Carbon isotopic composition of individual n-alkanes in asphaltene pyrolysates of biodegraded crude oils from the Liaohe Basin, China

Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C₁₆–C₂₉ range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.     

Raman spectroscopic study of hydrous <Emphasis Type="Italic">γ</Emphasis>-Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> to 56.5 GPa

 Raman spectra of a single-crystal fragment of hydrous γ-Mg₂SiO₄, synthesized in a multianvil press, have been measured in a diamond-anvil cell with helium as pressure-transmitting medium to 56.5 GPa at room temperature. All five characteristic spinel Raman modes shift continuously up to the highest pressure, showing no evidence for a major change in the crystal structure despite compression well beyond the stability field of ringwoodite in terms of pressure. At pressures above ∼30 GPa a new mode on the low-frequency site of the two silicate-stretching modes is clearly identifiable, indicating a modification in the spinel structure which is reversible on pressure release. The frequency of the new mode (802 cm⁻¹ extrapolated to 1 bar) suggests the presence of Si–O–Si linkages and/or a partial increase in the coordination of Si. Direct determination of the subtle structural change causing the new Raman mode would require high-pressure, single-crystal synchrotron X-ray diffraction experiments. The Raman modes of hydrous and anhydrous Mg-end-member ringwoodite are nearly identical up to 20 GPa, suggesting that protonation has only minor effect on the lattice dynamics over the entire pressure stability range for ringwoodite in the mantle. Received: 7 December 2001 / Accepted: 16 April 2002     

Time-resolved luminescence of Fe3+ and Mn2+ ions in hydrous volcanic glasses

 Time-resolved luminescence spectra of natural and synthetic hydrous volcanic glasses with different colors and different Fe, Mn, and H₂O content were measured, and the implications for the glass structure are discussed. Three luminescence ranges are observed at about 380–460, 500–560, and 700–760 nm. The very short-living (lifetimes less than 40 ns) blue band (380–460 nm) is most probably due to the ⁴T₂(⁴D) →⁶A₁(⁶S) and ⁴A₁(⁴G) →⁶A₁(⁶S) ligand field transitions of Fe³⁺. The green luminescence (500–560 nm) arises from the Mn²⁺ transition ⁴T₁(⁴G) →⁶A₁(⁶S). It shows weak vibronic structure, short lifetimes less than 250 μs, and indicates that Mn²⁺ is tetrahedrally coordinated, occupying sites with similar distortions and ion–oxygen interactions in all samples studied. The red luminescence (700–760 nm) arising from the ⁴T₁(⁴G) →⁶A₁(⁶S) transition of Fe³⁺ has much longer lifetimes of the order of several ms, and indicates that ferric iron is also mainly tetrahedrally coordinated. Increasing the total water content of the glasses leads to quenching of the red luminescence and decrease of the distortions of the Fe³⁺ polyhedra. Received: 30 July 2001 / Accepted: 15 November 2001     

Calculation of the reservoir age from organic and carbonate fractions of sediments in the Gulf of Cariaco (Caribbean Sea)

A set of 24 AMS ¹⁴C measurements were performed on different sediment fractions from short gravity cores taken from the Gulf of Cariaco (northeastern Venezuela) in order to construct a detailed sedimentary archive for recent centuries. A local reservoir effect was expected because of i) strong upwelling from the neighboring Cariaco Trough and anoxia and ii) the specific geomorphological setting related to active faults with seeps and diapirism. Measurements were thus performed on different components: sediment bulk organic fraction (SBOF), pteropods shells (surface water), bivalve shells (bottom), and plant fragments. Based on comparisons of the different results, we discuss different age corrections and calibrations, which lead us to consider a negligible local reservoir correction (ΔR) for the bivalve and pteropod shells, which show no reservoir age for carbonate and an absence of water stratification. However, a local 633 ± 64 yr ΔR appears in the organic fraction of the sediment, and its origin is primary related to the upwelling mechanism.     

浙江南部近海沉积物柱状样中脂类生物标志物的组成及形态分布

湖泊沉积物中直链脂肪族化合物(MCCs)对气候变化响应敏感,环境条件的变化可促使MCCs在游离态和结合态间发生转化,是古气候重建的重要生物标志物。以往研究中对样品前处理通常采用混合溶剂提取法得到MCCs游离态组分,而以化学键合、物理吸附等形式赋存的结合态组分无法通过溶剂提取,不能获取结合态组分特征对气候环境变化的指示信息。本文将热裂解这一有机质高效分解技术与气相色谱-质谱(GC-MS)联用,实现了对内蒙古伊和沙日乌苏湖泊沉积物有机质组成的精细刻画,并识别、分析了共计3类、71项结合态MCCs化合物。结果表明：热解温度是影响热裂解-气相色谱-质谱(Py-GC/MS)分析沉积物样品中结合态MCCs分布特征的主要因素,450℃以下热解能量较低导致结合态MCCs解析不充分,550℃和650℃下各类结合态MCCs(含正构烷烃、正构烯烃及α-正构脂肪酮)充分解析,可经GC-MS实现在线分离、识别;随着热解温度升高,裂解产物中MCCs平均链长趋于降低,过高的裂解能量影响了产物中MCCs化合物链长特征对气候变化指示的敏感性。经研究各类MCCs分布特征发现,550℃下正构烷烃平均链长特征与传统气候替代指标游离态正构烷烃单体碳同位素δ¹³C_27~33具有较好的相关性(R=0.83)。结合态正构烷烃ACL_25~31指标响应了区域有效降水变化特征,识别了区域内5.6ka、3.9ka前后的干旱期,反映了东亚夏季风强度变化,对应了北半球中纬度有效降水变化。

