HPLC-DAD-FD联用检测油气化探样品的芳烃

在成功实现HP1090型高效液相色谱仪(拥有DAD)和LS50型荧光分光光度计连接的基础上,建立了一套适合于检测油气化探样品中芳烃组分的高效液相色谱分析方法,大大提高了检测方法的选择性和灵敏度.该技术不仅解决了油气化探样品中芳烃组分的定性定量问题,提高了油气预测的准确性,而且也可在油与油、油与源对比,探索油气运移特征等有机地球化学研究中发挥重要作用.     

次火山热变质煤的物理测试特征

样品采自伊敏褐煤盆地中一个因次火山活动形成的烟煤区,包含了从褐煤到瘦煤的变质系列。红外光谱分析表明,煤的含氧基团在褐煤阶段已开始消失,烷基和芳环同步增加,在R°=1.10%时达最大值。顺磁共振自由基浓度和X-衍射参数La/Lc介于区域变质煤和岩浆接触热变质煤之间,芳核外官能团的热演化超前于芳核骨架及R°的演化。     

ASE3OO与快速索氏抽提仪处理沉积岩样品的地化参数对比

本文对加速溶剂萃取仪(ASE300)和快速索氏抽提仪提取的氯仿沥青“A”及由其分离出的饱和烃、芳烃、胶质和沥青质组分做了详细对比.结果表明:多数情况下ASE300抽提出的氯仿沥青“A”的量比快速索氏抽提仪抽提出的量略多,主要是胶质和沥青质量的增加;不同抽提装置得到的饱和烃和芳烃组分的色谱-质谱谱图高度一致,定量结果的相对偏差在5％以内.各组分的稳定碳同位素分析精度±0.5‰.所有的地化参数表明ASE300完全可以替代快速索氏抽提仪,从而降低消耗、提高分析效率.     

有机显微组分X射线衍射分析方法在油气评价中的应用

Ｘ射线衍射分析法适宜于分析有机显微组分的芳环层的层状结构。有机质的芳环层结构与其类型和演化程度有关。表征有机质芳环层的层状结构的主要参数：高度Ｌｃ、宽度Ｌａ、网面间距ｄｈｋ１和芳环层层数可作为油气勘探中判断源岩性质、类型、演化程度与生烃潜力的依据。文章还对参数的变化与意义进行了初步讨论。     

A new low-interference characterization method for hydrocarbons occluded inside asphaltene structures

Some hydrocarbons occluded inside asphaltene structures can be considered to be “original oil”, and are very important especially for severely post-altered crude oil in related geochemical studies such as oil/oil, oil/source correlation. The use of oxidising reagents could properly release these occluded hydrocarbons, and make possible direct study of these compounds without interference from the segments chemically bonded to the asphaltene molecule. Interference from adsorbed and/or co-precipitated compounds can be avoided by applying an asphaltene purification procedure.     

Geochemistry of biotite from charnockitoids in the granite-forming series (Nimnyr Block of the Aldan Shield)

The geochemical evolution of biotite (Bt) from garnet-bearing associations in the granite-forming series of the Nimnyr Block (Aldan Shield) is considered. The series includes the primary rock (gneiss or basic rock), autochthonous enderbite- or charnockite-gneiss (Lc1), migmatitic leucosome (Lc2, Lc4), and paraautochthonous charnockite (Lc3-ch1) and (Lc5-ch2 → grn). Bt in each series is characterized by an individual, significant difference in the concentrations of Ti, V, Cr; rarely Al, Fe, Mg, and Rb; and very rarely La, Ce, Nd, and Gd. The uniform trend of evolution of Bt compositions in the series was established for Al, K_Al, (K + Na)/Al, rarely for Mg, Ti, and К. In contrast to the series with ch2, Bt becomes enriched in LREEs from autochthonous Lc1 to allochthonous Lc2 and Lc3. The different compositional variations of Bt in relation some minor elements is explained by the different composition of the material, which underwent melting, temperature variations (from 820 to 750°C), and changes in pH of the mineral-forming medium.     

