美国Sunniland等地原油和油源岩中噻吩类化合物的对比研究

本文用色谱-质谱分析了美国南佛罗里达盆地Sunnliland原油和油源岩抽提物中的噻吩类化合物,并将它们与源自页岩的原油进行了对比,发现源自碳酸岩与页岩的原油有着不同的噻吩类化合物分布。结合其他地球化学参数,如:正烷烃、甾烷和萜烷,噻吩类化合物将是很有用的油-油和油-源对比工具。     

准噶尔盆地陆梁油气田原油的生物降解作用与油气成藏

1原油的生物降解现象 陆梁油气田原油可按饱和烃色谱图上正构烷烃的完整程度和m/z 177质量色谱图上25-降藿烷的存在与否,分为3类.第1类:饱和烃分布完整,不存在25-降藿烷,主要分布于中侏罗统西山窑组X4段;第2类:饱和烃分布完整但存在25-降藿烷,主要分布于中侏罗统西山窑组X1段;第3类:饱和烃分布差异较大,从仅缺损部分低碳数正构烷烃到几乎完全缺损正构烷烃,而且存在25-降藿烷,主要分布于下白垩统吐谷鲁群.原油中25-降藿烷的存在,表示了该原油曾经遭受过"严重"级别的生物降解.     

生物降解原油研究的新方法

利用沥青质包裹烃和沥青质钌离子催化氧化（RICO）产物中的生标对生物降解原油进行了研究。研究表明，虽然原油中的生标受到了严重破坏，但利用这两种方法在沥青质中均可以获得较为完整的生标系列。与其它方法相比，这两种方法简单方便，结果较为可靠、准确，可能是生物降解原油研究的发展方向。     

原油与沥青质热解产物的GC-MS分析

较严重生物降解的原油没有正构烷烃,甚至缺失类异二戊烯烃,给油源研究造成一定困难.这种降解油中沥青质含量很高,用沥青质热解可产生相当量的正构烷烃和其它的烃类成分,例如:类异戊二烯烃、甾烷、萜烷、芳烃等成分也会有所变化.本文研究它们的变化特点、变化的幅度,找出一定的规律性,以对利用原油沥青质热降解产物用于油源对比时分析它们的相似性有所帮助.实验证明,总体上看沥青质的热降解产物与原油的烃类分布上比较相似,但并不一致,有的差距比较大,应该做一些校正,有的则比较稳定可靠.     

准噶尔盆地陆梁油田部分原油生物降解程度与重排藿烷的相互关系

1原油的分类 原油生物降解现象在准噶尔盆地普遍存在,在陆梁油田部分原油中,还普遍存在新藿烷系列和重排藿烷系列.据最新研究成果表明,陆梁油田原油来自同一油源,我们本次研究准噶尔盆地陆梁油田部分原油以同一油源为前提.     

原油与沉积物中的二苯并噻吩系列化合物的GC-MS分析及其在有机地球化学中的应用

近年来,人们对原油和沉积物中二苯并噻吩类化合物进行了广泛研究,认识到该类化合物蕴藏着丰富的地质-地球化学信息,尤其在油/源和油/油对比、烃源岩和原油成熟度确定以及烃源岩沉积环境特征探讨等方面展示了广阔的应用前景。色谱-质谱技术为二苯并噻吩类化合物研究提供了良好的     

石油和生油岩中萜烷、甾烷、芳代甾烷的GC-MS分析

在有机地球化学研究中,生物标志化合物由于有明显的生物继承性、热作用敏感性、结构的稳定性,所以占有重要地位。本文仅就松辽盆地原油或生油岩中萜烷、甾烷和芳化甾烷的GC—MS分析方法和鉴定作一论述。     

