A computational chemical study of penetration and displacement of water films near mineral surfaces

A series of molecular dynamics simulations have been performed on organic–water mixtures near mineral surfaces. These simulations show that, in contrast to apolar compounds, small polar organic compounds such as phenols can penetrate through thin water films to adsorb on these mineral surfaces. Furthermore, additional simulations involving demixing of an organic–water mixture near a surfactant-covered mineral surface demonstrate that even low concentrations of adsorbed polar compounds can induce major changes in mineral surface wettability, allowing sorption of apolar molecules. This strongly supports a two-stage adsorption mechanism for organic solutes, involving initial migration of small polar organic molecules to the mineral surface followed by water film displacement due to co-adsorption of the more apolar organic compounds, thus converting an initial water-wet mineral system to an organic-covered surface. This has profound implications for studies of petroleum reservoir diagenesis and wettability changes.     

Phenols in hydrothermal petroleums and sediment bitumen from Guaymas Basin, Gulf of California

The aliphatic, aromatic and polar (NSO) fractions of seabed petroleums and sediment bitumen extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry (free and silylated). The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolyzates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore sediments are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds in samples with a high degree of thermal maturity. Phenols are one class of oxygenated compounds found in these samples. A group of methyl-, dimethyl- and trimethyl-isoprenoidyl phenols (C27-C29) is present in all of the seabed NSO fractions, with the methyl- and dimethyl-isoprenoidyl phenols occurring as major components, and a trimethyl-isoprenoidyl phenol as a minor component. A homologous series of n-alkylphenols (C13-C33) has also been found in the seabed petroleums. These phenols are most likely derived from the hydrothermal alteration of sedimentary organic matter. The n-alkylphenols are probably synthesized under hydrothermal conditions, but the isoprenoidyl phenols are probably hydrothermal alteration products of natural product precursors. The suites of phenols do not appear to be useful tracers of high temperature hydrothermal processes.     

原油极性组分的吸附与储层润湿性及研究意义

探讨了原油极性组分（非烃,沥青质）的吸附机理及其吸附性,润湿性特征;介绍了ＮＳＯ极性化合物与润湿性的关系。极性化合物的吸附可能是多种机理共同作用的结果,吸附作用可导致储层润湿性反转,润湿性是决定原油采收集的主要因素。通过改变储层润湿性,可能有利于提高原油采收率。极性化合物的吸附等特性在储层润湿性研究,油田开发管理中具有重要意义。     

Preservation of coal-waste geochemical markers in vegetation and soil on self-heating coal-waste dumps in Silesia,Poland

Occurrence and distributions of geochemical markers on vegetation and in soils covering two self-heating coal waste dumps were investigated with gas chromatography-mass spectrometry (GC–MS) and compared with those of bitumen expelled on the coal waste dump surface. Presence of biomarkers, alkyl aromatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), and such polar compounds as phenols indicate that components of self-heating coal wastes indeed migrate to soils and plants surface and their characteristic fingerprints can be applied in passive monitoring to investigate migration of contaminants from self-heating coal wastes. Moreover, results allow to discriminate between the Upper- and Lower Silesian coal basins, notwithstanding value shifts caused by heating. Mechanisms enabling the migration of geochemical compounds into soils include mixing with weathered coal-waste material, transport in gases emitted due to self-heating and, indirectly, by deposition of biomass containing geochemical substances. Transport in gases involves mostly lighter compounds such as phenols, methylnaphthalenes, methylbiphenyls, etc. Distributions and values of geochemical ratios are related to differences in their boiling temperatures in the case of lighter compounds but preserve geochemical features in the case of heavier compounds such as pentacyclic trierpanes.     