吐哈盆地台北凹陷侏罗系煤系源岩地球化学分类及意义

烃源岩的沉积环境、母源输入与有机质性质有着密切联系,吐哈盆地台北凹陷不同层系、不同地区侏罗系煤系烃源岩由于其沉积环境、母源输入的不同,导致其地球化学指标差异;通过对源岩地球化学指标相关性分析表明,姥植比（Pr/Ph）是反映源岩沉积氧化还原环境和水体盐度的重要指标;C29ααα20R在C27～C29规则甾烷ααα20R中的相对含量也是反映沉积水体盐度的重要指标。同时发现源岩类型划分的主控指标是族组成中芳烃、沥青质组分含量及饱芳比、非沥比等四项指标,姥植比、伽马蜡烷指数为源岩类型划分的次控指标,据此将台北凹陷侏罗系煤系烃源岩划分为三类。     

Peculiarity of ultrametamorphism in the juncture zone of the Aldan shield and Dzhugdzhur-Stanovoi folded area

The processes of ultrametamorphism in the juncture zone between the Aldan shield and Stanovoi folded area are manifested in granitization (volume-for-volume replacement of gneisses by trondhjemite gneisses Lc1) and subsequent migmatization with formation of several leucosome generations Lc2, Lc3, Lc4, and Lc5, which is confirmed by U-Pb zircon dating. It was established that the granitization stage is marked by the input of Si, Na, and Ba and removal of practically all major (including K) and minor elements. Formation of migmatite leucosomes is accompanied by further depletion in transition (Ti, Mg, Fe, V, Cr, Ni) and light rare-earth (La, Ce, Nd, and Eu) elements, and accumulation of HFSE (Pb, U, Th, Nb, Ta, Y) as well as medium and heavy rare-earth elements (Sm, Gd, Yb, Lu). Leucosomes Lc4, in addition, are enriched in K, Rb, and especially HREE due to the appearance of garnet, while Lc5 leucosomes become higher in K, Sr, and Pb. The study of relations of trondhjemite gneisses and migmatite leucosomes with protolith, geochemical features, and opposite trends in variations of Zr/Hf, Zr/Nb, Nb/La, and Eu/Eu*, and LREE/HREE ratios in the series of granitization and migmatization indicate that the trondhjemite gneisses were formed during deep-fluid-assisted infiltration granitization under the amphibolite facies conditions, while migmatite leucosomes were generated during evolving anatexis under conditions of subsequent diatexis and continuing fluid reworking. With time, the composition of the fluid changed changed, the role of K increased, and leucosomes acquired granitic composition. Unlike common K and K-Na types of ultrametamorphism, the considered juncture zone is characterized by specific type of ultrametamorphism-Na type, with formation of granitic leucosomes in subordinate amounts at the final stages.     

北羌塘盆地三叠系康南组砂岩地球化学特征及其对物源区和构造背景的制约

沉积盆地中碎屑砂岩的地球化学特征主要受物源区的制约,分析碎屑砂岩的化学成分可以揭示盆地砂岩的物源属性和构造背景。笔者对北羌塘盆地三叠系康南组碎屑砂岩进行全岩分析。样品具有高SiO2含量,K2O/Na2O值变化较大,TFe2O3+MgO含量中等。稀土元素配分模式图显示富集轻稀土元素,（La/Yb）N=3.96~9.25,平均为6.32,δEu明显负异常;δCe呈弱负异常。碱土金属元素和化学蚀变指数（CIA）以及成分变异指数（IPV）说明其源区物质较新鲜,成熟度相对较低,化学风化作用较弱-中等。此外,微量元素Th/U、La/Sc、Th/Sc等值以及TiO2-Ni、La/Th-Hf、Co/Th-La/Sc和Th/Sc-La/Sc源岩判别图解反映砂岩的物源具有长英质特征。砂岩的SiO2-K2O/Na2O、La-Th、La/Y-Sc/Cr双变量图解,La-Th-Sc、Th-Sc-Zr/10、Th-Co-Zr/10三变量图解以及Th/U、Rb/Sr等值表明北羌塘三叠系康南组碎屑砂岩的物源区构造背景以大陆岛弧为主,兼有被动大陆边缘构造背景特征。     

东营凹陷沙四段碳酸盐岩稀土元素地球化学特征

东营凹陷古近系沙河街组碳酸盐岩的成因一直存在湖相与海相之争。沙四段碳酸盐岩呈厚薄不等的夹层赋于陆相碎屑岩中。本文对研究区代表性碳酸盐岩样品稀土元素地球化学特征的分析表明:东营凹陷古近系沙四段碳酸盐岩的∑LREE > ∑MREE > ∑HREE,MREE相对于HREE富集;不具备Ce/Ce^*负异常特征;Y/Ho值为25.5~34.1,La/La^*值为0.99~1.21;Y/Ho-La/La^*呈负相关关系。所有这些特征均与湖相成因碳酸盐岩一致,沙四段碳酸盐岩的形成应为湖相成因。     