     

An application of least-squares inverse analysis in kinetic interpretations of hydrous pyrolysis experiments

A least-squares inverse method is applied to the estimation of optimum kinetic parameters with statistical error bounds from concentration data obtained in isothermal hydrous pyrolysis experiments. The inverse method requires the specification of a data-parameter relationship (e.g., classical kinetic theory), the prior covariance matrices of data and parameter errors, as well as the prior central estimates of data and parameters. The reaction scheme considered is the common case of kerogen breakdown by Gaussian-weighted independent parallel first-order reactions and bitumen cracking by a single first-order reaction. The nonlinearity of the problem is reduced by a logarithmic transformation, which suggests a parameterization in terms of logarithmic concentrations, activation energies, and logarithmic Arrhenius factors. The linearized variance analysis is valid for the case studied, and the posterior covariance matrix reveals which parameters are constrained by the data. We find that the statistical errors in the average activation energy and the associated Arrhenius factor are strongly correlated. Hence, the parameters which determine the temperature dependence of the reaction rate have not been resolved independently. Furthermore, the kinetic results are very sensitive to the presence of a distribution of activation energies in kerogen breakdown. This distribution is not constrained by the data. As a consequence, neglecting the consideration of distributions of activation energies results in activation parameter values which are much too low. This is the major reason for the commonly encountered discrepancy between kinetic parameter values obtained from hydrous pyrolysis and micropyrolysis experiments, respectively.     

奥陶系未成熟藻干酪根水解下动力学参数的计算

利用爱沙尼亚奥陶系含藻干酪根未成熟生油岩样品的加水热模拟实验结果,计算了下古生界藻干酪根在各不同演化阶段的平均表观活化能和频率因子。发现其演化的整个过程不完全符合化学反应的一级反应,而是分段符合,动力学参数随演化程度的升高而先降低后增加。其计算结果对于我国下古生界及中上元古界生油层盆地模拟和资源评价具有重要的参考价值。     

Analysis of modern and fossil plant cuticles by Curie point Py-GC and Curie point Py-GC-MS: Recognition of a new, highly aliphatic and resistant biopolymer

This paper investigates to what extent the chemical constituents of plant cuticles (waxes and cutin) can survive diagenesis. Recent and fossil plant cuticles were analyzed by means of Curie point pyrolysis-gas chromatography and Curie point pyrolysis-gas chromatography-mass spectrometry. Recent cuticles were analyzed without treatment, after solvent extraction and after cutin depolymerization. Extensive series of straight-chain alkanes, alk-1-enes and α,ω)-alkadienes dominate the pyrolysates, especially after removal of the wax and cutin. ¹³C-NMR spectroscopy of the residue after removal of the cutin confirmed the presence of a new, highly aliphatic biopolymer and a polysaccharide fraction.The abundance of straight-chain alkanes, alk-1-enes and α,ω-alkadienes in the fossil plant cuticles indicates the chemical resistence of the biopolymer to diagenesis and may explain the occurrence of straight-chain aliphatic moieties in organic-matter-rich sediments and coals as revealed by “C-NMR spectroscopy and flash pyrolysis methods. The highly aliphatic biopolymer may function as an important oil precursor.     

Geochemistry of coalbed gas – A review

Coals are both sources and reservoirs of large amounts of gas that has received increasing attention in recent years as a largely untapped potential energy resource. Coal mining operations, such as ventilation of coalbed gas from underground mines, release coalbed CH₄ into the atmosphere, an important greenhouse gas whose concentration in the atmosphere is increasing. Because of these energy and environmental issues, increased research attention has been focused on the geochemistry of coalbed gas in recent years. This paper presents a summary review of the main aspects of coalbed gas geochemistry and current research advances.     

原油裂解成气反应机理、介质影响因素与判识评价

原油裂解成气是近年来天然气勘探领域重大的理论进展之一,其直接关系到勘探工作的决策和部署.对原油裂解气的裂解反应机理、介质影响因素与判识评价进行了较为详细的总结和评述,认为常用的原油热裂解一级动力学模拟模型可能不适合于地质温度条件下特别稳定的重烃气体;地质温度条件下原油加氢裂解的重要性可能被忽视;疏导体系及储层条件下的重烃反应损耗也是形成实际天然气藏的重要途径之一;目前的判识评价指标尚不能从本质上反映原油裂解气与干酪根裂解气的差异.