The global distribution of polycyclic aromatic hydrocarbons in recent sediments

Polycyclic aromatic hydrocarbons (PAH) and their alkyl homologs are distributed in sediments throughout the world. The qualitative PAH pattern is remarkably constant for most of the locations studied, and the quantitative PAH abundance increases with proximity to urban centers. These findings are consistent with anthropogenic combustion's being the major source of these compounds. Two non-combustion sources of PAH have also been noted: retene coming from abietic acid and perylene probably coming from various extended quinone pigments.     

柴达木盆地北缘中侏罗统石门沟组煤中多环芳烃分布特征及其地质意义

多环芳烃(PAHs)是古环境、古野火以及古气候的重要地质记录,本文通过气相色谱质谱法(GC- MS)研究了柴达木盆地北缘中侏罗统石门沟组煤中多环芳烃分布特征,检测出一系列二环至七环芳烃化合物,包括高等植物衍生多环芳烃(卡达烯、6- 异丙基- 1- 异己基- 2- 甲基萘、惹烯、西蒙内利烯以及二氢惹烯)和燃烧衍生多环芳烃(荧蒽、芘、苯并\[a\]蒽、、苯并荧蒽、苯并\[e\]芘、苯并\[a\]芘、茚并\[cd\]芘、苯并\[ghi\]苝和晕苯)等。这些多环芳烃的检出表明石门沟组煤沉积于具有显著陆源高等植物输入的微咸水湖沼环境,成熟度较低(平均随机反射率为056%)。石门沟组煤中高等植物衍生多环芳烃以极高的惹烯含量为特征,且存在较高丰度的西蒙内利烯和二氢惹烯,卡达烯丰度极低,反映出成煤期陆地植被类型以松柏类植物的针叶林为主,气候温暖湿润。同时,煤中丰富的燃烧衍生多环芳烃证实了柴达木盆地北缘中侏罗世存在广泛的陆地古野火,较高的大气氧气浓度(256%)可能是该时期野火频发的一个重要诱因。本次研究为柴达木盆地中侏罗世古野火事件的研究提供了重要的分子化石证据,也是对中侏罗世古环境和古气候研究的有益补充。     

Polycyclic aromatic hydrocarbons in an anoxic sediment core from the Pettaquamscutt River (Rhode Island,U.S.A.)

Fifteen sections from an anoxic sediment core were analyzed for polycyclic aromatic hydrocarbons (PAH). Two types of PAH were observed: (a) those from combustion sources such as pyrene and chrysene and (b) those from natural sources such as retene and perylene. The combustion PAH levels in core sections dated between 1900 and 1970 were much higher than in earlier sections; this indicated an anthropogenic origin of these PAH at this location. The perylene and retene core profiles show significant anomalies during the period 1850–1880. Organic carbon does not fluctuate markedly but δC-13 of organic carbon shows several unexplained excursions; one of which correlates with the perylene and retene anomalies.     

鄂尔多斯盆地盐池-定边地区长7段烃源岩芳烃地球化学特征

基于鄂尔多斯盆地盐池-定边地区13口井16块长7烃源岩样品的GC-MS分析资料,研究了源岩的芳烃地球化学特征,进行了生源和沉积环境的分析,并探讨了芳烃系列成熟度评价参数在该地区的有效性。研究结果显示:研究区源岩主要以二环和三环芳烃类化合物为主,而四环和五环芳烃类化合物较低,芴含量较高,普遍含有1,2,5-TMN和1,2,5,6-TeMN且部分样品含量偏高,并检测出一定含量的惹烯、苝、和芘等陆源高等植物生物标志化合物,表明研究区源岩形成于滨浅湖弱氧化-弱还原的环境中,高等植物的输入对该地区源岩的形成占有一定贡献。芳烃中烷基萘、烷基菲和烷基二苯并噻吩等成熟度参数表明源岩样品现今正处于成熟阶段。虽然利用不同系列芳烃类化合物求取的等效镜质体反射率存在一定差异,但能定性地反映出源岩的热演化程度。     

Biogenic and abiogenic polynuclear aromatic hydrocarbons in sediments from two remote Adirondack lakes

