Molecular characterization of sulfur compounds in some special sulfur-rich Chinese crude oils by FT-ICR MS

Routine GC/MS analysis may apply to the volatilized Low-Molecular-Weight compounds in saturate and aromatic hydrocarbon fractions;thus,relative studies using this technique inevitably bring about some limitations on distribution of miscellaneous sulfur atom.In this article,Fourier Transform Ion Cyclotron Resonance Mass Spectrometry(FT-ICR MS)with high resolution is employed to investigate the distribution of organic sulfur compounds(OSCs)in the crude oil typically derived from the Eogene carbonate-evaporite sediments with further chemical compositional characterization in molecular level by miscellaneous atomic type,carbon number,and double bond equivalent(DBE).A variety of miscellaneous atomic types with S1,S2,S3,OS,OS2,O2S,O2S2,NS,and NOS etc.(S1 means those OSCs with one sulfur atom in a molecule)were identified in OSCs in these oil samples.High levels of alkyl thioether series compounds with one ring structure were presented mainly in the crude oil in the Jianghan Basin whereas high amounts of benzothiophene,dibenzothiophene etc.compounds with higher values in DBE and carbon number range occurred in the sulfur-rich heavy oil in the Jinxian Sag.Although carbonate-evaporite sediments deposited in the saline lacustrine facies in the Eogene basin both occurred in the Jinxian Sag and Jianghan Basin,obviously,they possess different chemical diagenetic pathway of sulfur under various microbial reactions,leading to diverse distributional characteristics on biomarkers,OSCs,and even different hydrocarbon generation mechanism of immature crude oil.     

Identification and formation of sulfur-containing steroids in sulfur-rich heavy oils in the Jinxian Sag, Bohai Bay Basin, North China

High abundant sulfur-containing steroids were identified and detected in saturate hydrocarbon fractions of heavy oil with a high sulfur content in the Jinxian Sag,Bohai Bay Basin,North China.These sulfur-containing steroids were structurally merged into the D-ring of steroid nucleus with thiophene ring and/or combined into the C-22 in the side-chain.Based on the previous reports of sulfur-containing steroids with methylthio-steroids and intra-molecular form,four formation mechanisms of sulfur-containing steroids and diagenetic pathway of steroids under S-rich conditions were proposed in this paper according to the double bond positions in the sterene compounds.Hydrogenation and sulfurization both occurred in the diagenetic processes of olefinic bond in the side-chain of steroids:abiogenic chemical hydrogenation of H2S and HS-leads to the formation of regular steranes;a successful sulfurization process leads to the formation of the side-chain sulfur-containing steroids whereas unsuccessful cyclization and/or sulfurization result in the generation of short-chain steranes.This kind of mechanism of hydrogenation/sulfurization of side-chain olefinic bond provides a potential genesis clue for the occurrence of high abundance of short-chain steranes(higher than the common regular steroids,phytane and n-alkanes)in S-rich heavy oils and source rocks in the Jinxian Sag,Bohai Bay Basin,North China.     

Potential petroleum sources and exploration directions around the Manjar Sag in the Tarim Basin