塔里木盆地寒武系原油微量元素特征及意义

塔里木盆地是中国最大的内陆含油气盆地,有关盆地内主力烃源岩层位时代目前仍存在一定争议。油-油对比能够 发现原油间的亲缘关系,明确不同类型原油地球化学特征,是解决这一问题的有效手段。中深1井及中深1C井发现的中寒 武统阿瓦塔格组、下寒武统肖尔布拉克组原油可以作为重要的端元油类型参与油-油对比。本文通过对比两种寒武系原油 及盆地内多种轻质原油微量元素组成,发现根据多种过渡金属元素比值进行聚类分析可将盆地内轻质原油分为I类和II类, Cr/V,Ni/Mn,Ni/Mo比值是原油分类的良好指标。I类原油较II类原油具有较低的Cr/V比及较高的Ni/Mn与Ni/Mo比,表明 其烃源岩沉积环境相对还原。本次分类结果与前人有机地球化学研究相符,表明无机地球化学指标可作为原油分类的重要 参考,具有较大的应用潜力。     

注水开发过程中原油的水洗作用初探

注水开发过程中的水洗作用是一个以往被忽略,但又十分重要的问题.通过对3口井、时间间隔为20年的6个原油样品系统的地球化学测试与对比研究,探讨了注水开发过程中水洗作用对原油的改造作用以及各种地球化学参数的变化特征和规律.结果表明,在注水开发过程中,水洗作用对芳烃的影响远大于饱和烃,主要表现在芳烃组分的含量明显降低,一些芳烃类化合物的含量和芳烃参数也发生了显著的变化.认为这些变化是注水开发过程中原油遭受水洗作用的特征性标志,并对油源对比和油气运移等研究具有参考意义.     

The Neoproterozoic Kolet Um Kharit bimodal metavolcanic rocks, south Eastern Desert, Egypt: a case of enrichment from plume interaction?

Neoproterozoic metavolcanic rocks of Kolet Um Kharit (KUKh) in the southern Eastern Desert of Egypt have been traditionally regarded as a bimodal island-arc sequence. However, geological and geochemical arguments presented here make this interpretation doubtful. Geochemically, these rocks are classified into mafic (tholeiitic basalts) and felsic (high-K rhyodacites to rhyolites) groups. Both the KUKh mafic and felsic metavolcanic rocks show similar geochemical characteristics, implying a genetic link. They have comparable trace element ratios, such as Zr/Nb (27–30 vs. 20–36), Y/Nb (5.44–6.25 vs. 5.05–5.9), K/Rb (577–1164 vs. 573–937), Ba/La (4.29–25–9 vs. 11.4–16.2), Nb/Yb (1.82–2.03 vs. 1.76–1.99). Similarly both groups have parallel LREE-enriched patterns (La/Yb_CN=2.37–2.81 vs. 2.55–3.17); and negative Nb and Ta anomalies (Nb/La_pm=0.51–0.58 vs. 0.45–0.52 and Ta/La_pm=0.51–0.62 vs. 0.49–0.55). The observed negative Nb and Ta anomalies in the KUKh metavolcanic rocks cannot be attributed to crustal contamination or fractional crystallization. These rocks could represent either a remnant of break-up LIP or were derived from an enriched mantle source containing subduction components beneath an intraoceanic back-arc basin. The recognition of the KUKh rocks as derived from an enriched mantle source revives interest in models that involve enrichment from “plume” interaction during the evolution of the Arabian-Nubian Shield.     

内蒙古西部额济纳旗祥探8井华力西期风化壳 原油地球化学特征

根据对祥探8井华力西末期风化壳原油地球化学特征的分析,原油具有饱和烃含量高,芳烃、非烃、沥青质含量低和全油C同位素轻的特点,生物标志化合物藿烷系列具有C30藿烷含量高,伽马蜡烷含量相对较高等特点,指示生烃母质类型好,沉积环境为高含盐的还原环境,烃源岩演化程度较高。与祥探9井烃源岩生物标志化合物特征一致,指示与石炭系烃源岩具有良好的亲缘关系。     

内蒙古西部额济纳旗祥探8井华力西期风化壳原油地球化学特征

根据对祥探8井华力西末期风化壳原油地球化学特征的分析,原油具有饱和烃含量高,芳烃、非烃、沥青质含量低和全油C同位素轻的特点,生物标志化合物藿烷系列具有C30藿烷含量高,伽马蜡烷含量相对较高等特点,指示生烃母质类型好,沉积环境为高含盐的还原环境,烃源岩演化程度较高。与祥探9井烃源岩生物标志化合物特征一致,指示与石炭系烃源岩具有良好的亲缘关系。     