Sediment cores from Sagamore Lake and Woods Lake in New York State's Adirondack Park, an area remote from industrial activities, were analyzed for polynuclear aromatic hydrocarbons (PAH) by high resolution gas chromatography/mass spectrometry (GC/MS). Their composition and distribution with depth in the sediment indicate that the parental PAH in the surface sediments are primarily produced by anthropogenic combustion of fossil fuels. Perylene in deep sediments is apparently transformed from natural precursors in the reducing environment, however, the exact precursors remain unknown. The rather even sediment distributions of the non-parental PAH differ from the parental, suggesting biogenic origins. Based on their chemical structures, retene and alkylated and partially hydrogenated phenanthrenes are believed to be biogenically converted from abietic acid; hydrochrysenes and hydropicenes, from pentacyclic triterpenes.     

伊通地堑下第三系原油和生油岩中芳构化五环三萜及其地球化学意义

详细研究了吉林伊通地堑下第三系生油岩和原油中的芳烃生物标志物，包括常规的多环芳烃，以及丰富的来源于高等植物的芳香二萜和芳构化的五环三萜。目前，原油中芳构化五环三萜类生物类生物标志物国内外均尚报道极少。还详细讨论了利用原油中最新发现的芳构化五环三萜在解决本区生物输入，油源对比以及石油成因等方面的重要意义。     

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

1IntroductionTheTarimBasin ,NWChina,istheonlybasininChinawherenotonlymarine ,butalsoter restrialindustrialoilandgaspoolsaredeveloped .TheterrestrialoilandgaspoolshavebeenfoundintheKuchedepressioninthenorthernpartofthebasinanditsfrontupliftarea (Fig .1) .ThesourcerocksoftheterrestrialoilandgaspoolsareTriassicandJurassiclacustrinemudstonesandswampcoals.ThebiomarkersfromthesaturatedfractionsofTriassicandJurassicterrestrialsourcerocksandFig .1 .LocationofTriassicandJurassicterrestrialsource…     

CHARACTERISTICS OF AROMATIC HYDROCARBONS IN CRUDE OILS

Crude oils from different basins in China ,Australia and New Zealand were analyzed to character-ize aromatic hydrocarbons produced in different environments by means of GC/MS .The distributions of some common compounds such as naphthalene, phenanthrene, chrysene,pyrene, fluoranthene, fluorine,dibenzothiophene and dibenzofuran were found to be related to sedimentary environments.Especially the relative contents of fluorenes ,dibenzofurans and dibenzothiophenes can be used to di-vide the oils into three types(1) saline or marine carbonate environment;(2) fresh-brackish water lake;(3) swamp and coal-bearing sequence.A romatic biomarkers (e.g.retene, nor-abietene,derivatives of lupeol and β-amyrin)represent higher plant inpults with respect to the precursors of crude oils. High contents of sulphur-containing compounds like benzothiophene and dibenzothiophene series indicate a reducing sulphur-abundant diagenetic condition .The benzohopane series (C32-C35) was identified both in hypersaline and coal-bearing basins, and it is postulated to be the result of strong bacteria activity.In all the sam-ples, a complete series of alkyl benzenes was analyzed .The similarity of its carbon-number distrbu-tion with that of n-alkanes probably suggests their genetic relationship. The distribution of the methylphenanthrene series reflects the evolution degree of crude oils,MPI holding a positive correlation with C29-sterane 20S/(20S 20R).     

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

Ten series of aromatic hydrocarbon compounds (biphenyl, naphthalene, phenanthrene, anthracene, retene, chrysene, benzoanthracene, dibenzofuran, fluorene, dibenzothiophene) isolated from seven Triassic and Jurassic lacustrine mudstone samples and three swamp coal samples, as well as five crude oil samples collected in the Kuche depression of the Tarim Basin,NW China, have been analysed by GC-MS techniques. It is found that the relative abundances of dibenzofuran series are higher in the three swamp coal samples than those in the lacustrine mudstone samples. Based on the similar relative abundances of dibenzofuran series, especially dibenzofuran compound, in the TICs of aromatic hydrocarbons, crude oils from wells SA3 (K), YTK5(E,K) and QL1 (E) are thought to have been derived predominantly from the coals of the Lower Jurassic Yangxia Formation or Middle Jurassic Kezilenuer Formation, whereas those from wells YM7 (O) and YHI (E) were derived mainly from Triassic and Jurassic lacustrine mudstones in the Kuche depression. This is the first report about how to distinguish coal-generated oils from lacustrine mudstone-generated oils in the Kuche depression in terms of the dibenzofuran series.The present paper has enlightening and directive significance for further oil-source rock correlations and oil and/or gas exploration in the Kuche depression of the Tarim Basin.     

