Geochemical characterization of aromatic hydrocarbons in crude oils from the Tarim,Qaidam and Turpan Basins,NW China

Based on the systematic study of aromatic hydrocarbons in over 100 crude oil samples collected from the Tabei and Tazhong uplifts in the Tarim Basin,the western depression area in the Qaidam Basin and the Tabei depression in the Turpan Basin,the geochemical characteristics of the marine（Tarim Basin）,saline lacustrine（Qaidam Basin）,and swamp（Turpan Basin） oils were investigated.The marine oils from the Tarim basin are characterized by relatively low abundance of diaromatic hydrocarbons such as biphenyl and naphthalene,and relatively high abundance of triaromatic hydrocarbons including phenanthrene,dibenzothiophene and fluorene.In contrast,the swamp oils from the Turpan Basin are dominated by the highest relative abundance of diaromatic hydrocarbons and the lowest relative abundance of triaromatic hydrocarbons in all the oil samples in this study.The relative abundance of diaromatic and triaromatic hydrocarbons in the saline lacustrine oils from Qaidam Basin is between that in Tarim oils and Turpan oils.Aromatic parameters based on the isomer distributions of dimethylnaphthalenes（DMN）,trimethylnaphthalenes（TMN）,tetramethylnaphthalenes（TeMN） and methylphenanthrenes（MP）,i.e.,1,2,5-trimethylnaphthalene（TMN）/1,3,6-TMN ratio,1,2,7-TMN/1,3,7TMN ratio,（2,6-＋2,7-）-dimethylnaphthalenes（DMN）/1,6-DMN ratio,1,3,7-TMN/（1,2,5-＋1,3,7-）TMN,1,3,6,7-TeMN/（1,3,6,7-＋1,2,5,6-＋1,2,3,5-）-TeMN ratio and MP index,may reflect the diversity of organic source input,thermal maturity and depositional environments.In addition,the dibenzothiophenes（DBTs）/fluorenes（Fs） and dibenzofurans（DBFs）/Fs ratios were found to the very useful and effective in determining genetic types of crude oils for the marine,saline lacustrine,and swamp depositional environments,and for oil-oil correlations.

Treatment of tunnel wash waters-experiments with organic sorbent materials.PartⅠ:Removal of polycyclic aromatic hydrocarbons and nonpolar oil

Tunnel wash waters characterize all waters that run off after washing procedures of tunnels are performed.These waters represent a wide spectrum of organic and inorganic pollutants,such as polycyclic aromatic hydrocarbons(PAHs)and toxic metals.Removal of such contaminants from water runoff was investigated using laboratory tests after washing procedure was performed on two road tunnels in eastern Norway(Hanekleiv and Bragernes).Due to diverse character of both,treatment media and treated wash waters, the wh...

Direct Fingerprinting Polycyclic Aromatic Hydrocarbons in Heavy Oils by PY-GC/MS and Its Application to Hydrotreating Processes

An efficient analytical method combining pyrolysis and capillary GC/MS has been developed for determination and quantitation of targeted polycyclic aromatic hydrocarbons.The limit of detection ranged from 0.29 μg/g to 43.46 μg/g,and repeatability values were between 0.1% and 8.2% for blank spiked samples and between 0.1 % and 9.8% for real samples of heavy oils.Through application of the proposed method in hydrotreating processes,it has been found out that heavy oils before and after the specified hydroprocessing treatment exhibited a diverse PAHs distribution which might be determined by the discrepancy in their intrinsic contents and hydrogenation reactivity.Furthermore,the hydrogenation reactivity of different polycyclic aromatic hydrocarbons was further investigated and discovered to be more interrelated to molecular structure and rings alignment or conjugation mode.

