The effects of biodegradation on the compositions of aromatic hydrocarbons and maturity indicators in biodegraded oils from Liaohe Basin

By aid of gas chromatogram/mass spectrometry (GC-MS), the distributions and the compositions of biomarkers in a set of sequentially biodegraded oils from Liaohe Basin, China, have been quantitatively analyzed, and it has been found that during the biodegradation process of crude oils, the molecular maturity parameters such as Ts/Tm, homohopane C₃₁ 22S/(22S+22R) and sterane C₂₉ 20S/(20S+20R) ratios will be affected to different extent. The results show that except homohopane C₃₁ 22S/(22S+22R) ratio, Ts/Tm ratio will decrease with increasing biodegradation, but for C₂₉ 20S/(20S+20R) ratio, it will almost remain constant in slightly and moderately biodegraded oils, and then will increase quickly in severely biodegraded oils. The main reason is that there are some differences in the ability of resistant biodegradation for different isomer of biomarkers with different stereo configuration, resulting in the fact that destroying rate by bacteria for those biomarkers with weak ability will be higher than those with strong ability in resistant biodegradation. For example, 18α(H)-22,29,30-trisnorhopanes (Ts) will be destroyed more quickly than 17α(H)-22,29,30-trisnorshopanres (Tm), and 20R isomer is more quickly than 20S isomer for C₂₉ sterane, resulting in the relative ratios changed with increasing biodegradation. Therefore, much more attention should be paid to the biodegradation extent of crude oils and the type of biomarker maturity indicators, when the distributions and the compositions of biomarkers in biodegraded oils are used to determine the maturity of biodegraded oils.

     

Crude-oil hydrocarbon composition characteristics and oil viscosity prediction in the northern Songliao Basin

Crude oil hydrocarbon composition characteristics and oil viscosity prediction are important bases in petroleum exploration.A total of 54 oil/heavy-oil samples and 17 oil sands were analyzed and quantified using both comprehensive 2D gas chromatography(GC×GC)and comprehensive 2D gas chromatography/time-of-flight mass spectrometry(GC×GC/TOFMS).The results show that crude oil in the West slope is mainly heavy oil and its hydrocarbon composition is characterized overall by paraffinsmono-aromaticsnaphthenesnon-hydrocarbonsdi-aromaticstri-aromaticstetra-aromatics.Aromatics are most abundant and non-hydrocarbons are least abundant,whilst content differences among paraffins,naphthenes,aromatics,and non-hydrocarbons are less than 15%.There are two types of heavy oil,secondary type and mixing type.Biodegradation is the main formation mechanism of heavy oil.Biodegradation levels cover light biodegradation,moderate biodegradation,and severe biodegradation.With increasing biodegradation,paraffin content decreases while contents of aromatics and nonhydrocarbons increase.In contrast,naphthene content increases first and then decreases with increasing biodegradation.In severe biodegradation stage,naphthenes decrease more quickly than aromatics and non-hydrocarbons.This provides a new method for studying oil/heavy-oil biodegradation mechanism and biodegradation resistance of different hydrocarbons at different biodegradation stages.In the Longhupao-Daan terrace and Qijia-Gulong depression,most crude oil is conventional oil.Its composition is dominated by paraffins with the lowest content of aromatics.In some casual oil wells from the Longhupao-Daan terrace,crude oil from Saertu oil reservoirs is moderately biodegraded whereas crude oil from Putaohua oil reservoir is lightly biodegraded.Chemical parameters using saturate hydrocarbons and aromatics are usually not suitable for determining organic type and thermal maturity of biodegraded oil,especially of moderately or severely biodegraded oil,whilst Ts/(Ts+Tm)ratio can be used to determine thermal maturity of both conventional crude oil and heavy oil.     

Geochemical evolution during the cracking of crude oil into gas under different pressure systems