用GC-MS、GC-MS-MS方法检测某些有机质成熟度参数的比较

Tm／Ts,C29甾烷ααα20S／(20S+20R)是判断原油成熟度的重要参数。所以能否准确地检测这些化合物就显得尤为关键和重要。以往我们通常采用GC-MS单极质谱来检测原油和烃原岩抽提物中饱和烃里的萜烷和甾烷成分。但利用GC-MS单极质谱分析得到的m／z191质量色谱图中,Tm、Ts往往与三环和四环萜烷同时共流出,以至有时导致假的Tm／Ts比值。利用GC-MS单极质谱分析得到的m／z217质量色谱图中规则甾烷分布受重排甾烷的影响,很难区分C29甾烷和4-甲基甾烷(即没有办法排除共流峰的干扰)。这是因为Tm、Ts和C29甾烷等生物标记化合物在特定的色谱柱中有     

原油饱和烃指纹的内标法分析

采用内标法建立了原油中正构烷烃、生物标志物(甾、萜烷类)的分析方法。确定了样品前处理方法和组分定性定量方法。讨论了柱层析分离能力。结果表明,所有饱和烃组分均流入第一部分流出液F1中,分离能力较为满意。对48种甾、萜烷类生物标志物组分以及姥鲛烷、植烷和正构烷烃等进行了定性确认,定性化合物数量多,信息量大,易于据此进行可靠的油指纹分析鉴别。32个正构烷烃组分相对标准差为1.2%～7.4%;45个生物标志物组分相对标准偏差为2.5%～9.2%。分析精密度较好,满足油指纹鉴别需要。正构烷烃回收率为73%～116%;生物标志物为84%～106%;回收率结果较为满意。正构烷烃方法检出限为7.0μg/g;生物标志物为0.65μg/g,满足原油样品分析要求。通过本方法对自不同和相同平台的原油样品进行饱和烃浓度分析,并采用浓度数据进行鉴别,结果与实际情况相符。     

吐鲁番-哈密盆地煤成油研究

吐鲁番-哈密盆地是典型的煤成油盆地,主要源岩为中、下侏罗统煤系,煤成油的主要贡献者是基质镜质体及木栓质体。原油主要地球化学特征是富含链烷烃(70％—80％)、高姥/植比(6—8)、富重碳同位素(δ~(13)C为—26‰至—23‰PDB)和C_(29)甾烷占绝对优势,煤的生烃过程具多阶性,早生早排是煤成油的基本特征。     

COMPARATIVE STUDY OF THIOPHENIC COMPOUNDS IN SUNNILAND OILS AND SOURCE ROCKS VERSUS OTHER OILS IN U. S. A.

This paper analyzed thiophenic compounds in Sunniland oils and source rock extractsfrom the South Florida Basin, USA using GC-MS, and compared them with those of oilsfrom shales. We found that oils derived from carbonates versus shales have different distribu-tions of thiophenic compounds. Used in conjunction with such other geochemical parametersas n--alkane, sterane and terpane compositions, thiophenic compounds will be a useful toolfor oil--oil and oil--source correlations.     

Chromatographic investigations on biodegraded crude oils

Summary Microorganisms have been isolated from a biodegraded crude oil from the Gifhorn trough, Lower Saxony. A non-degraded crude oil, related to the same source rock as the biodegraded one, was inoculated with the microorganisms found and the course of biodegradation thus initiated was followed by gas and liquid chromatographic techniques. The influence of biodegradation on commonly used oil-to-oil correlation parameters was investigated in detail.Originally presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984.     

Geochemical characterisation of heavily biodegraded tar sand bitumens by catalytic hydropyrolysis

Catalytic hydropyrolysis was used to release the aliphatic biomarkers covalently bound within the asphaltene structure of highly biodegraded Nigerian tar sand bitumens. Unlike the free aliphatic hydrocarbons extracted from the bitumen, the hydropyrolysis products of the asphaltenes afford aliphatic biomarkers having the characteristics of the initial unaltered oil, which had been trapped within the asphaltene matrix of the bitumen and protected from biodegradation processes. The biomarker profiles obtained allow proper characterisation of the bitumen in terms of source and thermal maturity. Catalytic hydropyrolysis is also capable of releasing aromatic hydrocarbons that can be used in the geochemical characterisation of the bitumen.     