Since the discovery of the Tahe oilfield, it has been controversial on whether the main source rock is in the Cambrian or Middle-Upper Ordovician strata. In this paper, it is assumed that the crude oil from the Wells YM 2 and TD 2 was derived from the Middle-Upper Ordovician and Cambrian source rocks, respectively. We analyzed the biomarkers of the crude oil, asphalt-adsorbed hydrocarbon and saturated hydrocarbon in bitumen inclusions from the Lunnan and Hade areas in the North Uplift of the Tarim Basin. Results show that the ratios of tricyclic terpane C₂₁/C₂₃ in the crude oil, asphalt-adsorbed hydrocarbon and saturated hydrocarbon in bitumen inclusions are less than 1.0, indicating that they might be from Upper Ordovician source rocks; the ratios of C₂₈/(C₂₇+C₂₈+C₂₉) steranes in the saturated hydrocarbon from reservoir bitumen and bitumen inclusions are higher than 25, suggesting that they might come from the Cambrian source rocks, however, the ratios of C₂₈/(C₂₇+C₂₈+C₂₉) steranes in oil from the North Uplift are less than 25, suggesting that they might be sourced from the Upper Ordovician source rocks. These findings demonstrate that the sources of crude oil in the Tarim Basin are complicated. The chemical composition and carbon isotopes of Ordovician reservoired oil in the Tarim Basin indicated that the crude oil in the North Uplift (including the Tahe oilfield) and Tazhong Depression was within mixture areas of crude oil from the Wells YM 2 and TD 2 as the end members of the Cambrian and Middle-Upper Ordovician sourced oils, respectively. This observation suggests that the crude oil in the Ordovician strata is a mixture of oils from the Cambrian and Ordovician source rocks, with increasing contribution from the Cambrian source rocks from the southern slope of the North Uplift to northern slope of the Central Uplift of the Tarim Basin. Considering the lithology and sedimentary facies data, the spatial distribution of the Cambrian, Middle-Lower Ordovician and Upper Ordovician source rocks was reconstructed on the basis of seismic reflection characteristics, and high-quality source rocks were revealed to be mainly located in the slope belt of the basin and were longitudinally developed over the maximum flooding surface during the progressive-regressive cycle. Affected by the transformation of the tectonic framework in the basin, the overlays of source rocks in different regions are different and the distribution of oil and gas was determined by the initial basin sedimentary structure and later reformation process. The northern slope of the Central Uplift-Shuntuo-Gucheng areas would be a recent important target for oil and gas exploration, since they have been near the slope area for a long time.     

Magnetic and mineralogical characteristics of hydrocarbon microseepage above oil/gas reservoirs of Tuoku region, northern Tarim Basin, China

The Tuoku region in northern Tarim Basin of China is a key area for studying oil/gas reservoir rocks. The magnetic and mineralogical parameters of well cuttings from two wells, well S₇, situated on oil/gas field, and well S₆, at an oil/water interface, were measured. The two wells are located in the same structure with similar strata and types of lithology, but well S₆ is a showing well of oil and gas 5 km northwest of well S₇. The purpose of this paper is to evaluate the possibility and distribution of secondary magnetic alteration that may have occurred due to hydrocarbon migration above an oil/gas accumulation. It is concluded that the magnetism of well cuttings from major strata in well S₇, including source rocks, oil reservoir rocks and cap rocks, and in Quaternary (Q) soil is higher than that from well S₆. The Cambrian oil-bearing strata and cap rocks have even higher magnetism in well S₇. The shape and parameters of magnetic hysteresis loops indicate that soft (H _c<20 mT,H _s<0.3 T) ferrimagnetic components dominate the magnetic carriers within the strongly magnetic strata of well S₇, whereas a mixed paramagnetic and ferrimagnetic distribution occurs in well S₆ (for example, low coecivityH _c and nonsaturating magnetized character). Analysis of heavy minerals shows that the contents of iron oxide (magnetite, maghemite and hematite) in well S₇ are often higher than those in well S₆. The magnetite content in samples of cuttings from Cambrian rocks can reach 9.7% in oil-bearing strata in well S₇, and in strata Ekm and N₁j are 1.215% and1.498%, respectively. Typical spherical magnetite grains are found within the main source rocks and the soils in well S₇. By analysis of surface microtexture and of trace element contents, we infer that the spherical magnetite is composed of aggregates of ultrafine particles that are probably authigenic magnetite formed in a hydrocarbon halo background. Project supported by the National Natural Science Foundation of China and the Geological Industry Foundation of China (Grant No. 49374216) and Foundation of the State Key Laboratory of Oil/Gas Reservoir Geology and Exploitation of China (Grant No. 9608).     