Two comparative simulation experiments(a normal atmospheric-pressure opening system and a 20 MPa closed system)were conducted to study the geochemical evolution of n-alkane,sterane,and terpane biomarkers in the process of oil cracking into gas under different pressures.With an initial experimental temperature set at 300°C,the temperature was increased to 650°C at a heating rate of 30°C/h.The products were tested every 50°C starting at 300°C,and a pressure of 20 MPa was achieved using a water column.The low-maturity crude oil sample was from the Paleogene system in the Dongying sag in eastern China.The threshold temperature obtained for the primary oil cracking process in both pressure systems was 450°C.Before the oil was cracked into gas,some components,including macromolecular n-alkanes,were cracked into medium-or small-sized n-alkanes.The secondary oil cracking of heavy hydrocarbon gases of C2–5to methane mainly occurred between 550°C to 650°C,and the parameters Ln(C1/C2)and Ln(C1/C3),as well as the dry coefficients,increased.Overpressure inhibited the oil cracking process.In the 20 MPa system,the oil conversion rate decreased,the temperature threshold for gas generation rose,and oil cracking was inhibited.Compared with the normal pressure system,high-carbon n-alkanes and other compounds in the 20 MPa pressure system were reserved.Furthermore,the parameters∑C21-/∑22+,Ln(C1/C2),and Ln(C1/C3),as well as the dry coefficients,decreased within the main temperature range.During secondary oil cracking(550°C to 600°C),the Ph/nC18and Pr/nC17decreased.High pressure influenced the evolution of the biomarkers Ts and Tm,C31homohopane,C29sterane,and their related maturity parameters to different extents during oil cracking under different temperature ranges.     

The effects of biodegradation on the compositions of aromatic hydrocarbons and maturity indicators in biodegraded oils from Liaohe Basin

By the aid of GC-MS technique, a series of sequentially biodegraded oils from Liaohe Basin have been analyzed. The results show that the concentrations and relative compositions of various aromatic compounds in the biodegraded crude oils will change with increasing biodegradation degree. The concentrations of alkyl naphthalenes, alkyl phenanthrenes, alkyl dibenzothiophene are decreased, and the concentration of triaromatic steroids will increase with increasing biodegradation degree in biodegraded oils. Those phenomena indicate that various aromatic compounds are more easily biodegraded by bacteria like other kinds of hydrocarbons such as alkanes, but different series of aromatic compounds have a varied ability to resistant to biodegradation. The ratios of dibenzothiophene to phenenthrene (DBTH/P) and methyl dibenzothiophene to methyl phenanthrene (MDBTH/MP) are related to the features of depositional environment for source rocks such as redox and ancient salinity. However, in biodegraded oils, the two ratios increase quickly with the increase of the biodegradation degree, indicating that they have lost their geochemical significance. In this case, they could not be used to evaluate the features of depositional environment. Methyl phenanthrene index, methyl phenanthrene ratio and methyl dibenzoyhiophene ratio are useful aromatic maturity indicators for the crude oils and the source rocks without vitrinite. But for biodegraded oils, those aromatic maturity indicators will be affected by biodegradation and decrease with the increase of the biodegradation degree. Therefore, those aromatic molecular maturity indicators could not be used for biodegraded oils.     

Chemical characterization of naturally weathered oil residues in the sediment from Yellow River Delta, China

With its close proximity to Shengli Oilfield, China’s second largest oilfield, the Yellow River Delta is at high risk for crude oil contamination. The massive oil discharge in oilfield may offer a chance for a natural experiment to investigate compositional changes of oil residues and study the stability of source- and weathering-dependent molecular parameters in oil residues after spills. The results demonstrate that the conventional diagnostic ratios, such as C₂₉20S/(20S + 20R), C₂₉/C₃₀H, C₃₀βα/αβ, C₃₁22S/(22S + 22R), C₂-DBTs/C₂-PHENs, C₃-DBTs/C₃-PHENs, DBT/MCHRY, CHRY/PHENs, are also valid for oil source identification even after extensive weathering of spilled oils in terrestrial environment, although some exceptions were encountered for extensively weathered sample. Moreover, the ratios of selected specific biomarkers (the oleanane index, the gammacerane index) have been developed and assessed as source indicators. Finally, we find that some maturity parameters based on alkyl naphthalenes and methyl phenanthrenes in petroleum geochemistry, such as the methylnaphthalene ratios (TMNr, TeMNr, PMNr), the methylphenanthrene ratios (MPI-1, MPDF), can be applied for the source identification and correlation at their lightly to moderately weathered stage.     