柴达木盆地西部原油极性化合物特征及其地球化学意义

柴达木盆地西部原油主要形成于高盐强还原环境和有机质低成熟演化阶段。这种特殊成油环境，为研究原油中极性生物标志物示踪作用提供了有利条件。对6个原油胶质馏分硅醚衍生物进行了GC—MS分析，从中检出丰富的脂肪酸、烷基醇、脂肪酸甘油—酯、酰胺和甾烯醇化合物，并且脂肪酸甘油—酯为首次从原油中检出。研究认为，这些生物标志化合物主要来自母源。它们的分布特征为链状化合物以短链组分为主，甾醇主要为C27甾烯醇，指示成油母质主要为菌藻类；高丰度脂肪酸甘油—酯的存在，提出生物油脂是这些原油的重要成油母质。原油中存在不饱和链状化合物及其高的CPI值和甾烯醇都说明原油具有低的成熟度。通过原油极性和烷烃化合物的对比研究，认为成油物质及其低演化产物的可溶有机质胶质组分，对原油的形成可能起了重要的作用。     

Molecular analysis of petroleum derived compounds that adsorb onto gas hydrate surfaces

Field observations have shown that some streams of water, gas and crude oil do not form gas hydrate plugs during petroleum production even when operating within thermodynamic conditions for hydrate formation. Also, when studied under controlled laboratory conditions, some oils are found to form hydrate dispersed systems whereas others form plugs. Oils with low tendency to form hydrate plugs are believed to contain natural hydrate plug inhibiting components (NICs) that adsorb onto the hydrate surface, making them less water-wet and preventing the particles from agglomerating into large hydrate clusters. The molecular structure of the NICs is currently unknown. In this work, hydrate adsorbing components were extracted from crude oils using freon hydrates as an extraction phase. The fractions were found to be enriched in polar material, and more polar material is associated with hydrates generated in biodegraded crude oils than in non-biodegraded oils. Various fractionation schemes and analytical techniques have been applied in the search for molecular characterisation. The average molecular weights were found to be approximately 500 g/mole. GC–MS chromatograms show a large UCM (Unresolved Complex Mixture). Thus, GC–MS has a limited potential for identification of compounds. A commercial biosurfactant was used as a model compound in the search for similar structures in the extracts. The results from analysis of the hydrate adsorbing components suggest that the type and structure are more important for hydrate morphology than the amount of material adsorbed.     

Adsorbed oil of gas condensate fields

The pore space of reservoir rocks has a lot of active centers capable to form different types of bonds (from hydrogen to chemical). Therefore, almost any hydrocarbon can be adsorbed to a particular extent on the internal pore surface and form an adsorbed layer, which has a definite spatial configuration and makes contact with a certain part of the rock surface. Study of gas condensate reservoirs brings up the question of the composition of adsorbed hydrocarbons. The properties of such hydrocarbons in many giant gas condensate fields are of special interest as these compounds can serve as an additional source of resources after production of mobile-gas reserves. The performed study of gas condensate reservoirs of the Karachaganak, Astrakhan, and Yamburg fields has shown that their adsorbed hydrocarbons (adsorbed oil) have polar components with sulfur and oxygen atoms.     

Simulation of thermal stress influence on the Boom Clay kerogen (Oligocene,Belgium) in relation to long-term storage of high activity nuclear waste: I. Study of generated soluble compounds

Closed pyrolyses were performed on the Boom Clay kerogen to simulate the weak thermal stress applied during the in situ CERBERUS heating experiment (80 °C for 5 a). Two stronger thermal stresses, encompassing the range generally considered for the long-term disposal of high-activity nuclear waste (80 °C for 1 ka and 120 °C for 3 ka), were also simulated. Quantitative and qualitative studies were carried out on the products thus generated with a focus on the C₁₂₊ fraction, especially on its polar components. It thus appeared that the soluble C₁₂₊ fractions generated during these simulation experiments comprise a wide variety of polar O- and/or N-containing compounds, including carboxylic acids and phenols. The nature and/or the relative abundance of these polar compounds exhibit strong variations, with the extent of the thermal stress, reflecting the primary cracking of different types of structures with different thermal stability and the occurrence of secondary degradation reactions. These observations support the idea that the compounds, generated upon exposure of the Boom Clay kerogen to a low to moderate thermal stress, may affect the effectiveness of the geological barrier upon long-term storage of high-activity nuclear waste.     