Hydrocarbon source systems and formation of gas fields in Sichuan Basin

The formation of large and middle gas fields in Sichuan Basin is investigated based on source wntrolling theory and hydrocarbon source systems. It is indicated that Є₁, S_l, P₁, P₂ and T₃ are the main source beds and Є₁/Z₂ d, C₂ h/S₁, P₁/P₂, P₂ ch/P₂, T_1,2/P,T3 x /T3 x are important hydrocarbon source systems in the basin. All these source systems are the prospective formations and exploration spaces of large and middle gas fields. It is also emphasized that hydrocarbon generation intensity is the most important geochemical factor to estimate large and middle gas fields. Project supported by the “85–102” Chinese National Key Science and Technology Project.     

Cracking conditions of crude oil under different geological environments

There are mainly 3 kinds of existing states of oil generating from source rocks, that is, dispersive liquid hydrocarbon inside of source rock, dispersive liquid hydrocarbon outside of source rock and concentrated liquid hydrocarbon outside of source rock. Because of the differences in thermal history and medium conditions around, and the interaction of organic and inorganic matter, the liquid hydrocarbon with 3 kinds of existing state has different cracking conditions. The gas generation dynamics experiments of crude oil matching different mediums indicate that the distribution of activation energy of methane changes a lot according to medium difference. The carbonate has a main influence on oil cracking conditions and can largely reduce its activation energy, which reflects the lower cracking temperature of crude oil. The mudstone takes a second place and the sandstone is the smallest. The catalytic cracking function to the oil of the carbonate, of the mudstone and of the sandstone changes weaken in turn. The corresponding R _o values of main gas generation period in different mediums are as follows: 1.5%–3.8% with pure crude oil, 1.2%–3.2% with dispersive crude oil in carbonate, 1.3%～3.4% with dispersive crude oil in mudstone and 1.4%–3.6% with dispersive crude oil in sandstone. The influence of pressure to crude oil cracking is relatively complicated. In the low heating speed condition, pressure restrains the oil cracking and gas generation, but in the high heating speed condition, pressure has an indistinctive influence to the oil cracking and gas generation. Pressure also makes a different effort in different evolvement stage. Taking the middle and lower Cambrian source rocks in the Tarim Basin as an example, primary oil generating quantity is 2232.24×10⁸t, residual oil and oil cracking gas quantity is 806.21×10⁸t and 106.95×10¹²m³ respectively.     

Kinetics of hydrocarbon generation for Well Yingnan 2 gas reservoir,Tarim Basin,China

Well Yingnan 2, an important exploratory well in the east of Tarim Basin, yields high commercial oil and gas flow in Jurassic. Natural gas components and carbon isotopic composition indicate that it belongs to sapropel type gas. Because this region presents many suits of hydrocarbon source rocks, there are some controversies that natural gases were generated from kerogen gas or crude oil cracking gas at present. By using the kinetics of hydrocarbon generation and carbon isotope, natural gas of Well Yingnan 2 is composed mainly of crude oil cracking gas, about 72%, it is generated from secondary kerogen gas of Cambrian-Lower Ordovician source rock and crude oil cracking gas of Mid-Upper Ordovician oil reservoir. The main oil and gas filling time is 65 Ma later in the Jurassic gas reservoir of Well Yingnan 2, so the gas reservoir belongs to late accumulation and continuous filling type.

     

Long-term effects of crude oil on microbial processes in subarctic marine sediments: Studies on sediments amended with organic nutrients

Subarctic marine sediments amended with various organic compounds were exposed to fresh Cook Inlet crude oil at a concentration of 50 ppt for either 6 or 8 months. After the sediments were initially treated, they were returned to the approximate location where they were collected and left to be exposed to natural environmental conditions until they were retrieved for analysis. As a result of crude oil treatment, the activities of the enzymes that hydrolyse structural polysaccharides were reduced and the activities of the enzymes that hydrolyse storage polysaccharides were stimulated. In addition to these changes, we observed changes in phosphatase activity, nitrogen fixation rates, potential denitrification rates, methane concentrations, CO₂ production rates, and the glucose uptake and mineralization rates. The effect of the crude oil perturbation was different depending on the organic compound used in the amended sediments. Many of these differences could be explained by the effect of crude oil on the hydrolases which were responsible for degrading the compound in question. The results of this study suggest the effect of crude oil on microbial processes may be affected by the type of organic material present in the impacted marine sediment. This study also illustrates the value of measuring hydrolase activity in studies designed to determine the effects of this or any other pollutant on microbial processes in marine sediments.     