Transport and behavior of marine oil spill containing polycyclic aromatic hydrocarbons in mesocosm experiments

Polycyclic aromatic hydrocarbons(PAHs)are one of the most important groups in oil,and re sponsible for major toxic and/or carcinogenic impact on humans and wildlife.It is important to understand the behavior of PAHs in marine environment after an oil-spill incident.However,interaction between petroleum PAHs and microbial communities in a marine environment remains unclear.Therefore,a series of mesocosm experiments were conducted.in which water-accommodated fraction(WAF)of oil was generated to simulate an oil-spill scenario and to analyze the transport and behavior of marine oil spill containing PAHs with and without dispersants.Results indicate that the application of dispersant could increase the concentration of total PAHs in water column due mainly to significant increase in the concentration of highmolecular weight(HMW)PAHs at a lower removal rate.At the end of the 7-day experiment,significant amount of HMW PAHs were accumulated in sediment.In general,the application of dispersant did not increase the sediment uptake of PAHs but increased the PAHs concentration in water column.

Geochemical characteristics of aromatic hydrocarbons in saline lacustrine crude oils and their significance as exemplified by the south area of western Qaidam Basin

Based on quantitative GC-MS analysis of 40 crude oil samples collected from the south area of western Qaidam Basin,one of the largest saline lacustrine basins in China,the geochemical characteristics of aromatic hydrocarbons in oils were studied systematically in this paper.Among those constitutes,naphthalene(43% 59%),phenanthrene(12% 21%) and taromatic-sterane series(6% 28%) were the main ones of aromatic hydrocarbons.The ratio of aromatic hydrocarbon maturity parameter vs.saturated hydrocarbon maturity parameter C 29 20S/(20S+20R) shows that some aromatic hydrocarbon maturity parameters are not suitable for low-mature oils,including MPI,MNR,DNR,etc.Meanwhile,maturity parameters for dibenzothiophene and taromatic-sterane series are more appropriate for low maturity saline lacustrine crude oils.Based on the ratio of 4,6-DMDBT/1,4-DMDBT,the R c values are within the range of 0.59% 0.72%.However,the abundance of dibenzothiophene(DBT) is low,and the dibenzofuran(DBF) content is even lower,suggesting that the crude oils were formed in a saline lacustrine anaerobic environment.The high abundance of C 26 triaromatic steroid also indicates that the source material is brackish water-saline water with strong reducibility.

Geochemical characteristics of aromatic hydrocarbons in crude oils from the Linnan Subsag, Shandong Province, China

Abundant aromatic fractions were detected in oils from the Linnan subsag, including aphthalenes, phenanthrenes, triaromatic steroids, biphenyl, fluorenes, dibenzothiophenes, dibenzofuranes, as well as some typical higher plant-sourced compounds, such as pyrene, benzopyrene, fluoranthene, chryaene, benzofluoranthrene, perylene and cadalene. Occurrences of biomarkers indicate that oils from the Linnan subsag are typical terrestrially genetic oils. Developed in the depositional environment is a strong reduction condition typical of brackish-saline lake. Thermal evolution has entered into the mature-high mature stage.

Carbon isotopic compositions of mono-, di-, tri-aromatics provide insights into the source of sulfur-rich crude oils in the Huanghekou Depression, Bohai Bay Basin

The stable carbon isotope compositions (δ13C) of individual aromatic hydrocarbons have been analyzed in sulfur-rich and sulfur-lean crude oils from the Huanghekou Depression, Bohai Bay Basin. The δ13C values of individual aromatic hydrocarbons, including alkylbenzenes, alkylnaphthalenes, alkylphenanthrenes, alkylfluorenes and alkyldibenzothiophenes, are reported. The main aims are to find out the origin of these oils and their relationship to paleoclimate. The distribution of aromatic hydrocarbons and maturity parameters show the oils all stay in the low-mature to mature stage. Meanwhile, aromatic hydrocarbons are mainly derived from the diagenetic/catagenetic origin. The δ13C values for 1,2,4-trimethylbenzene (−30.7‰ to −28.8‰) and 1,2,3,4-tetramethylbenzene (−32.4‰ to −26.3‰) indicate the algae-derived organic matter for alkylbenzenes. Some isomers, such as 1,7-+1,3-+1,6-dimethylnaphthalene, 1,2,5-trimethylnaphthalene, 1,2,5,6-+1,2,3,5-tetramethylnaphthalene, 1,10-+1,3-+3,10-+3,9-dimethylphenanthrenes, 1,6-+2,9-+2,5-dimethylphenanthrenes and 4,9-+4,10-+1,9- dimethylphenanthrenes show isotopic depletion (−34.9‰ to −25.2‰), indicating the major contribution of algae for these compounds. Meanwhile, isotopically depleted (−33.6‰ to −26.7‰) alkyldibenzothiophenes represent the algae input. δ13C values for mainly algae-derived naphthalene to trimethylnaphthalenes of sulfur-rich oils are more enriched than those of sulfur-lean oil, with the most significant difference of 4.4‰, indicating that the aridity of the environment and stratified water column result in the enrichment in 13C.