酒西盆地石油非均质性的控制因素

运用先进的分析测试手段对来自酒西盆地六个油田的 2 0多个油样进行了全油碳同位素、饱和烃气相色谱与质量色谱及正构烷烃分子碳同位素等较为全面的分析与研究。确定源岩相、水洗、生物降解作用与成熟度不是酒西盆地石油非均质性的控制因素。最后选取 1 5个油样进行中性吡咯氮化合物分析,用中性吡咯氮中的咔唑类化合物作为运移参数,较为详细地研究原油的运移分馏作用。此类化合物作为运移参数的基本原理是石油运移过程中,不同结构的咔唑类化合物与水及岩石中矿物发生吸咐作用的强烈程度不同,导致不同的运移分馏作用。根据咔唑类化合物的变化得出控制酒西盆地石油组成非均质性的主要因素是油气运移分馏作用,证实酒西盆地石油运移方向主要是从西至东,青西凹陷是其油源区。     

大别-苏鲁超高压变质岩研究新思路: 偏光显微镜阴极发光技术的应用

利用偏光显微镜阴极发光技术可观察到其他常规成分结构测试法不易识别或容易忽略的多种矿物的生长结构, 该技术是进行后续成分分析的有效预研究手段, 可为重建矿物形成演化过程提供重要信息.该技术在国际岩石矿物学、油气储层及矿床学领域应用广泛, 但在变质岩研究领域的应用较薄弱.综述该技术在国际超高压变质岩研究领域的应用, 并利用其对大别-苏鲁超高压变质带经典地区的超高压榴辉岩、云母片岩、大理岩进行初步研究, 讨论它在多期微细矿物相快速鉴别、生长环带、微量元素分布规律、双晶纹、出溶结构等内部结构表征方面的应用价值和前景.偏光显微镜阴极发光技术与拉曼光谱、扫描电镜、电子探针等分析技术相结合, 可为我国超高压变质岩的研究开辟和扩展一条新思路.      

水体中挥发酚测定中的流动注射分光光度法研究进展

挥发酚是水体中的重要污染物,对生态环境和人体健康有着严重的危害,美国环保署已将11种酚类化合物列入环境优先污染物之中。文章概括了挥发酚的气相色谱法、蒸馏后溴化容量法、重量法、薄层色谱法、液相色谱法、光度法等检测方法的特点,重点介绍了流动注射分光光度法在挥发酚测定中的原理及在水质分析中的应用,讨论了该法的影响因素,包括缓冲溶液pH、氧化剂、空气峰以及实际水样的影响,并对这一领域的发展趋势进行了展望。引用文献54篇。     

Molecular level analysis of long term vegetative shifts and relationships to soil organic matter composition

Soil organic matter (SOM) is one of the earth’s largest reservoirs of actively cycled carbon and plays a critical role in various ecosystem functions. In this study, mineral soils with the same parent material and of similar approximate age were sampled from the same climatic region in Halsey, Nebraska to determine the relationship between overlying vegetation inputs to SOM composition using complementary molecular level methods (biomarker analyses and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy). Soil samples were collected from a native prairie and cedar and pine sites planted on the native prairie. Free and bound lipids isolated from the pine soil were more enriched in aliphatic and cutin-derived compounds than the other two soils. Cinnamyl type lignin-derived phenols were more abundant in the grassland soil than in the pine and cedar soils. Acid to aldehyde ratios (Ad/Al) for vanillyl and syringyl type phenols were higher for the pine soil indicating a more advanced stage of lignin oxidation (also observed by ¹³C NMR) in the soil that has also been reported to have accelerated carbon loss. In agreement with the more abundant aliphatic lipids and cutin-derived compounds, solid state ¹³C NMR results also indicated that the SOM of the pine soil may have received more aliphatic carbon inputs or may have lost other components during enhanced decomposition. The observed relationship between vegetation and SOM composition may have important implications for global carbon cycling as some structures (e.g. aliphatics) are hypothesized to be more recalcitrant compared to others and their accumulation in soils may enhance below ground carbon storage.     

Research and Application of New Methods to Oil-Gas Geochemical Exploration

Based on the results of researches and applications for many years, it has been discovered that new methods and techniques for geochemical exploration of oil and gas such as AC, altered carbonate, Hg in absorption phase, Ks, Fe2+ ,δ13C, fluorescence in two and three dimensions, and N2 and O2 in heat release can give full play in the following five fields: (1) optimization of the favourable target or hollow zones and structural zones in a region; (2) evaluation of oil traps and delineation of prospective oil and gas areas; (3) prediction of deep-seated oil-bearing horizons; (4) evaluation of the genesis of oil and gas geochemical anomalies and determination of the types of oil and gas accumulations; (5) forecast of the burial depths of oil and gas pools.     

