Characterization of high molecular weight biomarkers in crude oils

High-temperature gas chromatography (HTGC) has enhanced our ability to characterize hydrocarbons extending to C₁₂₀ in crude oils. As a result, hydrocarbons in waxes (> C₂₀) have been observed to vary significantly between crude oils, even those presumed to originate from the same source. Prior to this development, microcrystalline waxes containing hydrocarbons above C₄₀ were not characterized on a molecular level due to the analytical limitations of conventional gas chromatography. Routine screenings of high pour-point crude oils by high-temperature gas chromatography has revealed that high molecular weight hydrocarbons (> C₄₀) are very common in most oils and may represent 2% of the crude oil. Precise structures, origins, and significance of these high molecular weight compounds remain elusive. As a preliminary step to expand our knowledge of these compounds their general molecular structures and formulas have been investigated in this study. Initial results suggest that the major high molecular weight compounds include a homologous series of n-alkanes, methylbranched alkanes, alkylcyclopentanes, alkylcyclohexanes, alkylbenzenes and alkylcycloalkanes.     

Identification and geochemical significance of some aromatic components of coal

The aromatic fraction of a Homestead, Kentucky, coal extract was analyzed by combined gas chromatography-mass spectrometry using glass capillary columns. The aromatic fraction was further analyzed by gas chromatography using sulfur specific flame photometric detection. Seventy-eight compounds were identified, some of which have been traced to their possible biological origins. Sulfur-containing aromatic compounds are thought to originate from reaction of elemental sulfur or pyrite with hydrocarbons.     

油藏色谱指纹非均质性形成机理及其稳定性实验模拟

从油田开发动态地球化学监测的基本地质概念模型出发，应用油藏流体非均质性理论，分析了不同地质时期原油色谱指纹变化的地质因素。通过指纹GC／MS鉴定和实验模拟地下不同温度和不同时间的开采条件，分析了油藏开采过程中色谱指纹的变化规律。结果表明：原油色谱指纹稳定性主要和化合物的性质、含量以及色谱柱分离度有关。油藏开采过程中，适当碳数范围内的原油色谱指纹在井底和井口的不同温度条件下以及同一单层在一定的观测时间范围内具有稳定性。研究结果对进一步开拓原油色谱指纹在油田开发管理中的应用具有重要的理论价值。     

Distribution of carbazole derivatives in petroleum

Carbazole, its alkyl derivatives and higher benzologs have been selectively isolated from six different crude oils. In all samples, benzocarbazoles are major constituents of a series which may extend up to dibenzocarbazole derivatives. The distribution includes unsubstituted parent compounds and shows a maximum content of methyl and dimethyl substituted species. Sixteen individual constituents have been identified by means of comparison with reference compounds using gas chromatography, mass spectrometry and high resolution spectrofluorimetry. So far, no generally acceptable explanation has been given for the origin of these compounds, which presumably are the most stable ones in their respective series of aromaticity. Thus, carbazole derivatives may result from a complex sequence of reactions during kerogen formation, not allowing the recognition of precursing molecules. The geochemical significance of this series of nitrogen compounds needs to be clarified, requiring further studies.     

Study on identification of leather industry wastewater constituents and its photocatalytic treatment

The present research work was intended to find out the useful information on identification, separation and photocatalytic degradation of organic compounds present in leather industry wastewater. The separation of organic compounds present in leather industry wastewater was carried out by solvent extraction. The separated crude extracted products were purified through column chromatography and characterized by UV–vis spectrophotometer, gas chromatography–mass spectrophotometer, liquid chromatography–mass spectrophotometer, ¹H and ¹³C Fourier-transform nuclear magnetic resonance spectroscopy. The elemental analysis of wastewater and solid residue was carried out by inductively coupled plasma-optical emission and X-ray fluorescence spectroscopy. The organic compounds such as nonadec-1-ene, 2-phenylethanol, 2,4-di-tert-butylphenol and other organic compounds in the leather industry wastewater were identified. Out of these organic compounds, 2-phenylethanol was photocatalytically degraded using standard Degussa P-25 TiO₂ (100 mg) photocatalyst under the irradiation of UV light. Result has been shown that 2-phenylethanol was transformed into 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol then the prolonged time (30 h) irradiation leads to 100 % degradation of 2-phenylethanol. Further possible degradation mechanism of 2-phenylethanol was proposed based on the electrospray ionization mass spectrometry analysis of degraded samples. The degradation of 2-phenylethanol was confirmed by chemical oxygen demand analysis of degraded samples. The physicochemical parameters such as pH, color, chemical oxygen demand, total dissolved solids, electrical conductivity and ionic chromatography analysis of the leather industry wastewater were also measured.     