Status quo of soil petroleum contamination and evolution of bioremediation

Along with the rapid development of oil industries internationally,petroleum prospecting and exploitation activities are growing intensively.Especially in China,with the fastest economic growth in the world and shortage of petroleum resources,we are leading the practices of petroleum deep exploitation.Obviously,the risk of damage to the natural environment from these activities is high.Oil contamination in soils and groundwater is becoming a big issue along with pesticide pollution,which makes organic pollution prevention and control （OPPC） much more complex.In this paper,based on recent research on oil-contaminated soil at home and abroad,we make comments on the remediation technologies for polluted soil,emphasizing bioremediation techniques and degradation mechanisms in order to push forward research into bound organic pollution prevention and control （OPPC）,especially in China.

Emissions of particulate matter and associated polycyclic aromatic hydrocarbons from agricultural diesel engine fueled with degummed,deacidified mixed crude palm oil blends

Mixed crude palm oil （MCPO）, the mixture of palm fiber oil and palm kernel oil, has become of great interest as a renewable energy source. It can be easily extracted from whole dried palm fruits. In the present work, the degummed, deacidified MCPO was blended in petroleum diesel at portions of 30% and 40% by volume and then tested in agricultural diesel engines for long term usage. The particulates from the exhaust of the engines were collected every 500 hr using a four-stage cascade air sampler. The 50% cut-off aerodynamic diameters for the first three stages were 10, 2.5 and 1μm, while the last stage collected all particles smaller than 1 μm. Sixteen particle bounded polycyclic aromatic hydrocarbons （PAHs） were analyzed using a high performance liquid chromatography. The results indicated that the size distribution of particulate matter was in the accmnulation mode and the pattern of total PAHs associated with fine-particles （〈 1 μm） showed a dominance of larger molecular weight PAHs （4--6 aromatic rings）, especially pyrene. The mass median diameter, PM and total PAH concentrations decreased when increasing the palm oil content, but increased when the running hours of the engine were increased. In addition, Commercial petroleum diesel （PB0） gave the highest value of carcinogenic potency equivalent （BaPeq） for all particle size ranges. As the palm oil was increased, the; BaPeq decreased gradually. Therefore the degununed-deacidified MCPO blends are recommended for diesel substitute.

Alkyl Naphthalenes and Phenanthrenes:Molecular Markers for Tracing Filling Pathways of Light Oil and Condensate Reservoirs

Condensates and light oils are generally characterized by high maturity, low concentration of sterane and terpane biomarkers and low content of non-hydrocarbon fraction. As a result, some commonly-used sterane, terpane and carbazole migration parameters in conventional oil reservoirs may have a certain limitation in condensate and light oil reservoirs for their poor signal-noise ratios in the gas chromatography-mass spectrometry （GC-MS）. Naphthalene, phenanthrene and their methylated substituents, however, are present in significant concentrations in condensates and light oils. Taking the Fushan depression （in the Beibuwan Basin, Northern South China Sea） as an example, this paper attempts for the first time to use polycyclic aromatic hydrocarbon （PAH）-related parameters to trace migration directions and filling pathways for condensate and light oil reservoirs. The result shows that TMNr （i.e. 1, 3, 7-TMN/（1, 3, 7-TMN ＋ 1, 2, 5-TMN）, TMN： trimethylnaphthalene））, MPI-1 （i.e. 1.5×（2-MP ＋ 3-MP）/（P ＋ 1-MP ＋ 9-MP）, P： phenanthrene MP： methyiphenanthrene）, MN/DMN （∑methylnaphthalene/∑dimethylnaphthalene, %） and MN/TMN （∑nethylnaphthalene/∑trimethylna- phthalene, %） can be used to trace the filling pathways of condensate and light oil reservoirs. These parameters, together with geological consideration and other bulk oil properties （e.g. the gas to oil ratio and density）, suggest that the condensates and light oils in the Huachang oil and gas field are mainly sourced from the Bailian sag that is located to the northeast of the Huachang uplift in the Fushan depression.