Comparative study of electrospray and photospray ionization sources coupled to quadrupole time-of-flight mass spectrometer for olive oil authentication

The use of fast and reliable analytical procedures for olive oil authentication is a priority demand due to its wide consumption and healthy benefits. Olive oil adulteration with other cheaper vegetable oils is a common practice that has to be detected and controlled. Rapid screening methods based on high resolution tandem mass spectrometry constitute today the option of choice due to sample handling simplicity and the elimination of the chromatographic step. The selection of the ionization source is critical and the comparison of their reliability necessary. The possibilities of the direct infusion electrospray ionization (ESI) and the recently introduced atmospheric pressure photospray ionization source (APPI), coupled to quadrupole time-of-flight (QqTOF), have been critically studied and compared to control olive oil adulteration. These techniques are very rapid (approximately 1 min per sample) and have high discrimination power to elucidate key components in the edible oils studied (olive, hazelnut, sunflower and corn). Nevertheless, both sources are complementary, being APPI more sensitive for monoacyl- and diacylglycerol fragment ions and ESI for triacylglycerols. In addition, methods reproducibility's are very high, especially for APPI source. Mixtures of olive oil with the others vegetable oils can be easily discriminated which has been tested by using principal components analysis (PCA) with both ESI-MS and APPI-MS spectra. Analogously, linear discriminant analysis (LDA) confirms methods reproducibility and detection of other oils used as adulterants, in particular hazelnut oil, which is especially difficult given its chemical similarity with olive oil.     

Increasing antibiotic activity against a multidrug-resistant Acinetobacter spp by essential oils of Citrus limon and Cinnamomum zeylanicum

The genus Acinetobacter has gained importance in recent years due to involvement in serious infections and antimicrobial resistance. Many plants have been evaluated not only for direct antimicrobial activity, but also as resistance modifying agents. The Essential oil of Citrus limon (EOCL) addition at 156.25?μgmL(-1) (MIC/8) sub-inhibitory concentration in the growth medium led to MIC decrease for amikacin, imipenem and meropenem. The Essential oil of Cinnamomum zeylanicum (EOCZ) addition at 78.125?μg?mL(-1) (MIC/8) sub-inhibitory concentrations in the growth medium caused drastic MIC reduction of amikacin. Results of combining antibiotics and essential oils had shown us a synergistic effect with both essential oils/amikacin combinations. An additive effect was observed with the combinations of both essential oils and gentamicin. The results of this study suggest that essential oil of C. limon and C. zeylanicum may suppress the growth of Acinetobacter species and could be a source of metabolites with antibacterial modifying activity.     

Chemical characterization of gorse pyrolytic oils by capillary gas chromatography

Thermochemical conversion of biomass produces solid charcoal, gaseous fuels, and condensable oils. Because these oils vary widely in composition depending on the cellulosic feedstock and the operating conditions used, analysis of the oils is necessary in order to determine the best ways of utilizing or disposing of them. The major components of the organic oil from pyrolysis of gorse have been characterized by capillary gas chromatography – mass spectrometry. A qualitative study of the aqueous oil from the same source has also been attempted.     

Trace elements in Nigerian oil sands and extracted bitumens

The Nigerian oil sands are very extensive with an estimated in place reserves of bitumen/heavy oil of over 30 billion barrels. Instrumental Neutron Activation Analysis (INAA) has been used to determine the trace and minor elements in the raw oil sands and bitumens. About 43 trace elements in the raw oil sands and 30 in bitumen extracts were determined. The results are compared with values of Canadian bitumens and some Nigerian conventional light crude oils. In general, the Nigerian bitumens has higher hydrocarbon concentration than the Athabasca bitumen but slightly lower than in the Nigerian crude oils. The sulphur, vanadium and nickel contents of the Nigerian bitumens and crude oils are appreciably lower than those of Athabasca bitumen, thus indicating that the extraction and refining of Nigerian tar sand oil would pose less technological and environmental problems than the Athabasca syncrude.     