分子有机地球化学与古气候、古环境研究

分子有机地球化学可以从分子级水平研究地质体中有机分子化合物的演化规律。本文报道了应用生物标志化合物指标探讨古气候和古环境,例如探讨古生物(含古植物)的输入,淡水、半咸水和高盐度水古环境的判识以及大气飘尘的来源和成因等。     

东疆地区原油芳烃地球化学特征及其意义

在对东疆地区(包括吐哈盆地和三塘湖盆地)原油饱和烃生物标志物地球化学特征研究基础上,对原油芳烃馏分进行全面分析及地球化学特征研究;通过深入剖析原油芳烃系列组成,明确东疆地区原油类型划分,根据烷基奈、"三芴"系列及卡达烯、惹烯等化合物的分布特征,进一步揭示三塘湖盆地石炭系原油母源沉积水体盐度低、还原性弱,成油母质中包含丰...     

Petroleum geochemistry of the Potwar Basin,Pakistan: II – Oil classification based on heterocyclic and polycyclic aromatic hydrocarbons

In a previous study, oils in the Potwar Basin (Upper Indus) of Pakistan were correlated based on the dissimilarity of source and depositional environment of organic matter (OM) using biomarkers and bulk stable isotopes. This study is aimed at supporting the classification of Potwar Basin oils into three groups (A, B and C) using the distribution of alkylnaphthalenes, alkylphenanthrenes, alkyldibenzothiophenes, alkyldibenzofurans, alkylfluorenes, alkylbiphenyls, triaromatic steroids, methyl triaromatic steroids, retene, methyl retenes and cadalene. The higher relative abundance of specific methyl isomers of naphthalene and phenanthrene and the presence of diagnostic aromatic biomarkers clearly indicate the terrigenous and oxic depositional environment of OM for group A oil. Group B and C oils are of marine origin and the aforementioned heterocyclic and polycyclic aromatic hydrocarbons (HCs) differentiate them clearly into two different groups. The relative percentages of heterocyclic aromatic HCs reveal that the distribution of these compounds is controlled by the depositional environment of the OM. Sulfur-containing heterocyclic aromatic HCs are higher in crude oils generated from source rocks deposited in suboxic depositional environments, while oxygen-containing heterocyclic aromatic HCs in combination with alkylfluorenes are higher in marine oxic and deltaic oils. Biomarker and aromatic HC parameters do not indicate significant differences in the thermal maturity of Potwar Basin oils. Triaromatic and methyl triaromatic steroids support the division of Potwar Basin oils into the three groups and their relative abundances are related to source OM rather than thermal maturity. Significantly higher amounts of C₂₀ and C₂₁ triaromtic steroids and the presence or absence of long chain triaromatic steroids (C₂₅, C₂₆, C₂₇, and C₂₈) indicates that these compounds are probably formed from different biological precursors in each group. Different isomers of methyl substituted triaromatic steroids are present only for short chain compounds (C₂₀–C₂₂) and the origin of these compounds may be short chain methyl steranes from unknown biological precursors.     

Polycyclic aromatic hydrocarbons in the Murchison meteorite

More than thirty polycyclic aromatic hydrocarbons, including nine heterocyclic aromatic compounds, have been identified in solvent extracts of the Murchison meteorite by gas chromatography-mass spectrometry using bonded-phase fused silica columns. Structural isomers of several alkylated aromatic hydrocarbons, including methylpyrene and methylphenanthrene were chromatographically separated, thus allowing calculations of the amount of alkyl substituted compounds in the solvent extracts. The ratio of odd-carbon number to even-carbon number was found to be approximately 0.1. Based on these data and literature data from model pyrolysis experiments, a temperature of 1000°C is suggested for the formation of polycyclic aromatic hydrocarbons in the solar nebula or premeteoritic body. The value of 1000°C is within the range of temperatures for the condensation of the nebular material from the initial high temperature phases to the lower temperature phases at which chemical and isotopic equilibria were frozen. A simple model for the abiotic synthesis of heterocyclic compounds from simple aliphatic precursors is also presented.     