Laboratory Investigation into the Evaporation of Natural-Gas Condensate Oils: Hints for the Sanchi Oil Spill

The Sanchi oil tanker collision in the East China Sea on January 6th, 2018 has caused worldwide attention due to its uniqueness. A considerable amount of highly volatile natural-gas condensate oil was spilled, burned and sank with the Sanchi tanker, this entirely new kind of maritime disaster has posed massive unknowns to the public. In this study, for better understanding of the evaporative behavior of condensate oils, two condensate oils were investigated under various laboratory conditions. The overall result demonstrates that the evaporation of condensate oils is highly dependent on the air-exposed time and the total loss of condensate oils could be more than 90% within a short time. However, a certain amount of the high-molecular weight and toxic oil contents such as phenanthrenes still highly remain in the aquatic system even after a long evaporation process, indicating their detrimental potentials to the aquatic organisms. Based on these data, for the Sanchi oil spill accident, it is assumed that although the evaporation weathering of the total condensate oil mass is probably tremendous, the long-term ecological risks of the remaining oil components in the marine environment are strongly recommended to be carefully evaluated.

Aromatic Hydrocarbons as Indicators of Origin and Maturation for Light Oils from Panyu Lower Uplift in Pearl River Mouth Basin

Aromatic fractions of six light oils and two source rock samples from Panyu（番禺） lower uplift of Pearl River Mouth basin were analyzed using GC-MS（gas chromatography-mass spectrometric） technique.Thirteen aromatic series of hydrocarbons detected such as biphenyls,naphthalenes,phenanthrenes,dibenzothiophenes（more than two hundred aromatic hydrocarbon compounds） were used to analyze the origin and maturity of the light oils.This study indicates that the distribution of aromatic hydrocarbon compounds in the light oils of wells L1 and P1 differs from those of wells P2,P3 and P4.The light oil samples from wells L1 and P1 contain more dibenzofuran and fluorence hydrocarbons and less naphthalene hydrocarbons.The contents of fluorene,dibenzothiophene and dibenzofuran in the two groups of light oils also show their difference in sedimentary environment.Moreover,the diversity of the relative distributions of biphenyl and naphthalene is apparent between the two groups of light oils.As mentioned above,the origin of the light oils from wells L1 and P1 varies from that of wells P2,P3 and P4.According to the result of oil-source correlation,the light oils from wells P2,P3 and P4 mainly originated from the source rocks in the Enping（恩平） Formation.Accordingly,the light oils from wells L1 and P1 may have been derived from the lacustrine shales in the Wenchang（文昌） Formation or from the mixed source of the Wenchang Formation and the Enping Formation.Applying maturity parameters of methylnaphthalenes,methylphenanthrenes and methyldibenzothiophenes from the aromatic hydrocarbons to the study of the maturity of light oils from Panyu lower uplift indicates that the maturity has reached the high mature stage.