某些油气田地表土壤的磁性与烃运移相互关系研究

根据鄂尔多斯盆地靖边气田上方的ＭＩ０２线、江苏储家楼油田与江汉盆地花园油田地表十字剖面土壤磁性的测量结果，研究地表是否存在与深部油气藏中烃类垂向运移相关磁性蚀变带的可能性及其分布形式．结果表明，ＭＩ０２线样品显示了明显的高磁性异常特征，并与酸解烃之间呈很强的正相关．磁滞回线形态与参量显示出明显的亚铁磁性特征．电子探针分析结果表明，样品中主要磁性矿物（磁铁矿）中高温杂质元素含量很低．江汉盆地花园油田十字剖面磁滞回线参量（饱和磁化强度Ｊｓ与饱和等温剩磁Ｊｒ）的高异常位于油田周边，油田顶部土壤呈典型顺磁性特征．储家楼油田地表土壤的高磁性异常主要位于油田上方，它们均与盖层中的断裂构造对应，储家楼油田的高磁性样品中发现的典型球粒状磁铁矿为次生低温磁铁矿，它与烃运移之间存在成因关系．     

Hydrocarbon gases (C1–C5) and organic matter in bottom sediments of the Ivankovo Reservoir on the Volga River

The results of studying the composition of hydrocarbon gases (C₁–C₅) and organic matter in bottom sediments of the Ivankovo Reservoir in 1995, 2004, and 2005 are given. The methods used in the study include vapor-phase gas chromatography, instrumental pyrolysis gas chromatography, and mass-spectrometry for determining organic carbon δ ¹³C_org. The gas field of bottom sediments in different regions of the reservoir varies widely in terms of gas saturation and the spectrum of hydrocarbon gases. This suggests the heterogeneous composition of organic matter in the sediments and different conditions of its input and transformation processes. The gases were found to contain saturated hydrocarbons from methane to pentane C₁–C₅, including isomers i-C₄ and i-C₅ and unsaturated compounds C₂–C₄. A correlation was found to exist between methane distribution and the distribution of its more high-molecular homologues, which confirms their genetic relationship in bottom sediments. The obtained results show an increase in the rate of microbiological processes and organic matter transformation for most regions in the Ivankovo Reservoir. The only exceptions are the zones of Moshkovichskii Bay and the sections at Gorodnya and Konakovo, where technogenic organic matter is being accumulated. The high information value of hydrocarbon gases as biogeochemical markers of the sources of organic matter and the rates of its transformation is demonstrated. The isotopic composition of organic-matter carbon in the bottom sediments of the Ivankovo Reservoir δ ¹³C varies from ?26.21 to ?30.86‰.     

Carbon isotopic compositions of 1,2,3,4-tetramethylbenzene in marine oil asphaltenes from the Tarim Basin: Evidence for the source formed in a strongly reducing environment

Although 1-alkyl-2,3,6-trimethylbenzenes and a high relative amount of 1,2,3,4-tetramethylbenzene have been detected in marine oils and oil asphaltenes from Tabei uplift in the Tarim Basin, their bio-logical sources are not determined. This paper deals with the molecular characteristics of typical ma-rine oil asphaltenes from Tabei and Tazhong uplift in the Tarim Basin and the stable carbon isotopic signatures of individual compounds in the pyrolysates of these asphaltenes using flash pyrolysis-gas chromatograph-mass spectrometer (PY-GC-MS) and gas chromatograph-stable isotope ratio mass spectrometer (GC-C-IRMS), respectively. Relatively abundant 1,2,3,4-tetramethylbenzene is detected in the pyrolysates of these marine oil asphaltenes from the Tarim Basin. δ 13C values of 1,2,3,4-tetrame-thylbenzene in the pyrolysates of oil asphaltenes vary from-19.6‰ to-24.0‰, while those of n-alkanes in the pyrolysates show a range from-33.2‰ to-35.1‰. The 1,2,3,4-tetramethylbenzene in the pyro-lysates of oil asphaltenes proves to be significantly enriched in 13C relative to n-alkanes in the pyro-lysates and oil asphaltenes by 10.8‰―15.2‰ and 8.4‰―13.4‰, respectively. This result indicates a contribution from photosynthetic green sulfur bacteria Chlorobiaceae to relatively abundant 1,2,3,4-tetramethylbenzene in marine oil asphaltenes from the Tarim Basin. Hence, it can be speculated that the source of most marine oil asphaltenes from the Tarim Basin was formed in a strongly reducing water body enriched in H2S under euxinic conditions.     