Hydrogen isotope type-curves of very hot crude oils

Several crude oil accumulations in the Pannonian Basin are trapped in uncommonly hot (>170°C) reservoirs. Their maturities range from mature to very mature on the basis of cracking parameters of their biological marker homologous series (ratio of products to reactants). A stable carbon isotopic study of these oils, poor in biological markers commonly used for correlation purposes, did not provide a reliable oil-to-oil correlation. As an alternative tool, the hydrogen isotope compositions of oil fractions separated on the basis of different polarities were measured, and hydrogen isotope type-curves were generated for a set of mature to very mature crude oil samples. This method of presenting hydrogen isotope composition of fractions as type-curves is novel. Nineteen samples (17 crude oils from SE-Hungary, 1 oil condensate and 1 artificial oil) were chosen for the present study. The aim was to examine the applicability of hydrogen isotope type-curves in oil-to-oil correlation and to test the simultaneous application of carbon and hydrogen isotope type-curves in the field of petroleum geochemistry. We have shown that, although the conventionally used co-variation plots proved to be inadequate for the correlation of these hot and mature oils, the simultaneous use of carbon and the newly introduced hydrogen isotope type-curves allows us to group and distinguish oils of different origins.     

A Multivariate Analysis on the Influence of Indigenous Crude Oil Components on the Quality of Produced Water. Comparison Between Bench and Rig Scale Experiments

A matrix of 30 crude oils have been analyzed to investigate if there is any correlation between the physiochemical properties of the crude oils and the quality of the produced water. As an approach to study produced water quality, oil. and brine water (3.5 wt%) have been mixed together, and transmission profiles from the separation process have been investigated by means of Turbiscan LAb. The Turbiscan LAb enables the study of stability of colloidal dispersions without any dilution or modification of the sample. The oil-in-water emulsions (30:70) were made by mixing oil and water at low speed to be sure that they separate within a short period of time. Drop size distributions were investigated for all crude oil emulsions by using a Coulter Counter (COULTER Multisizer II). The correlations between transmission profiles and crude oil characteristics were made by using principal component analysis (PCA), a method that helps visualize the most important information contained in a data set and find combinations of variables that describe major trends. A Vortoil K-liner hydrocyclone connected to a mixing rig has been used to separate oil and water in larger scale experiments. The objective with these experiments was to compare the results with separation experiments done at bench scale. Six crude oils have been investigated at the separation rig, and both droplet size distribution and dispersed oil concentration have been performed. The main conclusions from this work are that Turbiscan LAb is a suitable technique to study the separation of oil-in-water with good reproducibility. The results from the multivariate data analysis show that the crude oils group according to if they are light or heavy and according to if they get high or low transmission. From the larger scale experiments it has been shown that the droplet sizes, oil/water density differential, and viscosity have a significant impact on separation efficiency.     

Effects of conventional heating on the stability of major olive oil phenolic compounds by tandem mass spectrometry and isotope dilution assay

The quality of olive oils is sensorially tested by accurate and well established methods. It enables the classification of the pressed oils into the classes of extra virgin oil, virgin oil and lampant oil. Nonetheless, it would be convenient to have analytical methods for screening oils or supporting sensorial analysis using a reliable independent approach based on exploitation of mass spectrometric methodologies. A number of methods have been proposed to evaluate deficiencies of extra virgin olive oils resulting from inappropriate technological treatments, such as high or low temperature deodoration, and home cooking processes. The quality and nutraceutical value of extra virgin olive oil (EVOO) can be related to the antioxidant property of its phenolic compounds. Olive oil is a source of at least 30 phenolic compounds, such as oleuropein, oleocanthal, hydroxytyrosol, and tyrosol, all acting as strong antioxidants, radical scavengers and NSAI-like drugs. We now report the efficacy of MRM tandem mass spectrometry, assisted by the isotope dilution assay, in the evaluation of the thermal stability of selected active principles of extra virgin olive oil.