Typical end-member oil derived from Cambrian-Lower Ordovician source rocks in the Tarim Basin, NW China

Based on GC-MS data of saturate and aromatic hydrocarbon fractions in crude oils from Well TD 2 and the Yingmaili and Tazhong area in the Tarim Basin, the end-member oil derived from Cambrian-Lower Ordovician source rocks was determined. The analytical results show that the crude oil from Well TD2 is rich in 3-6 ring polycyclic aromatic hydrocarbons without alkyl group, suggesting that this oil was altered by an abnormally thermal event. It contains a complete series of normal alkanes and 25-norhopanes,

The distribution characteristic and its significance of compound specific isotopic composition of aromatic hydrocarbon from marine source rock and oil in the Tarim Basin, western China

Aromatic hydrocarbons are generally main distillation of crude oil and organic extract of source rocks. Bicyclic and tricyclic aromatic hydrocarbons can be purified by two-step method of chromatography on alumina. Carbon isotopic composition of in- dividual aromatic hydrocarbons is affected not only by thermal maturity, but also by organic matter input, depositional envi- ronment, and hydrocarbon generation process based on the GC-IRMS analysis of Upper Ordovician, Lower Ordovician, and Cambrian source rocks in different areas in the Tarim Basin, western China. The subgroups of aromatic hydrocarbons as well as individual aromatic compound, such as 1-MP, 9-MP, and 2,6-DMP from Cambrian-Lower Ordovician section show more depleted 13C distribution. The δ13C value difference between Cambrian-Lower Ordovician section and Upper Ordovician source rocks is up to 16.1%o for subgroups and 14%o for individual compounds. It can provide strong evidence for oil source correlation by combing the δ13C value and biomarker distribution of different oil and source rocks from different strata in the Tarim Basin. Most oils from Tazhong area have geochemical characteristics such as more negative δI3Cg_Mp value, poor gam macerane, and abundant homohopanes, which indicate that Upper Ordovician source rock is the main source rock. In contrast, oils from Tadong area and some oils from Tazhong area have geochemical characteristics such as high 613C9-MP, value, abun dant gammacerane, and poor homohopanes, which suggest that the major contributor is Cambrian-Lower Ordovician source rock.

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 YH1 (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.

Oil and gas potential assessment for coal measure source rocks on absolute concentration of n-alkanes and aromatic hydrocarbons

Absolute concentration of normal alkanes(n-alkanes) and aromatic hydrocarbons in bitumen extracted from source rocks in the period of thermodegradation from Turpan-Hami Basin suggests that aromatic hydrocarbons are dominant in coal and carbargilite while n-alkanes are dominant in mudstones. Bulkrock analysis and gas chromatograph/mass spectrum(GC-MS) of source rocks shows aromatic hydrocarbons are dominant in total ion chromatograms(TIC) of samples with poor perhydrous macerals while n-alkanes are dominant in TICs of samples with abundant perhydrous macerals. The identification of oil-prone and gas prone property based on GC-MS of bitumen "A" together with bulkrock analysis indicates that source rocks from Shengbei area are more oil-prone while source rocks from Qiudong and Xiaocaohu areas are more gas-prone,coinciding with the distribution of oil and gas reservoirs in Taibei Sag. Ratios used to identify oil-prone and gas-prone property for source rocks from Turpan Basin are proposed:n-alkanes >110 μg·mg-1,aromatics <15 μg·mg-1,and n-alkanes/aromatics >8 for oil-prone source rock bitumen while n-alkanes<82 μg·mg-1,aromatics >40 μg·mg-1,and n-alkanes/aromatics <1.5 for gas-prone source rock bitumen.

Preliminary Study on PAHs Distribution in High-grade Oil Shale and Its Spontaneous Combustion Product in Fushun,Liaoning Province

Spontaneous combustion of oil shale is very common as a result of long-time exposure to the air in the Fushun West Open-Pit Mine and West Dump. The PAHs in the high-grade off shale and its spontaneous combustion product were analyzed semiquantitatively by GC-MS in order to investigate their distribution in different states and their potential negative effects on the environment. Totally 57 and 60 PAHs and their alkyl homologues were identified in the two analyzed samples, among which the alkyl derivatives were predominant, taking up to about 65% in the total PAHs. Those low-molecular mass PAHs （3- or 4-ring） were the main compounds in the two samples. Ten of sixteen USEPA priority pollutant PAHs were detected in two samples, of which phenanthrene was the richest whose contents were 6.93% and 15.03%. Based on comparison of analysis results, the amount and contents of PAHs, except for triaromatic steroid group, were higher in the burning oil shale. So it can be determined that the effects caused by spontaneous combustion of oil shale would be more serious and that the effects of the Fushun oil shale and its spontaneous combustion on the environment should not be ignored in the future work.