Aliphatic hydrocarbons in the bitumens of the Puertollano oil shales

The aliphatic fraction of the bitumens from 3 bands of the Puertollano oil shale field have been studied by gas chromatography and gas chromatography/mass spectrometry. Previous work published over the last years reached different conclusions about the origin of the organic matter in the Puertollano oil shales. A reappraisal of some of the biomarkers was then needed for a better understanding of the aliphatic hydrocarbons assemblage. The identified compounds, mainly n-alkanes in the medium to high boiling point region, acyclic isoprenoids and hopane-related compounds point towards a predominant algal/bacterial input. No unequivocally higher plant derived biomarkers have been detected in significant amounts, suggesting that the bulk of the organic matter derive from authocthonous organisms living in the basin. The biomarker maturity ratios indicate that the 3 Puertollano oil shales have similar maturities and are close to the onset of oil generation, assessing a slightly higher maturity than that determined by petrographic techniques.     

Nitrogen-heterocyclic compounds in meteorites: significance and mechanisms of formation

Samples of the Murchison (C2), Murray (C2) and Orgueil (C1) carbonaceous meteorites were analyzed for nitrogen-heterocyclic compounds using gas chromatography, cation and anion exclusion liquid chromatography and mass spectrometry. The purines adenine, guanine, hypoxanthine and xanthine were identified in formic acid extracts of all samples, in concentrations ranging from 114–655 ppb. Purines have not previously been found in the Murray meteorite and adenine. hypoxanthine and xanthine have never simultaneously been detected in meteorite extracts. All four biologically significant purines, as well as the pyrimidine uracil have now been identified in these meteorites. A number of other, previously reported N-heterocyclic compounds such as certain hydroxypyrimidines and s-triazines could not be detected in any of the extracts. Laboratory data indicated that both these classes of compounds may be formed from structurally simple precursors (such as guanylurea in the case of s-triazines) during the extraction and analysis of meteorite extracts.We find that the suite of N-heterocyclic compounds identified in meteorites do not, at present, permit a clear distinction to be made between mechanisms of synthesis such as the Fischer-Tropsch type and other candidates. Secondary reactions and conversions in meteorite parent bodies, of HCN and other nitriles produced by Miller-Urey type reactions as well as by Fischer-Tropsch type reactions, must also be considered.     

Curtisite,idrialite and pendletonite,polycyclic aromatic hydrocarbon minerals: Their composition and origin

The rare polycyclic aromatic hydrocarbon minerals curtisite, pendletonite and idrialite have been analyzed by chromatography, and ultraviolet and mass spectrometry. Pendletonite is nearly pure coronene; the other minerals contain over 30 homologous series of CH, CHS and CHN compounds, with the total number of chemical components well above one hundred. The chemistry of the contributing compounds reflects the origin of the minerals in medium-temperature pyrolysis of organic matter. The components were further modified by extended equilibration at elevated temperatures in the subsurface and by recrystallization during migration. In this last step the high-melting pendletonite achieved its exceptional purity.     

土壤中25种有机氯农药和多氯联苯的气相色谱分析方法研究

研究了土壤中17种有机氯农药和8种多氯联苯组分的气相色谱分析方法。采用加速溶剂萃取技术提取,优化了萃取条件。提取液用固相萃取技术进行净化,采用20 mL含3%(体积分数)甲苯的正己烷-乙酸乙酯(体积比8∶2)进行淋洗,得到很好的净化效果。方法检出限在0.06~0.27μg/kg,线性范围在1.38~55.2 ng/mL,目标化合物的平均添加回收率在65%~97%,相对标准偏差(RSD,n=6)小于17.11%。方法快速、灵敏、准确,适合批量样品的分析。     

Methylbiphenyl,ethylbiphenyl and dimethylbiphenyl isomer distributions in some sediments and crude oils

Petroleum samples and organic extracts from two sedimentary sequences have been analysed using capillary gas chromatography and GC-MS techniques for isomeric methylbiphenyls, ethylbiphenyls and dimethylbiphenyls. The relative abundances of isomers with substituents in the ortho positions decrease with increasing depth (maturity) in both sedimentary sequences. Accordingly, these compounds appear to offer potential as indicators of thermal maturity of sediments.     