Influences of the basin brines on extractable bitumen of Kupferschiefer from southwestern Poland

A study of the influences of the basin brines on hydrocarbon generation of the Kupferschiefer in southwestern Poland has been carried out.The samples from the Konrad and Polkowics mines were analyzed by orgainc geochemical,microscopic and FTIR methods.The results indicate that organic matter of Kupferschiefer tends to decrease with the ascending,oxidizing brines,In the Konrad profile,the Kupferschiefer was strongly oxidized.The extract yields were depleted up to 50mg Ext/g Corg.Gas chromatography(GC) and gas chromatography-mass spctrometry(GC/MS) data indicate that the depletion occureed predominantly in saturated hydrocarbon compounds.The identified n-alkanes in smpale KD1 were depleted at least to 5000μg/g Corg.The aromatic compounds show a fidderent trend of variation.The concentrations of phenanthrene alkylphenanthrenes(Ph-PAH) and naphthalene alkylnaphthalenes(Na-PAH) show a decrease,whereas sulfur polyaromatic hydrocarbons(S-PAH)and oxygen polyaromatic hydrocarbons(O-PAH) show an incrase under the influences of oxidizing brines,In the Polkowice profile,organic matter under the influences of oxidizing fluids shows a simlar trend of varation as in the Konrad mine.Analyses of polar compounds shed light on the oxidation processes at the molecule level.The dominant products of oxidation are aliphatic acid.alcohol and ester.FTIR results indicate that the oxidation of organic matter led to a decrease in aliphatic CH3 and an increase in C-O,C=O bands.     

泥炭的热模拟研究──过渡带气形成机理探讨

本文对现代泥炭进行了低温长时间模拟实验研究,并探讨了过渡带气的形成机理。甘南泥炭气、液态烃产率高。液态烃由热解油和残余气仿沥青“Ａ”两部分组成,热解油中以Ｃ_５─Ｃ_１４较轻馏分为主,残余氯仿沥青“Ａ”则以非烃、沥青质为主。随热演化程度增高,烃类增加,非烃和沥青质急剧减少。模拟气体组成以非烃气体（ＣＯ_２等）为主,随温度升高,气态烃产率升高,烃类气体中以甲烷为主。２００℃～４００℃温度下产生的甲烷碳同位素δ１３Ｃ为－５３.８２～－３３.６６‰。研究表明低热演化阶段伴随腐殖物质的降解和干酪根的分子重排作用能产生甲烷同位素较轻的生物－热催化过渡带气。     

Polycyclic aromatic hydrocarbons (PAHs) in lake sediments record historic fire events: Validation using HPLC-fluorescence detection

Understanding the natural mechanisms that control fire occurrence in terrigenous ecosystems requires long and continuous records of past fires. Proxies, such as sedimentary charcoal and tree-ring fire scars, have temporal or spatial limitations and do not directly detect fire intensity. We show in this study that polycyclic aromatic hydrocarbons (PAHs) produced during wildfires record local fire events and fire intensity. We demonstrate that high performance liquid chromatography with fluorescence detector (HPLC-FLD) is superior to gas chromatography–mass spectrometry (GC–MS) for detecting the low concentrations of sedimentary PAHs derived from natural fires. The HPLC-FLD is at least twice as sensitive as the GC–MS in selective ion monitoring (SIM) mode for parent PAHs and five times as sensitive for retene. The annual samples extracted from varved sediments from Swamp Lake in Yosemite National Park, California are compared with the observational fire history record and show that PAH fluxes record fires within 0.5 km of the lake. The low molecular weight (LMW) PAHs (e.g., fluoranthene, pyrene and benz[a]anthracene) are the best recorders of fire, whereas the high molecular weight (HMW) PAHs likely record fire intensity. PAHs appear to resolve some of the issues inherent to other fire proxies, such as secondary deposition of charcoal. This study advances our understanding of how PAHs can be used as markers for fire events and poses new questions regarding the distribution of these compounds in the environment.     

