ODP184航次岩芯海底沉积物元素相态研究及其对有机质和轻烃的指示意义

分析了ODP184航次1 146站位海底岩芯沉积物中的Cu、Fe、Ni等7种元素的总量和相态分布及变化规律;研究发现,各元素的总量及相态的剖面分布受生物作用、有机质络合吸附、共沉淀等多种因素控制;沉积物主要来自陆源.元素Cu、Co、Ni的有机结合态及总量的分布规律表明深部地层中存在大量有机物;结合岩芯沉积物中有机气体及相关地质背景,认为该区具有良好的油气赋存条件;对各元素的相态与轻烃及各有机指标进行聚类分析,发现虽然可交换态的Cu、Fe、Ni在元素各相态中所占的比例较少,但却是指示油气存在的有效指标.     

Stabilization of extracellular polymeric substances (Bacillus subtilis) by adsorption to and coprecipitation with Al forms

Extracellular polymeric substances (EPS) are continuously produced by bacteria during their growth and metabolism. In soils, EPS are bound to cell surfaces, associated with biofilms, or released into solution where they can react with other solutes and soil particle surfaces. If such reaction results in a decrease in EPS bioaccessibility, it may contribute to stabilization of microbial-derived organic carbon (OC) in soil. Here we examined: (i) the chemical fractionation of EPS produced by a common Gram positive soil bacterial strain (Bacillus subtilis) during reaction with dissolved and colloidal Al species and (ii) the resulting stabilization against desorption and microbial decay by the respective coprecipitation (with dissolved Al) and adsorption (with Al(OH)_3(am)) processes. Coprecipitates and adsorption complexes obtained following EPS-Al reaction as a function of pH and ionic strength were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The stability of adsorbed and coprecipitated EPS against biodegradation was assessed by mineralization experiments for 1100 h. Up to 60% of the initial 100 mg/L EPS-C was adsorbed at the highest initial molar Al:C ratio (1.86), but this still resulted only in a moderate OC mass fraction in the solid phase (17 mg/g Al(OH)_3(am)). In contrast, while coprecipitation by Al was less efficient in removing EPS from solution (maximum values of 33% at molar Al:C ratios of 0.1-0.2), the OC mass fraction in the solid product was substantially larger than that in adsorption complexes. Organic P compounds were preferentially bound during both adsorption and coprecipitation. Data are consistent with strong ligand exchange of EPS phosphoryl groups during adsorption to Al(OH)_3(am), whereas for coprecipitation weaker sorption mechanisms are also involved. X-ray photoelectron analyses indicate an intimate mixing of EPS with Al in the coprecipitates, which is not observed in the case of EPS adsorption complexes. The incubation experiments showed that both processes result in overall stabilization of EPS against microbial decay. Stabilization of adsorbed or coprecipitated EPS increased with increasing molar Al:C ratio and biodegradation was correlated with EPS desorption, implying that detachment of EPS from surface sites is a prerequisite for microbial utilization. Results indicate that the mechanisms transferring EPS into Al-organic associations may significantly affect the composition and stability of biomolecular C, N and P in soils. The observed efficient stabilization of EPS might explain the strong microbial character of organic matter in subsoils.     

Organic geochemical characterization of the New Albany Shale group in the Illinois Basin

Benzene extractable aliphatic hydrocarbons from the New Albany Shale in the Illinois Basin were characterized by gas chromatography and mass spectrometry, and the total organic matter of the shale was characterized by solid state carbon-13 cross polarization magic angle spinning nuclear magnetic resonance. Core samples from a northwest-trending cross-section of the Illinois Basin were studied. Gas chromatography (GC) and gas chromatography-mass spectrometric analysis (GC/MS) data indicate a regional variation of the aliphatic composition of the shale extracts. A positive, linear relationship between the two ratios, pristane/n-C₁₇ and phytane/n-C₁₈, is indicated. The NMR results indicated that organic matter deposited in northwestern Illinois shale is relatively high in aliphatic hydrocarbon content while, in contrast, organic matter found in southeastern Illinois shale is relatively low in aliphatic hydrocarbon content. Our findings suggest that the organic variation of the shale is mainly due to the differences in thermal maturity of the shale organic matter and the use of pristane/n-C₁₇ ratio as a thermal parameter in the study of oil may be extended to the study of the ancient sediments.     