奥连特盆地斜坡带原油地化特征、充注模式及勘探实践

奥连特盆地斜坡带原油油品分布复杂,重质原油开发难度大、不经济,中轻质原油分布规律不清,严重制约斜坡带油气勘探。本文从原油地化分析入手,通过分析原油分布特征和地化特征,明确重油成因机理,建立原油充注模式,指出中轻质油有利发育区,以有效指导油气勘探。研究结果如下:(1)斜坡带原油正构烷烃具有前峰型碳分布形式,表明原油主要为海相母源;(2)原油具有“双低+双高”族组成,表明原油为烃源岩低熟-成熟阶段产物;(3)重油主要为生物降解成因,证据1为:饱和烃总离子流图发育UCM现象,证据2为:检测发现25-降藿烷标志性化合物;(4)地化分析表明同一样品中同时存在降解原油和未降解原油特征,表明原油为两期充注成因;(5)据此建立油气两期充注模式:早期常规原油充注,中期原油普遍遭受生物降解,原油变重,晚期常规原油充注与降解原油混合控制平面原油油品分布特征,并指出斜坡带砂岩尖灭条带下倾方向是常规油有利分布区,部署探井、评价井获得了成功。     

Progress in Study of Potash Resources of Oil (Gas) Field Brine in China

With a population of 1.3 billion, China is a large agricultural country. However, China is short of potash resources as the external dependence is more than 50% for many years. With the limited possibility for increasing potash reserves from surface salt lakes, and the challenge of finding potash deposit from marine strata has not been yet overcome, the oil (gas) field brine resources has become the preferred source for the urgent needs of potash. In recent years, a lot of exploration and research work on the oil (gas) field brine has been done under the guide of “oil and potash co-exploration” policy and delightful achievements have been obtained. The research achievements at Qaidam Basin, Sichuan Basin, Jianghan Basin and Tarim Basin were summarized in the present paper. All of the above basins are the most important areas with great prospects of oil (gas) field brine. This paper mainly focused on three aspects, the brine characteristics, the brine geochemistry and resource assessment. After the summary, the characteristics of oil (gas) field brine and the progress in study of that were gotten in different basins. It was suggested that the research work of (gas) field brine at Qaidam Basin should be emphasized. It was concluded that the evaluation work of oil (gas) field brine resources is insufficient at the four basins, and it is urgent to establish oil (gas) field brine resources evaluation criteria and methods.     

面向灾害风险评估的热带气旋路径及强度随机模拟综述

历史热带气旋记录时间序列较短空间差异大,热带气旋灾害风险评估经常面临样本不足,特别是超强台风及巨灾记录历史样本的问题,从而导致传统概率统计方法失效。过去20多年来,逐渐发展出一套完整的方法体系进行热带气旋路径及强度随机模拟,其特点是充分利用历史总体样本信息,生成大量符合历史样本特征的热带气旋路径及强度随机事件样本集,从而有效地解决了局地历史样本不足的问题。在回顾热带气旋的年频次、季节分布、路径分布、强度及影响范围时空规律研究进展基础上,系统综述了用于热带气旋路径及随机模拟的起始点模型、行进模型、终止点模型、洋面强度模型、陆地衰减模型及结果检验方法等领域的进展及不足,然后对其在世界各地的应用进行了概述,并对未来研究改进方向及应用领域进行了展望。     

Characterization of fresh and weathered petroleum for potential impacts to soil fertility