Geochemical characteristics and accumulation of marine oil and gas around Halahatang depression,Tarim Basin,China

There exists a petroleum system rich of oil and gas around Halahatang depression, where the oil and gas possess obvious local distinctions of properties in different parts. The research proved that the discovered crude oil and natural gas in the region derived mainly from O₂₊₃ source rock, and the differences of its properties were controlled by the oil and gas filling intensity. The comprehensive study result shows the oil and gas reservoirs of the region mainly underwent three important accumulation phases: late Caledonian-Early Hercynian epoch, late Hercynian epoch, and Yanshan-Himalayan epoch. In the first phase, the oil and gas derived mostly from Cambrian source rock, which formed the primary ancient oil reservoirs, then suffered strong degradation and remained a great quantity of pyrobitumen in the high position of Tabei uplift in the present. In the second phase, the O₂₊₃ source rock of Manjia’er depression started its generation of hydrocarbon, which accumulated in the high position of Tabei up-lift afterwards, and then biodegradated to heavy oil in the late Hercynian epoch. In the last phase, the O₂₊₃ source rock of southern Halahatang depression and margin of Manjia’er depression started its peak of generating liquid hydrocarbon, which mostly accumulated in the trap formed before the Indo-China and Yanshan epoch, and in somewhere the heavy oil suffered dilutions in various degrees or serious gas invading, to lead to obvious crude oil divergence.

     

Classification and origin of natural gases from Lishui Sag,the East China Sea Basin

Natural gases discovered up to now in Lishui Sag, the East China Sea Basin, differ greatly in gaseous compositions, of which hydrocarbon gases amount to 2%–94% while non-hydrocarbon gases are dominated by CO₂. Their hydrocarbon gases, without exception, contain less than 90% of methane and over 10% of C₂ ⁺ heavier hydrocarbons, indicating a wet gas. Carbon isotopic analyses on these hydrocarbon gases showed that δ ¹³C₁, δ ¹³C₂ and δ ¹³C₃ are basically lighter than ?44‰, ?29‰ and ?26‰, respectively. The difference in carbon isotopic values between methane and ethane is great, suggesting a biogenic oil-type gas produced by the mixed organic matter at peak generation. δ ¹³ \(C_{CO_2 } \) values of nonhydrocarbon gases are all heavier than ?10‰, indicating a typical abiogenic gas. The simulation experiment on hydrocarbon generation of organic matter in a closed gold-tube system showed that the proportion of methane in natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit is obviously higher than that in natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit, consequently the proportion of heavier hydrocarbons of the former is remarkably lower than that of the latter. Moreover, δ ¹³C₁ values of natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit are about 5‰ heavier than those of natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit while δ ¹³C₂ and δ ¹³C₃ values of the former are over 9‰ heavier than those of the latter. Currently the LS36-1 oil-gas pool is the only commercial oil-gas reservoir in Lishui Sag, where carbon isotopic compositions of various hydrocarbon components differ greatly from those of natural gases produced by the Lingfeng Formation organic matter but are very similar to those of natural gases derived from the Yueguifeng Formation organic matter, therefore, natural gases in the LS36-1 oil-gas pool are mainly derived from the Yueguifeng Formation lacustrine source rock rather than the Lingfeng Formation marine or Mingyuefeng Formation coal-measures source rocks.     