Molecular Organic Geochemistry of Crude Oils from the Albertine Graben, Uganda： Possible Implications on the Expulsion of the Oils from the Source Rocks

Twelve representative crude oil samples recovered from six oil fields in the Albertine Graben, Uganda were chosen for this study. The study aimed to understand the genetic relationships between the oils, the inferred depositional environment of the source rocks, maturity of the crude oils, and to gain some insight on the expulsion of the oils from source rocks. The work involved geochemical bulk analysis （asphaltene and liquid chromatographic separations）, GC-FID （gas chromatography with a flame ionization detector）, and GC-MS （gas chromatography-mass spectrometry） of saturate and aromatic fractions. Bulk analysis shows that the oils are dominated by saturate hydrocarbon fractions （48.7%-62.0%） and are highly waxy （35-56.2 wt%） with low sulfur content （〈 0.1 wt%）. The high saturate hydrocarbon and high wax contents are probably due to organic matter input from land plants and/or long-chain alkanes from fresh water algae in lacustrine systems. The low sulfur contents alongside the high wax abundances are consistent with elastic-dominated source rock facies deposited in a non-stratified lacustrine environment. Data from GC-FID and GC-MS analyses such as n-alkane distributions, pristane/phytane ratios, biomarker terpane and sterane, dibenzothiophene and phenanthrene parameters show that the oils belong to a single family and were derived from a elastic predominantly algal source rock deposited under suboxic conditions in a non-stratified freshwater to brackish water lacustrine environment. The data further show that the oils have a very narrow range of maturities and are generated in the peak oil window. The observed narrow range of maturities and inferred lacustrine depositional setting for the source rocks suggest that the kerogen responsible for the generation of the oils is likely to be predominantly type-1 known to display narrow activation energies. This in turn implies that the expulsion of the oil from the source rock occurred as a quick single event hence, the filling of reservoirs in the Albertine Graben probably did not involve late stage expulsion and multiple charges of oil.

Bioprospecting of Hydrocarbonoclastic Representative Bacteria

This study was designed and carried out to characterize hydrocarbonoclastic microbial communities in soil polluted with artisanal refined hydrocarbon at Trans Amadi, Phalga Local Government Area of Rivers State, Nigeria. Heterotrophic bacteria count ranged from 8.0 × 105 cfu/gm for sample TSAS1, and 2.1 × 106 cfu/gm for sample TSAS2 while TSAS3 was too numerous to count (TNTC). Hydrocarbon utilizing bacteria count ranged from 1.1 × 105 cfu/gm for TSAS1, and 5.9 × 104 cfu/gm for TSAS2, while TSAS3 was 5.4 × 104 cfu/gm. Physiochemical parameters of the soil were determined. The ranges obtained were pH 6.6, conductivity 125 μs/cm, temperature 27.3°C, moisture 7.72, total nitrogen 0.056%, phosphate 1.554 ppm, potassium 145.87 ppm, lead 7.02 ppm, cadmium 0.41 ppm, nickel 1.96 ppm, copper 1.14 ppm, total petroleum hydrocarbon 1487.24181 ppm, polycyclic aromatic hydrocarbon 12.85287 ppm. Isolates of hydrocarbon utilizing bacteria characterized belonged to the genera Escherichia coli, Klebsiella sp., Lactobacillus sp., Enterobacter sp., Serratia sp., and Proteus sp. The findings in this study have revealed the abilities of these groups of bacteria to be employed in bioremediation/biodegradation clean-up practices. Thus the polluted soil may harbour important genera of bacterial species that may have beneficial applications in environmental microbiology for future remediation processes.