The nature and fate of natural resins in the geosphere--VIII. NMR and Py-GC-MS characterization of soluble labdanoid polymers, isolated from Holocene class I resins

Soluble polylabdanoids isolated by sequential solvent extraction have been characterized by liquid-state ¹³C- and ¹H NMR and ¹³C-¹H HMQC (heteronuclear correlation) NMR spectroscopy in addition to solid-state NMR and Py-GC-MS techniques. Two Holocene resins originating from Santander, Colombia and Mombasa, Kenya were analyzed. Soluble polymers were isolated by extraction with a 1:1 (v/v) methylene chloride-methanol mixture following sequential extractions with methylene chloride and methanol. The molecular weight of polymer extracts was shown by GPC analyses to exceed that of non-polymeric occluded terpenoids. Py-GC-MS, solid-state ¹³C CP/MAS and ¹³C cross-polarization/depolarization NMR spectroscopy results indicated that chemical compositions of soluble polymers isolated from immature resins are highly representative of the structure of corresponding insoluble polymers, i.e. polylabdatrienes. These data provide evidence for cross-linking or cyclization of side-chain olefinic carbons during or shortly after polymerization. Generally, the characterization of soluble resin polymers by liquid-state NMR spectroscopy has proven to be an excellent means for investigating the maturation mechanism of polylabdanoid resinites, and has potential for furthering the application of Class I resinites as geothermal indicators.     

A molecular and carbon isotope biogeochemical study of biomarkers and kerogen pyrolysates of the Kimmeridge Clay Facies: palaeoenvironmental implications

Structures and carbon isotopic compositions of biomarkers and kerogen pyrolysis products of a dolomite, a bituminous shale and an oil shale of the Kimmeridge Clay Formation (KCF) in Dorset were studied in order to gain insight into (i) the type and extent of water column anoxia and (ii) changes in the concentration and isotopic composition of dissolved inorganic carbon (DIC) in the palaeowater column. The samples studied fit into the curve of increasing δ¹³C of the kerogen (δ¹³C_TOC) with increasing TOC, reported by Huc et al. (1992). Their hypothesis, that the positive correlation between TOC and δ¹³C_TOC is the result of differing degrees of organic matter (OM) mineralisation in the water column, was tested by measuring the δ¹³C values of primary production markers. These δ¹³C values were found to differ on average by only 1‰ among the samples, implying that differences in the extent of OM mineralisation cannot fully account for the 3‰ difference in δ¹³C_TOC. The extractable OM in the oil shale differs from that in the other sediments due to both differences in maturity, and differences in the planktonic community. These differences, however, are not likely to have significantly influenced δ¹³C_TOC either. All three sediments contain abundant derivatives of isorenieratene, indicating that periodically euxinia was extending into the photic zone. The sediments are rich in organic sulfur, as revealed by the abundant sulfur compounds in the pyrolysates. The prominence of C₁-C₃ alkylated thiophenes over n-alkanes and n-alkenes is most pronounced in the pyrolysate of the sediment richest in TOC. This suggests that sulfurisation of OM may have played an important role in determining the TOC-δ¹³C_TOC relationship reported by Huc et al. (1992).     

东海宝云亭三井热解录井方法应用研究的探讨

有机地化(热解)录井是一种新的录井方法,在东海的油气勘探工作中已得到较好的应用效果。在试油前能将录井资料进行综合整理与解释,随钻预测钻井中的含油气层段,为油气层位的确定提供依据。     

油气生成热模拟实验研究进展

作为研究油气地球化学的一种重要手段－－热模拟被愈来愈广泛地应用。介绍了不同时期油气生成模拟实验研究的状况，阐述了模拟实验已解决的和尚存在的问题，进而指出了其发展趋势和应开展的工作。     

TSR对碳酸盐岩中沥青生烃影响的模拟实验

利用地层孔隙热压生排烃模拟仪实验装置,对采自四川盆地西北部广元矿山梁地区下寒武统具高有机质含量、高氢指数和低成熟度特征的固体沥青,开展了模拟地层条件下的"沥青+白云岩+去离子水"(系列A)和"沥青+白云岩+硫酸镁+去离子水"(系列B)生排烃实验。结果表明,这两个系列的气体产率具有较大差异,其中,加入硫酸镁的系列(系列B)发生了热化学硫酸盐还原反应(TSR),使气态烃和非烃气体的产率增大,同时也加速了重烃气体的裂解,导致重烃气体大量裂解的温度降低。     

油页岩原位裂解用注热管柱数值传热模拟与试验研究

油页岩作为一种非常规油气资源,有望成为石油的替代品。油页岩原位裂解技术对环境污染小,生成的油页岩油油品好,具有良好的开发前景。在原位裂解过程中,减少注热过程中的热量损失具有十分重要的意义,因此本文将对保温注热管柱的传热特性进行数值模拟和试验研究。通过传热学计算分析,保温注热管柱设计为外径?32mm的钢管,外层缠绕共计24mm的纳米保温材料。数值分析表明氮气流量越大,注热管柱出口温度达到稳定的时间越短,稳定温度也越高;当管柱氮气入口温度为500℃时,管柱出口温度在一定注气时间后均可达到400℃以上。在农安油页岩原位裂解先导试验工程中对注热管柱进行野外试验,管柱达到注热保温效果,井底温度达到设计温度,最终成功获得油页岩油。     

Aromaticity and degree of aromatic condensation of char

The aromatic carbon structure is a defining property of chars and is often expressed with the help of two concepts: (i) aromaticity and (ii) degree of aromatic condensation. The varying extent of these two features is assumed to largely determine the relatively high persistence of charred material in the environment and is thus of interest for, e.g., biochar characterization or carbon cycle studies. Consequently, a variety of methods has been used to assess the aromatic structure of chars, which has led to interesting insights but has complicated the comparison of data acquired with different methods. We therefore used a suite of seven methods (elemental analysis, MIR spectroscopy, NEXAFS spectroscopy, ¹³C NMR spectroscopy, BPCA analysis, lipid analysis and helium pycnometry) and compared 13 measurements from them using a diverse sample set of 38 laboratory chars. Our results demonstrate that most of the measurements could be categorized either into those which assess aromaticity or those which assess the degree of aromatic condensation. A variety of measurements, including relatively inexpensive and simple ones, reproducibly captured the two aromatic features in question, and data from different methods could therefore be compared. Moreover, general patterns between the two aromatic features and the pyrolysis conditions were revealed, supporting reconstruction of the highest heat treatment temperature (HTT) of char.     

Pyrolytic and spectroscopic study of a sulphur-rich kerogen from the “Kashpir oil shales” (Upper Jurassic, Russian platform)

The kerogen of an organic-rich sample, termed f top, from the Gorodische section (Russian platform) was studied using a combination of microscopic, spectroscopic and pyrolytic methods so as to examine its chemical structure, source organisms and formation pathway(s). This kerogen, which is mainly composed of orange gel-like, nanoscopically amorphous organic matter, exhibits a relatively high aliphatic character; organic sulphur is mainly present as di(poly)sulphides and alkylsulphides. The f top kerogen was chiefly formed via intermolecular incorporation of sulphur in algal or cyanobacterial lipids and carbohydrates. However, its formation also involved oxidative condensation via ether linkages. Comparison of f top sample with other S-rich kerogens points to a closer similarity with Monterey kerogens rather than with a kerogen from the bituminous laminites of Orbagnoux.