页岩中气体的超临界等温吸附研究

页岩气等温吸附实验多为临界温度以上的吸附实验,其得到的吸附量为过剩吸附量。为了研究页岩气超临界等温吸附机理,运用重力法,在临界温度以上,分别进行了甲烷和二氧化碳在页岩中的高压等温吸附实验。在分析经典型吸附和超临界吸附区别的基础上,通过修改的超临界等温吸附模型(Langmuir方程和微孔充填(Dubinin Radushkevich,D-R))对实验数据进行了拟合。结果表明:简单的Langmuir方程可近似拟合甲烷吸附实验数据,但精度不高,且无法拟合二氧化碳的吸附数据;将吸附相密度作为可优化参数,修改的微孔充填模型和Langmuir模型能很好地拟合甲烷和二氧化碳的吸附数据,其中修改的微孔充填模型拟合效果最好,且回归得到的超临界甲烷吸附相密度同文献报道的一致,表明吸附气可能以微孔充填的形式存在。      

Formation of black carbon-like and alicyclic aliphatic compounds by hydroxyl radical initiated degradation of lignin

Exposure of lignin-derived organic matter (OM) to hydroxyl radicals originating from Fenton type reactions generates condensed aromatic and alicyclic aliphatic compounds, as shown using ultrahigh resolution mass spectrometry. Although condensed aromatic compounds are common in soil and dissolved OM, their presence has been attributed largely to combustion. A non-pyrogenic route for the formation of condensed aromatic compounds from lignin is suggested here, specifically that hydroxyl radical-initiated oxidation of lignin is capable of producing black carbon-like condensed aromatic compounds. Alicyclic aliphatic compounds are also produced, likely as part of a concerted process involving ring opening, polymerization and/or cyclization and hydrogen abstraction. Hydroxyl radicals associated with lignin degradation are produced through photochemistry in aqueous systems and enzymatic microbial processes in soil.     

页岩气在孔隙表面的赋存状态及其微观作用机理

吸附态是页岩气的主要赋存状态之一，对吸附气含量的准确评价是页岩气勘探开发中的重要环节.在页岩吸附气含量评价过程中，所选用的等温吸附模型是否遵循页岩气的赋存状态及其微观作用机理，是决定模型适用性的关键所在，也是决定吸附气含量评价准确性的重要因素.因此，需要对页岩气在孔隙表面的赋存状态及其微观作用机理开展深入研究，为科学地优选或建立吸附气评价模型提供理论依据.利用巨正则蒙特卡洛（Grand Canonical Monte Carlo，简称GCMC）法分别模拟甲烷在有机质和伊利石孔隙中的吸附特征并得到分子构型，并进行分子动力学（MD）模拟使体系达到充分平衡.在此基础上，根据气体浓度分布、密度场分布以及分子间相互作用等特征阐明页岩气在孔隙表面的赋存状态及其微观作用机理.研究表明，页岩气在孔隙表面的吸附作用并非单层吸附，吸附相可划分为强吸附层、弱吸附层和二者之间的吸附层波谷.强吸附层主要受到矿物表面的吸附作用；吸附层波谷与弱吸附层既受到矿物表面的吸附作用，又受到不同吸附层之间的吸附作用.Langmiur模型与BET模型的假设条件与此机理不严格相符，可能对模型评价精度造成一定影响.对页岩气在孔隙表面赋存状态及其微观作用机理的研究，有望为吸附模型的优选或建立提供理论依据.      

鄂尔多斯盆地北部直罗组有机质特征及与铀成矿关系

本文研究了鄂尔多斯盆地典型铀矿床的有机质与铀成矿的关系。探讨了煤屑的赋存状态、煤质特征及成熟度,认为煤屑的演化程度均较低,处于低成熟阶段,有利于对铀的吸附。总体上看煤质有机质和铀矿化关系密切,铀含量与煤屑含量呈正相关关系,对铀矿物为吸附态形式。通过对该区油气包裹体的研究认为,该区存在多期次的成岩方解石胶结过程,并伴随多期次的油气包裹体发育,尤以晚期的胶结方解石矿物中存在丰富的晚期油气包裹体。研究认为晚期可能发生过油、气的运移和聚集,铀矿床的形成与赋矿砂岩中有机流体或还原性气体的充注和络合作用密切相关,因而这些丰富的有机流体和还原性气体对于铀的富集沉淀具有重要意义。     

Reservoir characteristics and methane adsorption capacity of the Upper Triassic continental shale in Western Sichuan Depression,China