Classification and origin of natural gases from Lishui Sag,the East China Sea Basin

Natural gases discovered up to now in Lishui Sag, the East China Sea Basin, differ greatly in gaseous compositions, of which hydrocarbon gases amount to 2%–94% while non-hydrocarbon gases are dominated by CO₂. Their hydrocarbon gases, without exception, contain less than 90% of methane and over 10% of C₂ ⁺ heavier hydrocarbons, indicating a wet gas. Carbon isotopic analyses on these hydrocarbon gases showed that δ ¹³C₁, δ ¹³C₂ and δ ¹³C₃ are basically lighter than −44‰, −29‰ and −26‰, respectively. The difference in carbon isotopic values between methane and ethane is great, suggesting a biogenic oil-type gas produced by the mixed organic matter at peak generation. δ ¹³ \( C_{CO_2 } \) values of nonhydrocarbon gases are all heavier than −10‰, indicating a typical abiogenic gas. The simulation experiment on hydrocarbon generation of organic matter in a closed gold-tube system showed that the proportion of methane in natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit is obviously higher than that in natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit, consequently the proportion of heavier hydrocarbons of the former is remarkably lower than that of the latter. Moreover, δ ¹³C₁ values of natural gases produced by terrigenous organic matter in the Lingfeng Formation marine deposit are about 5‰ heavier than those of natural gases derived from the aquatic and terrigenous mixed organic matter in the Yueguifeng Formation lacustrine deposit while δ ¹³C₂ and δ ¹³C₃ values of the former are over 9‰ heavier than those of the latter. Currently the LS36-1 oil-gas pool is the only commercial oil-gas reservoir in Lishui Sag, where carbon isotopic compositions of various hydrocarbon components differ greatly from those of natural gases produced by the Lingfeng Formation organic matter but are very similar to those of natural gases derived from the Yueguifeng Formation organic matter, therefore, natural gases in the LS36-1 oil-gas pool are mainly derived from the Yueguifeng Formation lacustrine source rock rather than the Lingfeng Formation marine or Mingyuefeng Formation coal-measures source rocks.

     

The distribution characteristic and its significance of compound specific isotopic composition of aromatic hydrocarbon from marine source rock and oil in the Tarim Basin,western China

Aromatic hydrocarbons are generally main distillation of crude oil and organic extract of source rocks. Bicyclic and tricyclic aromatic hydrocarbons can be purified by two-step method of chromatography on alumina. Carbon isotopic composition of individual aromatic hydrocarbons is affected not only by thermal maturity, but also by organic matter input, depositional environment, and hydrocarbon generation process based on the GC-IRMS analysis of Upper Ordovician, Lower Ordovician, and Cambrian source rocks in different areas in the Tarim Basin, western China. The subgroups of aromatic hydrocarbons as well as individual aromatic compound, such as 1-MP, 9-MP, and 2,6-DMP from Cambrian-Lower Ordovician section show more depleted 13 C distribution. The 13 C value difference between Cambrian-Lower Ordovician section and Upper Ordovician source rocks is up to 16.1‰ for subgroups and 14‰ for individual compounds. It can provide strong evidence for oil source correlation by combing the 13 C value and biomarker distribution of different oil and source rocks from different strata in the Tarim Basin. Most oils from Tazhong area have geochemical characteristics such as more negative 13C9-MP value, poor gammacerane, and abundant homohopanes, which indicate that Upper Ordovician source rock is the main source rock. In contrast, oils from Tadong area and some oils from Tazhong area have geochemical characteristics such as high 13C9-MP value, abundant gammacerane, and poor homohopanes, which suggest that the major contributor is Cambrian-Lower Ordovician source rock.     

