonate source rocks of the studied area. Since the biological constitution of this oil shale is rather simple, it is clear that these biomarkers most likely represent to certain extent the specific mo- lecular constitutions of the benthonic Rhodophyta identified in the ultrathin sections of the samples. Studies on its lithologic association and depositional sequences suggest that this suit of the carbona- ceous-siliceous mudstone formation, which contains oil shales, was probably developed in an under- compensation deep-bay environment when a maximum transgression occurred during the formation of the third member of Xiamaling Formation. The high concentration of SiO2 in this organic-rich rock and the positive correlation between TOC and some trace elements such as P, Cu, Ni, W and Mo indicate that this suit of rocks was affected by activities of bottom thermal currents as deposited.展开更多
文摘Molecular biomarkers are the important maturity parameters for sedimentary organic matter. They have also been widely used for determining the maturity of organic matter in ore deposits. However, during the study of organic matter in the Kupferschiefer from the Lubin mine, it had been found that the biomarkers were influenced by sulfide formation. In order to probe into the degree of influence on biomarkers, seven samples collected from a Kupferschiefer section from the Lubin mine were analyzed by various geochemical methods. The results indicated that in the samples with higher copper contents, the values of biomarkers are lower than in the samples with lower copper contents. In highly mineralized samples, hydrogen donation for thermochemical sulfate reduction (TSR) occurred in alkylated phenanthrenes and naphthalenes, leading to the decrease of 12 biomarker parameters during the Kupferschiefer mineralization.
基金support to this study by the NSFC Projects (Nos.40173004 and 40773040) is gratefully acknowledged
文摘The Fankou Pb-Zn deposit is a very important and famous deposit in China. The time of Pb-Zn enrichment has been debated for a long time in this deposit. A total of seventeen samples of three sections were taken from the Fankou mine for the study of mineralization time and the mechanism of ore formation. The samples were analyzed by microscope, Soxhlet-extract, GC, and GC/MS methods. The results indicated that organic bulk parameters vary with the Pb-Zn contents in different samples and clearly were influenced by ore sulfide formation. Organically geochemical parameters (MPI 1, CPI) indicate that the paleotemperatures in the Fankou deposit are lower than 80℃ in all three sections. Sulfides in the wall rocks might occur mainly during synsedimentation or early diagenesis by BSR or partly by PR, rather than by TSR at such low temperatures, this stage may be the first mineralization stage. Sulfides near the faults might be formed by TSR after sedimentation, this stage may be the second mineralization stage.
基金supported by the Science and Technology Major roject (2008A-0600) from CNPC
文摘MoS2 was used as an efficient catalyst for hydropyrolysis (Hypy) of three samples of sedimentary organic matter with different maturities. Through comparison with Soxhlet extraction (SE), it was found that MoS2 catalytic Hypy can remarkably promote the yields of total chloroform extracts, saturates, aromatics, hopanes and steranes. In addition, the difference of biomarker parameters indicated that isomerization of covalently-bound biomarkers is much more difficult than their free counterparts. Meanwhile, the high conversion of total organic carbon (TOC) in MoS2 catalytic Hypy of organic matter proved that the presence of dispersed molybdenum sulfide accelerated the breaking of C-C bonds and the release of hydrocarbons. To address the catalytic mechanism, a series of control experiments based on free Hypy and catalytic Hypy were conducted. The results showed that the calculated atomic ratio of carbon conversion/hydrogen conversion for catalytic Hypy was much larger than the presumed value of 1/2, indicating that intensive hydrogenation took place and significantly influenced the distribution of liquid products. Analysis of stable hydrogen isotope data, infrared spectra and m/z 83 ion chromatograph of the saturate fraction further confirmed this hypothesis. The difference of S content changing (AS) between catalyst-free Hypy and catalytic Hypy, and the thermal characteristics of the catalyst, indicated that active H2S was definitely generated and it probably initiated free radical reactions in the early stage of hydropyrolysis of organic matter.
文摘The contents of polycyclic aromatic sulfur compounds (PASCs) in the Kupferschiefer varied from sample to sample. Twenty PASCs were determined in the Kupferschiefer from Poland and Germany. Gold enrichment was only observed in samples with higher PASC contents. At the same time, all the samples with gold enrichment originated from areas close to the redox boundary (the front section of Rote Fule) that was formed by oxidizing brines in contact with the reducing Kupferschiefer. It is proposed that the gold-bearing solutions encountered PASCs in the Kupferschiefer. PASCs could easily displace chloride ions from aurous chloride complexes to form stable gold S-chelates. Subsequent oxidation of these gold organic compounds could destroy the organic components and lead to the formation of metallic gold.
基金Supported by the China State 973 Scientific Program Contribution (Grant No. G19990433)
文摘A suit of oil shales, predominated by black argillaceous silicalite and finely laminated black-brown shale, has been discovered in a set of carbonaceous-siliceous mudstone formations (350 m in thickness) in the third member of Xiamaling Formation of the Upper Proterozoic Qingbaikou Series (900―873 MaBP), Xiahuayuan, Hebei Province, China. The oil shale, combustible with strong bitumen odour, has su- per-high TOC contents ranging from 21.4% to 22.9%, bitumen “A” contents from 0.58% to 0.88% and oil length from 5.29% to 10.57%. The ultrathin section observation of the shale and the identification of its kerogen demonstrate that its hydrocarbon-generative parent material is mainly benthonic Rhodophyta whose specific tetrasporangia are legible and abundant. It is rarely reported in the literature that such a hydrocarbon-generative parent material, composed mainly of Rhodophyta and with extraordinarily high contents of TOC and bitumen “A”, developed into a set of high-quality source rocks. The extracts of the oil shale are characteristic of richness in 17α(H)-diahopanes and n-alkyl tricyclic terpenoids but low in steranes. Such a biomarker feature is obviously different from that of the extracts from other Proterozoic marine carbonate source rocks of the studied area. Since the biological constitution of this oil shale is rather simple, it is clear that these biomarkers most likely represent to certain extent the specific mo- lecular constitutions of the benthonic Rhodophyta identified in the ultrathin sections of the samples. Studies on its lithologic association and depositional sequences suggest that this suit of the carbona- ceous-siliceous mudstone formation, which contains oil shales, was probably developed in an under- compensation deep-bay environment when a maximum transgression occurred during the formation of the third member of Xiamaling Formation. The high concentration of SiO2 in this organic-rich rock and the positive correlation between TOC and some trace elements such as P, Cu, Ni, W and Mo indicate that this suit of rocks was affected by activities of bottom thermal currents as deposited.