Geochemical characteristics of Tertiary Sagara oil from an active forearc basin, Shizuoka, Japan

Abstract   The Sagara oil field is located in the Neogene Kakegawa Basin, close to the Izu collision zone at the junction between the main Japanese Islands and the Izu–Bonin Arc. The Sagara oil field is one of the few oil fields situated in a forearc basin on the Pacific side of Japan and is present in a sedimentary basin with poor oil-generating potential. Several crude oils from Sagara oil field were investigated to infer their origin. Organic geochemical characteristics of Sagara oils showed the influences of light biodegradation, migration-contamination, and migration-fractionation. The maturity levels of Sagara oils evaluated based on abundant alkylnaphthalenes corresponded to 0.9–1.2% vitrinite reflectance. Sagara oils were characterized by significant amounts of higher plant biomarkers, a high pristane/phytane ratio and an absence of organic sulphur compounds, suggesting a siliciclastic source rock deposited under nearshore to fluvial–deltaic environments. Numerous faults and fractures in the active forearc basin provided excellent conduits and facilitated upward migration of light hydrocarbons generated at greater depth in the Kakegawa Basin.     

Source,depositional environment and maturity levels of some crude oils in southwest Niger Delta,Nigeria

A suite of crude oil samples,that had not been previously characterized geochemically,was collected from two oil fields in the southwest Niger Delta Nigeria.The saturate biomarkers were used to evaluate geochemical characteristics such as depositional environments,sources of organic matter and extent of biodegradation using gas chromatography-flame ionization detector and gas chromatography-mass spectrometry.Distribution of n-alkanes(Pr/Ph,and isoprenoide/n-alkanes ratios),the abundance of hopanes,oleanane skeleton and C27-C29 steranes in the oils indicate that they were formed from mixed sources(marine and terrestrial kerogen) deposited in an oxic paleoenvironment with no particular maturity trend.These parameters also permit the source grouping of the oils into two families.     

Distribution and significance of C~_(40) alkanes in the extracts of Cretaceous source rocks from the Songliao Basin

Source rock extracts and crude oils from the Songliao Basin were analyzed by high-temperature gas chromatography (HTGC), gas chromatography-mass spectrometry (HTGC-MS) and gas chromatography-isotope ratio-mass spectrometry (GC-IRMS), for high molecular-weight alkanes. The distributions of n-alkanes in the Nenjiang Formation extracts are in the C14―C63 range; a bimodal distribution occurs in the C-21 and C21―40 regions. The C30―C37 n-alkanes are accompanied by C29―C35 hopanes, whereas the high molecular-weight C45―C47 n-alkanes co-occur with abundant isoalkanes, alkylcyclohexanes and alkylcyclopentanes. The high δ 13C values of the n-alkanes and the microscopic maceral compositions indicate a highly diversified organic source input for the Nenjiang Formation source rocks, ranging from aquatic plants, blue alge-bacteria, to land plant material. In contrast, n-alkanes in the rock extracts of the Qingshankou Formation are characterized by a single modal distribution, with relatively low abundances of C29―C35 hopanes, but high molecular-weight isoalkanes, alkylcyclohexanes and alkylcyclopentanes. The relatively low δ 13C values of C22―C44 n-alkanes and organic material compositions indicate that the source rocks in the Qingshankou Formation contain dominantly type I algal organic matter. The relative abundance of C 40 compounds in source rocks changes little at low maturity stage, but decreases drastically at higher maturity levels, with a concurrent reduction in the odd/even carbon predominance. In crude oils, in contrast, the relative abundance of C 40 compounds appears to relate closely with the oil source and oil viscosity.     

Late Cretaceous paleoenvironment and lake level fluctuation in the Songliao Basin,northeastern China

Study of Late Cretaceous lacustrine sedimentary strata in the eastern Songliao Basin, China revealed that the paleoclimate was relatively arid and hot during sedimentation of the upper Santonian of the Yaojia Formation, but became relatively humid and warm during deposition of the lower Campanian Nenjiang Formation. The upper Yaojia Formation was deposited in a freshwater lake environment, while the lower Nenjiang Formation was deposited in a slightly brackish to brackish environment. The average total organic carbon content in the upper Yaojia Formation is 0.15%, while the hydrogen index is 36 mg_HC/g_TOC, implying poor source rock for oil generation and the organic matter comprised of a mixture of woody and herbaceous organic matter. In contrast, the hydrogen index of oil shale and black shale of the lower Nenjiang Formation is 619 mg_HC/g_TOC, and total organic carbon content on average is 3.37%, indicating a mixed algae and herbaceous source of kerogen and an increase in aquatic bioproductivity. The black shale and oil shale have low Pristane/Phytane and C₂₉ 5α,14α,17α(H) ? stigmastane 20R/(20R + 20S) ratios, with maximum concentration of n‐alkanes at n‐C₂₃, implying an anoxic depositional environment with algae, bacteria and higher plants providing most of the organic matter. Relatively abundant gammacerane and a higher Sr/Ba ratio in the oil shales suggest the presence of brackish water and development of salinity stratification in the lake. During sedimentation of the upper Yaojia through the lower Nenjiang Formations, the level of Songliao lake increased and a deep‐lake environment was formed with bottom waters being oxygen depleted. Concomitantly, as the lake deepened bottom conditions were changing from oxic to anoxic, and the input of organic matter changed from predominantly higher plants to a mixture of bacteria, algae and higher plants providing favorable conditions for oil source rock accumulation.     