The well-developed continental shale sequences in the Western Sichuan Depression are characterised by extremely low porosity and permeability, complex lithologies and strong lateral facies changes. The overall lack of proper characterisation of the shale properties has restricted gas exploration and development in the region. In this study, shales from the fifth member of the Xujiahe Formation of the Upper Triassic (T₃x⁵) are comprehensively characterised in terms of their organic geochemistry, mineral composition, microscopic pore structure and gas content. In addition, the influence of various geological factors on the adsorbed gas content is investigated. We proposed a new model for predicting the adsorption gas content of continental shale. The T₃x⁵ shale sequence is found to be rich in organic matter but with variable mineral compositions, pore types and reservoir physical properties. The porosity and permeability of shales are better than those of siltstones and fine sandstones interbedded with the shale under an overall densification background. Mesopores (2–50 nm) are common in the shale sequence, followed by micropores and then macropores. The gas-adsorption capacity of organic-rich shales increases with increasing TOC and clay-mineral contents, maturity and pressure, but decreases with increasing quartz content, carbonate minerals and temperature. The gas-adsorption capacity can thus be expressed as a function of organic matter, clay-mineral content, temperature and pressure. The calculated results are in good agreement with the experiment results and indicate that adsorption gas in the studied shales accounts for 78.9% of the total gas content.     

Mechanistic roles of soil humus and minerals in the sorption of nonionic organic compounds from aqueous and organic solutions

Mechanistic roles of soil humus and soil minerals and their contributions to soil sorption of nonionic organic compounds from aqueous and organic solutions are illustrated. Parathion and lindane are used as model solutes on two soils that differ greatly in their humic and mineral contents. In aqueous systems, observed sorptive characteristics suggest that solute partitioning into the soil-humic phase is the primary mechanism of soil uptake. By contrast, data obtained from organic solutions on dehydrated soil partitioning into humic phase and adsorption by soil minerals is influenced by the soil-moisture content and by the solvent medium from which the solute is sorbed.     

几种纤维矿物粉尘的真空有机吸附及表面基团变化

利用真空有机吸附和红外光谱分析法,研究了几种纤维矿物粉尘对不同偶极矩的正己烷（偶极矩为０）、乙醚（偶极矩为１．１６）和吡啶（偶极矩为２．１９）的吸附特征及这种有机试剂对表面基团的影响。研究发现：纤维矿物粉尘对有机试剂的吸附能力并不完全与有机试剂的偶极矩大小成正比;部分纤维矿物粉尘对正己烷的吸附为化学吸附,吸附解吸后出现了１２６２￣１２６７ｃｍ＾－１、１３１１ｃｍ＾－１的新的ＩＲ谱带,它们应是部分纤     

现代松粉热模拟产气态烃、气态非烃及水分特征

研究表明,现代松粉热模拟实验释放水的产出分两个阶段,两类水,第一阶段,４００℃以前释放水为松粉内部以水分子形式存在的结合水,呈弱酸性（ｐＨ＝６）,为第一类水,第二阶段,４００℃以上温度释放水为松粉内部和高岭石内部结构水（－ＯＨ）,呈弱碱性（ｐＨ＝９）,为第二类水,现代松粉热模拟实验产出气体量随温度升主呈逐渐上升趋势,４５０℃以后上升梯度突然增大,所产气体分为两大类：Ｉ类为无机气体,由Ｎ２、Ｈ２和ＣＯ２气体组成,以ＣＯ２相对丰度最主为特征。ＣＯ２气主要来自有机酸的脱羧反应和离子太氧与有机质氧化还原反应产出ＣＯ２。Ｈ２气主要来自孢粉和烃,Ｃ４～Ｃ６异构饱和烃及丙烯、丁烯不饱和烃等分子物标志物,其中以甲烷相对丰度最高为特征,气态有机烃来自孢粉内有机物的热降解产物,松粉 拟实验中丰富的气态有机烃和无机气体的检测出,为研     

鄂尔多斯盆地东部太原组页岩气吸附特征及影响因素

鄂尔多斯盆地东部太原组在绥德地区发育一套潜在的烃源岩,总有机碳(Total Organic Carbon,TOC)含量为0.75%~5.71%(平均2.75%);镜质体反射率(Ro)为1.43%~2.12%(平均1.80%),处在高成熟-过成熟阶段,具有很好的生气潜力。为了探讨鄂尔多斯盆地东部太原组泥页岩的吸附特征,选取了研究区SSD1井10个泥页岩样品进行等温吸附、总有机碳含量、镜质体反射率、X-射线衍射和比表面积等测试分析,在此基础上探讨了盆地东部太原组富有机质泥页岩的吸附能力及其影响因素。结果表明:研究区SSD1井太原组10个泥页岩样品的兰氏体积为1.11~2.41m3/t,随着压力的增加,吸附能力迅速增加,当达到一定压力后达到饱和;泥页岩的吸附能力与总有机碳含量和黏土矿物含量有正相关关系;页岩比表面积与兰氏体积相关性不明显,推测样品孔隙大小及形态对气体的扩散和吸附有一定的影响。综合评价认为,总有机碳含量、黏土矿物含量是影响太原组泥页岩吸附能力的重要因素,这为盆地东部页岩气勘探提供参考。     