北羌塘三叠系康鲁组沉积岩地球化学特征及其物源区和构造背景分析

沉积盆地中碎屑沉积岩的地球化学特征主要受物源区的制约。对北羌塘盆地三叠系康鲁组碎屑沉积岩进行全岩测试,分析表明,样品的成分变异指数(ICV)和化学蚀变指数(CIA)变化不大,反映其源区物质较新鲜,成熟度相对较低,化学风化作用较弱-中等。岩石SiO₂含量普遍较高,TFe₂O₃+MgO含量相对较高,但K₂O/Na₂O比值变化较大。微量元素标准化蛛网图与后太古代页岩和上地壳相似,且REE配分模式图显示富集LREE,δEu明显负异常以及δCe呈弱负异常。此外,Th/U、La/Sc、Th/Sc、Ba/Sr等微量元素比值以及TiO₂-Ni、La/Th-Hf、Co/Th-La/Sc和Th/Sc-La/Sc判别图表明沉积物物源具有浅源、长英质的特征。沉积岩的SiO₂-K₂O/Na₂O、La-Th、La/Y-Sc/Cr双变量图解和La-Th-Sc、Th-Sc-Zr/10、Th-Co-Zr/10三变量图解,以及Th/U、Rb/Sr等比值特征表明北羌塘三叠系康鲁组沉积砂岩的物源区构造背景以大陆岛弧为主,兼有大洋岛弧和被动大陆边缘构造背景特征。     

Characterization of nC7-soluble fractions of the products from mild oxidation of asphaltenes

A significant quantity of hydrocarbons (including alkanes) is occluded in the skeleton of the asphaltene molecule. The hydrocarbons are probably remnants of the “original oil” which had been retained within the asphaltene matrix and protected from the secondary alteration processes that occurred subsequently in the oil reservoirs. In this work we report that oxidation of asphaltenes by stirring with 30%H₂O₂–HAc or NaIO₄–NaH₂PO₄ can release nC₇-soluble oxidized products, including the occluded hydrocarbons. Characterization of the nC₇-soluble fractions of oxidized products can be applied to highlight some geochemical problems, such as in studies of oil–oil correlation, oil–source correlation and secondary alterations of oil reservoirs. It will be especially useful to recover the original geochemical information of some oil reservoirs heavily degraded by post-depositional processes.     

内蒙古西乌旗地区晚石炭世石英闪长岩的岩石成因及构造意义

内蒙古西乌旗地区出露一些石英闪长岩,其LA-ICP-MS锆石U-Pb年龄为(304.64±0.82)Ma和(309.84±0.86)Ma,表明这套岩石形成于晚石炭世。地球化学分析表明,西乌旗地区石英闪长岩属于低Ti O2和高Al2O3钙碱性玄武岩系列;富集Rb、Ba、K大离子亲石元素(LILE),亏损Nb、Ta、Ti、P等高场强元素(HFSE),具有典型弧岩浆岩的特征,显示岩浆源区曾经历过俯冲带流体的交代作用;稀土元素丰度偏低,呈LREE富集HREE亏损的右倾模式;强不相容元素比值(La/Nb、La/Ta等)及判别图解表明晚石炭世石英闪长岩类似大陆边缘弧玄武岩,岩浆来源于浅部岩石圈地幔,系石榴石+尖晶石二辉橄榄岩源区中等程度(10%~20%)部分熔融的结果。综合研究区样品的地球化学特征,结合区域地质资料及对比分析前人成果,认为早石炭世末期西乌旗地区在强烈拉张的裂谷环境下形成了有限洋盆,由于洋盆发育不成熟或边伸展边向两侧俯冲—消减,形成了西乌旗地区类似大陆边缘弧玄武岩特征的晚石炭世石英闪长岩。     

Determination of naphthenic acids in crude oil by chemical ionization mass spectrometry

Naphthenic acids in petroleum are considered a class of biological markers. Their potential use in source correlation and as an indicator of biodegradation was reported in the past ( Dzidic et al. ,1988 ; Behar and Albrecht, 1984). Due to their highly complicated properties, detailed characterization of the acids is difficult. A method based on positive ion CI (chemical ionization) mass spectrometry using isobutane reagent gas to produce ( M 15)^ ions was applied to the analysis of naphthenic acid esters. Since the complex mixture of naphthenic acids cannot be separated into individual components, only the determination of relative distribution of acids classified in terms of hydrogen deficiency was possible. The identities and relative distribution of fatty and mono-, di-, tri-, and higher polycyclic acids were obtained from the intensities of the ( M 15 )^ ions according to z-series formula CπH2π 2 O2 of naphthenic acids. The components are characterized on the basis of group type and carbon number distributions. A comparison of the FAB and CI results showed that the group type distributions obtained bv both methods agree surprisingly well.The results indicated this method is simple, rapid and easy to operate. The geochemical implication of naphthenic acids was investigated by using a set of well-characterized crude oil samples. It is found that the naphthenic acid distribution can be used as a fingerprint for oil-oil and oil-source correlations.