The recognition of biodegraded petroleum-derived aromatic hydrocarbons in recent marine sediments

Aromatic hydrocarbon fractions isolated from sediments polluted with crude oil, from sampling stations in and around Sullom Voe, Shetland Islands, were found to exhibit, as the major feature in their gas chromatograms, an unresolved complex mixture or ‘hump’. This feature was absent from the gas chromatograms of the aromatic hydrocarbon fractions isolated from corresponding unpolluted sediments in the region. The observed aromatic hump had little resemblance to the distribution of aromatic hydrocarbons in a typical North Sea crude oil. Incubation studies, however, showed that such a hump was appearing when oil-spiked sediments were aerobically biodegraded. From these incubation studies it was also evident that alkylaromatic hydrocarbons in the crude oil were biodegraded before any change in the normal alkanes was apparent. Therefore, the presence of an unresolved complex mixture in the gas chromatograms of aromatic hydrocarbon fractions from recent sediments can act as a marker to recognize contamination by crude oil.     

An isotope study of the accumulation mechanisms of high-sulfur gas from the Sichuan Basin,southwestern China

The mechanism of hydrogen sulfide (H₂S) 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 H₂S 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 H₂S in natural gas is inherited from the gypsum or brine of the same or adjacent layer, indicating that the generation and accumulation of H₂S have the characteristics of either a self-generated source or a near-source.     

松辽盆地深部地壳构造特征与无机油气生成模式

松辽盆地中地壳有一低速-高导层(也称塑性层),中地壳的塑性层与松辽盆地的成因以及盆山耦合系统有关.盆地地幔流体活动有下列表现:(1)高热流、高地温场;(2)深大断裂与火山岩喷溢;(3)碱交代作用(如钠长石化、伊利石化);(4)Mg2 交代作用(如白云石化)等等.地球化学省与地球化学急变带控制了大油气田的分布并显示了盆地发生的壳-幔相互作用.中地壳的低速-高导层不是岩浆岩,而是一充满地幔流体的地质体,它们富含氢、碱金属(K 、Na )、卤素(F-、Cl-)、碳(甲烷、CO、CO2)、氮、硫等.在中地壳的温度压力条件下,在Fe、Ni等催化荆的参与下,H2与CO(CO2)可发生费-托合成烃的反应.实验表明:这个反应不仅可生成气态烃还可生成液态烃,并将发生碳同位素分馏作用.松辽盆地的U形运移模型受到质疑.按照石油无机生成的模型,松辽盆地的深部将会有更多的石油与天然气,庆深气田的发现便是一个明证.     

Cenozoic evolution of the sulfur cycle: Insight from oxygen isotopes in marine sulfate

We report new data on oxygen isotopes in marine sulfate (δ¹⁸O_SO4), measured in marine barite (BaSO₄), over the Cenozoic. The δ¹⁸O_SO4 varies by 6‰ over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The δ¹⁸O_SO4 does not co-vary with the δ³⁴S_SO4, emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the δ¹⁸O_SO4 over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The δ¹⁸O_SO4 also does not co-vary with the δ¹⁸O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the δ¹⁸O_SO4 to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the δ¹⁸O_SO4. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.     

Geochemical characteristics and accumulation of marine oil and gas around Halahatang depression,Tarim Basin,China

There exists a petroleum system rich of oil and gas around Halahatang depression, where the oil and gas possess obvious local distinctions of properties in different parts. The research proved that the discovered crude oil and natural gas in the region derived mainly from O₂₊₃ source rock, and the differences of its properties were controlled by the oil and gas filling intensity. The comprehensive study result shows the oil and gas reservoirs of the region mainly underwent three important accumulation phases: late Caledonian-Early Hercynian epoch, late Hercynian epoch, and Yanshan-Himalayan epoch. In the first phase, the oil and gas derived mostly from Cambrian source rock, which formed the primary ancient oil reservoirs, then suffered strong degradation and remained a great quantity of pyrobitumen in the high position of Tabei uplift in the present. In the second phase, the O₂₊₃ source rock of Manjia’er depression started its generation of hydrocarbon, which accumulated in the high position of Tabei up-lift afterwards, and then biodegradated to heavy oil in the late Hercynian epoch. In the last phase, the O₂₊₃ source rock of southern Halahatang depression and margin of Manjia’er depression started its peak of generating liquid hydrocarbon, which mostly accumulated in the trap formed before the Indo-China and Yanshan epoch, and in somewhere the heavy oil suffered dilutions in various degrees or serious gas invading, to lead to obvious crude oil divergence.