FTIR studies of deuterium incorporation into coal,associated mineral matter and hydrogenation residues

An Australian bituminous coal (Liddell) was hydrogenated with hydrogen/deuterium gas mixtures in the presence of tetralin. The nature and forms of deuterium in the insoluble (residue) products were investigated by Fourier transform infrared spectroscopy (FTIR).The results show that deuterium enters and is incorporated into not only aromatic and aliphatic organic structures in the coal but also hydroxyl groups of associated kaolinite. The results suggest that deuterium may be incorporated into organic structures in the coal via an additional reaction pathway involving exchange with kaolinite. This pathway of transfer of deuterium or hydrogen to the coal has not previously been demonstrated.     

鄂尔多斯盆地东部太原组页岩气吸附特征及影响因素

鄂尔多斯盆地东部太原组在绥德地区发育一套潜在的烃源岩,总有机碳(Total Organic Carbon,TOC)含量为0.75%~5.71%(平均2.75%); 镜质体反射率(R_o)为1.43%~2.12%(平均1.80%),处在高成熟—过成熟阶段,具有很好的生气潜力。为了探讨鄂尔多斯盆地东部太原组泥页岩的吸附特征,选取了研究区SSD1井10个泥页岩样品进行等温吸附、总有机碳含量、镜质体反射率、X-射线衍射和比表面积等测试分析,在此基础上探讨了盆地东部太原组富有机质泥页岩的吸附能力及其影响因素。结果表明: 研究区SSD1井太原组10个泥页岩样品的兰氏体积为1.11~2.41 m³/t,随着压力的增加,吸附能力迅速增加,当达到一定压力后达到饱和; 泥页岩的吸附能力与总有机碳含量和黏土矿物含量有正相关关系; 页岩比表面积与兰氏体积相关性不明显,推测样品孔隙大小及形态对气体的扩散和吸附有一定的影响。综合评价认为,总有机碳含量、黏土矿物含量是影响太原组泥页岩吸附能力的重要因素,这为盆地东部页岩气勘探提供参考。     

煤层气与页岩气吸附差异性分析

查明页岩气与煤层气的吸附差异对指导其勘探开发具有重要意义。通过测试不同成熟度和有机质(TOC)的煤与页岩的等温吸附曲线,结果表明:TOC含量是影响页岩吸附的主要因素,成熟度相当的煤与页岩相比,煤的吸附量远远大于页岩,主要是由于成藏特征、物质组成和孔隙结构不同造成的;页岩吸附过程中出现的异常吸附可能有其他的吸附理论支撑。      

Adsorption of xenon and krypton on shales

Parameters for the adsorption of Xe and Kr on shales and related samples have been measured by a method that uses a mass spectrometer as a manometer. The gas partial pressures used were 10^?11 atm or less; the corresponding adsorption coverages are only small fractions of a monolayer, and Henry's Law behavior is expected and observed. Heats of adsorption in the range 2–7 kcal/mol were observed. Henry constants of the order of magnitude 1 cm³ STP g^?1 atm^?1 at 0 to 25°C are obtained by extrapolation.Adsorption properties are variable by sample, but the general range suggests that shales might be sufficiently good adsorbents that equilibrium adsorption with modern air may account for a nontrivial fraction of the atmospheric inventory of Xe (perhaps even Kr). It seems doubtful, however, that this effect can account for the deficiency (approximately a factor of 25) of atmospheric Xe in comparison with the planetary gas patterns observed in meteorites. If gas is adsorbed on interior surfaces in shale clays and can communicate with sample exteriors only through very narrow (10^?7 to 10^?6 cm) channels, and thus only very slowly, equilibrium adsorption may make substantial contributions to experimentally observed ‘trapped’ gases without the need for any further trapping mechanism.     