The Discovery of Retene in Precambrian and Lower Paleozoic Marine Formations

Microscopic and SEM observations of thin sections and kerogens and GC-MS analyses of aromatic fractions in sediment extracts and pyrolysis products of kerogens provide strong evidence suggesting that in the Lower Yangtze Valley area the Sinian and Lower Paleozoic carbonate formations of marine facies received no higher plant input,but there was produced abundant retene during diagenesis and abietic acid substances are still its precursors.     

Gradual and stepwise pyrolyses of insoluble organic matter from the Murchison meteorite revealing chemical structure and isotopic distribution

To study the detailed structural and isotopic heterogeneity of the insoluble organic matter (IOM) of the Murchison meteorite, we performed two types of pyrolytic experiments: gradual pyrolysis and stepwise pyrolysis. The pyrolysates from the IOM contained 5 specific organic groups: aliphatic hydrocarbons, aromatic hydrocarbons, sulfur-bearing compounds, nitrogen-bearing compounds, and oxygen-bearing compounds. The release temperatures and the compositions of these pyrolysates demonstrated that the IOM is composed of a thermally unstable part and a thermally stable part. The thermally unstable part mainly served as the linkage and substituent portion that bound the thermally stable part, which was dispersed throughout the IOM. The linkage and substituent portion consisted of aliphatic hydrocarbons from C₄ to C₈, aromatic hydrocarbons with up to 6 rings, sulfo and thiol groups (the main reservoirs of sulfur in the IOM), and carboxyl and hydroxyl groups (the main reservoirs of oxygen). However, the thermally stable part was composed of polycyclic aromatic hydrocarbons (PAHs) containing nitrogen heterocycles in the IOM. Isotopic data showed that the aliphatic and aromatic hydrocarbons in the linkage and substituent portion were rich in D and ¹³C, while the thermally stable part was deficient in D and ¹³C. The structural and isotopic features suggested that the IOM was formed by mixing sulfur- and oxygen-bearing compounds rich in D and ¹³C (e.g., polar compounds in the interstellar medium (ISM)) and nitrogen-bearing PAHs deficient in D and ¹³C (e.g., polymerized compounds in the ISM).     

西藏措勤盆地下白垩统海相灰岩的芳烃地球化学特征

详细总结了西藏措勒盆地下白垩统海相灰岩的芳烃地球化学特征，包括萘、菲、芴、四环、五环及三芳甾烃系列化合物。总体组成以菲系列化合物占优势，四环和五环芳烃含量较高，其它芳烃含量较少为特征。样品中惹烯含量高，硫芴／氧芴值较高，且检出了一定含量的北、反映出该区海相灰岩的有机母源的多样性和具有利于有机质保存的还原沉积环境。应用萘、菲、芴、多环芳烃和三芳甾烃的各项成熟度参数分析了有机质的热演化特征，表明西藏措勤盆地下白垩统处于成熟阶段。     

Saturated and aromatic diterpenoids and triterpenoids in Eocene coals and mudstones from China

Several series of saturated, diaromatic, triaromatic C-ring cleaved and triaromatic diterpenoids and triterpenoids have been detected in 4 immature coal and mudstone samples. A number of these compounds appear to represent intermediates in a series of postulated pathways for progressive aromatization of biogenic diterpenoids and triterpenoids. Diagenetic pathways for the formation of tricyclic aromatic hydrocarbons from abietane and pimarane type diterpenoid precursors and for the formation of diaromatic, triaromatic C-cleaved and triaromatic hydrocarbons from β-amyrin and other triterpenoid precursors are proposed. Saturated and aromatized abietanes, pimaranes and phyllocladanes, which are the most abundant compounds in all 4 samples, indicate a predominant higher plant input which can be related to the Coniferales group but not to individual plant families. β-Amyrin and other triterpenoid-derived triaromatic and triaromatic C-ring cleaved hydrocarbons with triterpenoid structures are thought to be characteristic for angiosperms. The relative concentrations of the triaromatic and triaromatic C-ring cleaved hydrocarbons are higher in samples 9602 (mudstone) and 9603 (coal) than samples 9601 (coal) and 9604 (mudstone) indicating samples 9602 (mudstone) and 9603 (coal) contain relatively more angiosperm derived organic matter than samples 9601 (coal) and 9604 (mudstone). The distribution patterns and the relative concentrations of saturated and aromatic diterpenoids and triterpenoids thus are valuable markers for the determination of the relative contents of biological sources of organic material in geological samples.