胜利油田孤岛原油中有机硅化合物的发现及其石油地质意义

采用溶剂萃取法从胜利油田孤岛原油中分离得到浓缩的含氧化合物，再用柱色谱分离得到有机硅及其它组分。用红外、电子能谱、气相色谱－质谱法分离鉴定了有机硅组分。鉴定出的有机硅化合物有硅Ｓｉ₃－Ｓｉ₇的甲基硅氧烷和Ｓｉ₃－Ｓｉ₅的环甲基硅氧烷以及三甲基硅的衍生物。资料表明:在高等和低等生物体中还不能肯定含有Ｓｉ－Ｃ键的有机化合物。因此，原油中有机硅化合物的发现是原油无机成因的一个证据。本文还简要讨论了位于勃海湾盆地孤岛原油的无机成因的地质环境及其石油地质意义。     

重稠油非烃馏分含氮硫氧化合物的综合色谱分离方法

原油及油源岩非烃馏分的研究是有机地球化学的薄弱环节，至于有关重要稠油非烃馏分的地球化学研究报道更是寥寥无几。本研究结果表明重稠油非烃馏分含氮硫氧化合物的色谱分离分析方法主要与重稠油非烃馏分含氮化合物的种类，分子量和化学性质有关，因此分离方案常常是多步色谱分离方法的有机组合。本采用多步分离，梯度洗脱的综合色谱分离方案，目的在于将主要杂原子化合物与组成原油总体的烃类和含硫芳香化合物分开，减少非烃杂原子与吸附剂的持续时间，该方案能很好的兼顾重调油中化合物种类多、分子量跨度大、极性变化范围大等特性，并且有效地分离出重现性好可用于地球化学研究的含NSO类化合物。这种方案将会给重稠油非烃组分化学研究带来一次飞跃。     

短程选择离子扫描气相色谱-质谱法检测水中15种半挥发性有机物

通过优化色谱分离条件,改进质谱扫描方式,建立了气相色谱-质谱快速测定水中15种半挥发性有机物的方法。采用多梯度升温,缩短了色谱运行时间,可在17 min内完成检测;采用短程选择离子扫描方式,提高了方法的灵敏度,获得了较低的检出限和较高的回收率。方法检出限均低于1.0 ng/L,回收率为78.0%~103.0%。     

地下水中12项半挥发性有机污染物测定的质量控制

以正己烷液-液萃取、气相色谱(电子捕获检测器)和高效液相色谱(紫外、荧光检测器)检测地下水调查样品中12项半挥发性有机污染物组分的分析为例,从水样的储存、气相色谱进样口活性评定、试剂空白检查、萃取过程中乳化现象的消除等方面总结出一些经验。参照美国EPA方法中QA/QC的经验,建立了全国地下水调查样品中半挥发性有机污染物分析过程的质量控制流程程序,通过引用质量控制图直观评价批量样品分析的满意度,实现了分析流程的受控状态。     

Distribution of volatile organic compounds around a polluted river

The objectives of this study were to investigate the species and the concentration distribution of volatile organic compounds around a heavily polluted river. Air samples were collected seasonally at different locations near the polluted river. Samples were then analyzed by gas chromatography (electron capture detector for chlorinated organic compounds and flame ionization detector for ordinary hydrocarbons). The data was then analyzed by the statistical product and service solutions software. The results showed that total of 26 species of volatile organic compounds were identified. Each individual had its own concentration distribution pattern at different seasons and aliphatic volatile organic compounds displayed much higher concentrations than most benzenoic volatile organic compounds. In aliphatic volatile organic compounds, 1,2-dibromo-3-chloropropane, hexachlorobutadiene and 1,2-dibromoetane had much higher concentrations at the nearby environment of the river and they have been claimed to be carcinogenic to some experimental animals and possibly to human. Therefore, It is in doubt that for a long term, the volatile organic compounds evaporating out of the stream may threat the health of the residents living very close to the river. The concentrations of tetrachloroethene, 1,1,2,2-tetrachloroethane, hexachlorobutadiene, dibromoetane, dichlorobenzene and sec-butylbenzene appeared at the nearby environment of the river had significant correlations (P < 0.05) with those of each other or many other volatile organic compounds.     

Vitrinite secondary fluorescence: Its chemistry and relation to the development of a mobile phase and thermoplasticity in coal

Coal fractions obtained by a progressive solvent extraction scheme and HPLC (high-performance liquid chromatography) fractionation have been examined by fluorescence microscopy. The results show that aromatic oligomers, polar compounds and a small portion of aliphatics in the mobile phase are actively and highly fluorescent. It is concluded that these compounds are fluorophors responsible for the secondary fluorescence displayed by some vitrinite. The overall secondary fluorescence of vitrinite is a complex overlapping of the fluorescence signals of these compounds with intermolecular and interphase interactions. These interactions cause a certain degree of fluorescence quenching through radiationless processes.The aromatic network system within the vitrinite is apparently too condensed to display a visible fluorescence at a rank higher than subbituminous C/B as a result of self-quenching. It is suggested that the development of a ‘mobile phase’ during the bituminous stage of coalification is responsible for the secondary fluorescence of the vitrinite, as well as its thermoplastic behavior.     