温度对页岩吸附解吸的敏感性研究

页岩气的赋存方式主要是吸附,使吸附在页岩储层内表面的天然气解吸出来是提高页岩气井产量的最终目标。为了使吸附在页岩储层内的天然气完全地被采出来,提出了升温加速解吸的方法来提高页岩气采收率。通过室内吸附与解吸实验,对4块页岩岩心分别进行了不同温度下的等温吸附量与解吸量测定,分析影响页岩储层吸附量与解吸量的主要因素,研究提高储层温度来加速解吸页岩储层CH4吸附量的适应性。研究结果表明,页岩的吸附能力与页岩的有机碳含量和有机成熟度密切相关,随着页岩有机碳含量以及有机成熟度的提高,页岩的吸附能力增加。不同温度的吸附与解吸实验表明,温度越高,页岩的吸附能力越低,随着温度的升高,页岩气的解吸量增大。升温可以提高页岩气的解吸时间、解吸速度以及提高页岩气最终采收率。提高页岩储层温度进行加速解吸是一种提高页岩气产量的好方法,可以对页岩气藏开采和开发理论提供一定的指导意义。     

The importance of atmospheric input of terrestrial organic material to deep sea sediments

The concentrations of lipids were determined in atmospheric particle, gas and rain samples collected from the tropical North Pacific to assess lipid sources, transport mechanisms and fluxes to the ocean surface. Four lipid compound classes (aliphatic hydrocarbons, fatty alcohols, fatty acid esters, and salts) all unequivocally show a terrestrial vascular plant source. These aerosol lipids originate from wind erosion of Asian and American soils and direct emission from vegetation. The major fluxes result from rain rather than dry deposition. These fluxes are large enough to have a major potential impact on the inventory of terrestrially derived lipid material found in deep-sea sediments. This has been showm for n-alkanes, fatty alcohols, fatty acids, total lipids and for organic carbon. By comparing atmospheric and sediment trap fluxes with sediment accumulation rates, it is suggested that some biogenic terrestrial material is more protected from degradation than marine-derived material.     

Volcanic emissions and the early Earth atmosphere

Despite uncertainties in our understanding of early Earth volcanism and atmospheric composition, thermodynamic modelling is able to offer estimates of the global production of reactive trace species (NO, OH, SO₃, Cl, Br and I) from early Earth volcanism, and thereby to shed light on processes which may have been different in Earth’s early atmosphere. Model results show that thermal decomposition of magmatic H₂O, CO₂ and SO₂ in high-T mixtures of magmatic and atmospheric gases (at T > 1400 °C) generate high levels of reactive trace gas species. Production of these reactive trace species is insensitive to atmospheric CO₂ in mixtures where the atmospheric gas is the minor component and will hence continue during periods of low atmospheric CO₂. Fluxes of NO, OH, Cl, Br and I from early Earth volcanism are predicted to exceed those from modern Earth volcanism as the higher temperature of early Earth emissions compensates for lower levels of O₂ in the atmosphere, compared to the modern Earth. Under certain conditions, the volcanic NO flux from early Earth volcanism is found to be comparable to other sources of reactive N such as lightning NO and photochemical HCN. This is one possible source of fixed nitrogen which may alleviate any postulated Archean nitrogen crisis. Our thermodynamic model reveals that production of SO₃ (a potential precursor for near-source volcanic sulphate and hence ‘primary’ volcanic aerosol) is likely to be significantly lower from early Earth volcanism. Uncertainty in the pathway to near-source sulphate in modern volcanism (i.e., the reaction of SO₃ with water or direct emission) introduces a large uncertainty into the production rate of near-source volcanic sulphate on the early Earth.     

基于Ono-Kondo格子模型的页岩气超临界吸附机理探讨

页岩气吸附机理的研究对于页岩气成藏和储量评价具有重要意义.甲烷在地层温度和压力条件下处于超临界状态,页岩气的吸附实际上为超临界吸附,但其机理目前尚不明确.在建立Ono-Kondo格子模型的基础上,结合低温氮气吸附和高压甲烷等温吸附实验,对龙马溪组页岩的微观孔隙结构和超临界吸附曲线进行了分析.结果表明,页岩中发育的孔隙尺度较小,比表面积较大,吸附气主要赋存于微孔和中孔中;页岩的等温吸附曲线在压力较大时,必然存在下降的趋势,这并非异常现象,而是超临界甲烷过剩吸附量的本质特征.Ono-Kondo格子模型对页岩高压等温吸附曲线的拟合效果很好,相关系数均在0.99以上,说明该模型可以表征页岩纳米孔隙中超临界甲烷的吸附特征.基于拟合得到的吸附相密度可将过剩吸附量转换为绝对吸附量,并直接计算地层温度和压力下甲烷的吸附分子层数,计算层数均小于1,表明甲烷分子并没有铺满整个孔隙壁面.因此受流体性质、吸附剂吸附能力和孔隙结构3个方面的影响,页岩气的吸附机理为单层吸附,不可能为双层甚至多层吸附.