In many petroleum-producing regions, there are not adequate controls to prevent pipeline breaks and spills, and thus soil is frequently contaminated with petroleum hydrocarbons. Different petroleum oil compounds may produce negative impacts on soil fertility. In this study, four fresh crudes, a weathered petroleum, and oils from bioremediated and burned sites were investigated (specific gravities 0.83–1.27). Fourier transform infrared spectroscopy revealed three predominant polar functional groups to be more plentiful in the heavier crudes. The relative abundance of these groups was used to calculate an index that was directly correlated with specific gravity (R ² = 0.9960) and the percent of asphaltene plus (polars + resins) fractions in the oil (R ² = 0.9643). This index correlated exponentially to the water repellency caused by petroleum in an alluvial soil (R ² = 0.9928). Furthermore, extra-heavy oil at a concentration of 10,000 ppm, the maximum allowable oil concentration in the soil that is within regulatory norms in many US states and other countries, and with a specific gravity >1.002, showed severe water repellency. This study presents an alternative for determining soil remediation criteria based on the API gravity of the oil rather than the C-range of the hydrocarbon mixtures, simplifying analytical methods and systematically studying the interaction between the kinds of petroleum mixtures and potential impacts to soil fertility.     

一种有效的油气成藏研究手段——有机包裹体生物标志物分析：以渤海中部沙东南构造带为例

包裹体生物标志物分析实现了包裹体烃与储层烃的直接对比，是目前最有效的有机包裹体成分分析方法之一。由于一般情况下成熟早期原油密度较高，其中高分子量的生物标志物浓度亦高，因此，虽然该方法为群体包裹体分析结果，事实上包裹体生物标志物主要反映早期烃流体的特征，因而该方法可用于追朔油气成藏过程中石油组成的变化。本文详细介绍了压碎法包裹体烃生物标志物分析方法，并应用该方法分析了渤海中部沙东南构造带油气成藏过程。认为沙垒田凸起上CFD11-1油田的原油为沙河街组与东营组下段混合来源，其成藏过程是：早期沙河街组一段、三段形成的成熟度低到中等的油首先充注在近凹陷的构造中(如CFD18—2构造)，晚期(上新世时)东营组下段成熟油及沙河街组生成的高成熟油充注近凹的构造，并将早期注入的成熟度相对低的油向构造高部位排驱，排驱过程中有部分晚期生成的油气混合一起进入浅层，在远离凹陷的凸起上成藏(CFD11-1油藏)。作者认为，在近凹的低凸起及潜山构造是寻找轻质油和天然气的有利区带。     

Demethylated hopanes in crude oils and their applications in petroleum geochemistry

Analyses of some Australian crude oils show that many contain varying concentrations of A/ B-ring demethylated hopanes. These range from C₂₆ to C₃₄ and have been identified from their retention times and mass spectral data as 17α(H)-25-norhopanes. Comparison of hopane and demethylated hopane concentrations and distributions in source-related, biodegraded oils suggests that demethylated hopanes are biotransformation products of the hopanes. Further, it appears that the process occurs at a late stage of biodegradation, after partial degradation of steranes has occurred. Demethylated hopanes are proposed as biomarkers for this stage of severe biodegradation. The presence of these compounds in apparently undegraded crude oils is thought to be due to the presence of biodegraded crude oil residues which have been dissolved by the undegraded crude oil during accumulation in the reservoir sands. The timing of hopane demethylation, relative to the degradation of other compounds, has been assessed and the progressive changes in crude oil composition with increasing extent of biodegradation have been identified. The use of demethylated hopanes as maturity parameters for severely biodegraded crude oils, and the applicability of established biomarker maturity parameters to such oils, are also discussed.     

Neuro-fuzzy modelling in mining geochemistry: Identification of geochemical anomalies

Local and mine scale exploration models for anomaly recognition within known ore fields are discussed. Traditional geochemical exploration methods are based on multivariate statistical analysis, metallometry, vertical geochemical zonality and criteria of natural field geochemical associations, which suffer several shortcomings, including lack of a geostatistical generalised approach for separating anomalies from background. These shortcomings make the interpretation process time consuming and costly. Fuzzy set theory, fuzzy logic and neural network techniques seem very well suited for typical mining geochemistry applications. The results, obtained from applying the proposed technique to a real scenario, reveals significant improvements, comparing the results obtained from applying multivariate statistical analysis. Computationally, the introduced technique makes possible, without exploration drilling, the distinction between blind mineralisation and zone of dispersed ore mineralisation. The methodology developed in this research study has been verified by testing it on various real-world mining geochemical projects.