A comparison of organosulphur compounds produced by pyrolysis of asphaltenes and those present in related crude oils and tar sands

Asphaltenes and NSO fractions from a variety of oils and tar sands have been characterized by pyrolysis-gas chromatography (Py---GC) using both flame ionization and flame photometric detectors. Organosulphur compounds were not always produced by pyrolysis of the asphaltenes isolated from the biodegraded tar sand extracts although pyrolysis of the NSO fractions produced a series of thiophenes from all of the samples examined. These observations suggest that under certain conditions, asphaltene fractions may be affected by biodegradation, leading to preferential removal of the sulphur containing compounds. In addition, it was observed that Py---GC of asphaltenes permitted oils to be differentiated on the basis of their source rock lithology. Oils derived from carbonate source rocks produced thiophene/benzothiopene ratios <1 whilst the same ratio was >1 for oils derived from shales. Thiophene/dibenzothiophene ratios could be used in a similar manner.     

Organic geochemical characteristics of sediments from the anoxic brine-filled Tyro basin (eastern Mediterranean)

Soxhlet-extractable organic compounds of sediments from the anoxic brine-filled Tyro basin (eastern Mediterranean) were analyzed by gas chromatography and gas chromatography-mass spectrometry. Cholesterol and 22,29,30-trisnorhopan-21-one are the major compounds identified. The occurrence of this triterpenoid ketone, as well as 22,29,30-trisnorhop-6-en-21-one and diplopterol (both tentatively identified), is ascribed to an input of microbiota living at the brine-seawater interface.     

Effect of water washing on hydrocarbon compositions of petroleum sandstone reservoir rocks in Tarim Basin, NW China

Gross compositions and distribution of saturated and aromatic hydrocarbons in Carboniferous sandstone reservoire rocks in oil and water zones for Tzhong-10 well of the Zhongyang Uplift in the Tarim Basin were studied in dteail by means of Rock-Eval Pyrolysis,thin-chromatograph-flame ionization detection(TLC-FID),gas chromatography,gas chromatography-mass spectrometry.The results suggest that the gross composition of reservoir hydrocarbons between the oil zone and the water zone show significant differences,Water wahing has a dramatic effect on saturated hydrocarbon blomarkers,especially drimane series compounds,Drimane series compounds in the water zone have been depleted completely.However,the contents of tricyclic iterpanes and pentacyclic triterpanes tend to decrease slightly,but the water-zone reservoir hydrocarbons contian a large amount of gammacerane.This suggests that gammacerane be more resistant to water washing than diterpanes and homohopanes.The contents of pregnane,homopregrane,diasteranes relastively decrease as a result of water washing.Water washing has a noticeable effect on polycyclic aromatic hydrocarbon compounds,especially aromatic sulfur compounds,and the contents of dibenzothiophene series compounds and benzonaplyiothipophene decrease significantly as a result of water washing.However,the conterts of bicyclic and tricyclic aromatic hydrocarbons decrase slightly and those of tetracyclic and pentacyclic aromatic hydrocarbons,especially benzofluoranthene and benzopyrenes,increase markedly owing to adecrease in light aromatie hydrocarbons as a result of water washing.     

The use of high temperature gas chromatography to study the biodegradation of high molecular weight hydrocarbons

A consequence of the biodegradation of petroleum is that lower molecular weight compounds are removed preferentially to higher molecular weight (HMW) compounds greater than triacontane (n-C₃₀). The extent to which the latter compounds are biodegraded has rarely been studied. Reasons for this include the technical difficulties associated with carrying out biodegradability tests with solid, water-insoluble substances and the limits of the analytical techniques, such as gas chromatography (GC).A quantitative high temperature GC (HTGC) method was developed to monitor the biodegradation of the aliphatic fraction of a waxy Indonesian oil by Pseudomonas fluorescens. Recoveries of over 90% were obtained for n-alkanes up to hexacontane (C₆₀) using liquid-liquid continuous extraction. After only 14 days, 80% of the aliphatic hydrocarbons had been degraded. At the end of the 136-day study, 14% of the original fraction remained. This comprised mainly C₄₀₊ compounds. No decrease in the concentrations of compounds above C₄₅ was observed. However, the use of a rapid screening biodegradation method provided tentative proof that Pseudomonas fluorescens was capable of utilising n-alkanes up to C₆₀ once the bacteria had acclimated to HMW alkanes.