Genetic features of gas-condensate reservoirs in the Kekeya Field,southwest depression in the Tarim Basin,China

Oils, condensates and natural gases in the Kekeya Field, southeast depression of the Tarim Basin were studied for their geochemical characteristics. According to the distribution analysis of the C₂/C₃ values with C₁/C₂ values, C₂/C₃ values with C₁/C₃ values, as well as C₂/C₃ values with dryness index, there are two different types of natural gases in the studied field, which are spatially regularly distributed. One is the oil cracking gas, located on shallow reservoirs over X ²₅ reservoir, namely Upper oil legs; the other is kerogen cracking gas, located on X ²₇ reservoirs, X₈ reservoirs and E₂ k reservoirs, namely Lower oil legs. In addition, the distribution patterns of molar concentration of oils and condensates with different carbon numbers of the n-alkanes in the Kekeya Field indicate that the crude oils have experienced several kinds of secondary alterations, which were closely related to the charging of gaseous hydrocarbons after petroleum accumulation. These results indicate that, based on the research of δ ¹³C values of individual hydrocarbons, heptane values and isoheptane values of light hydrocarbons and aromatic maturity parameters for oils, condensates and natural gases, oils and gases were charged at different geological time in the Kekeya Field.

     

Genetic features of gas-condensate reservoirs in the Kekeya Field,southwest depression in the Tarim Basin,China

Oils, condensates and natural gases in the Kekeya Field, southeast depression of the Tarim Basin were studied for their geochemical characteristics. According to the distribution analysis of the C₂/C₃ values with C₁/C₂ values, C₂/C₃ values with C₁/C₃ values, as well as C₂/C₃ values with dryness index, there are two different types of natural gases in the studied field, which are spatially regularly distributed. One is the oil cracking gas, located on shallow reservoirs over X ₅ ² reservoir, namely Upper oil legs; the other is kerogen cracking gas, located on X ₇ ² reservoirs, X₈ reservoirs and E₂ k reservoirs, namely Lower oil legs. In addition, the distribution patterns of molar concentration of oils and condensates with different carbon numbers of the n-alkanes in the Kekeya Field indicate that the crude oils have experienced several kinds of secondary alterations, which were closely related to the charging of gaseous hydrocarbons after petroleum accumulation. These results indicate that, based on the research of δ ¹³C values of individual hydrocarbons, heptane values and isoheptane values of light hydrocarbons and aromatic maturity parameters for oils, condensates and natural gases, oils and gases were charged at different geological time in the Kekeya Field.     

Compound-specific stable carbon isotopic composition of petroleum hydrocarbons as a tool for tracing the source of oil spills

With the increasing demand for and consumption of crude oils, oil spill accidents happen frequently during the transportation of crude oils and oil products, and the environmental hazard they pose has become increasingly serious in China. The exact identification of the source of spilled oil can act as forensic evidence in the investigation and handling of oil spill accidents. In this study, a weathering simulation experiment demonstrates that the mass loss of crude oils caused by short-term weathering mainly occurs within the first 24h after a spill, and is dominated by the depletion of low-molecular weight hydrocarbons (相似文献   

Organic facies and geochemical aspects in Neogene neritic sediments of the Takafu syncline area of central Japan: Paleoenvironmental and sedimentological reconstructions

Abstract Organic petrological observations of kerogen macerals and organic geochemical analyses of carbon isotopes of kerogen macerals and biomarkers were conducted on Neogene neritic sediments of the Takafu syncline area of central Japan. The Senmi, Sakainomiya and Lower Shigarami Formations in that area were deposited at the neritic provinces on the southern edge of the paleo‐Japan Sea during the Late Miocene to Early Pliocene. Sedimentary organic matter in these formations was almost terrigenous in origin. Changes in kerogen maceral compositions reflect sedimentological and tectonic histories evaluated in previous studies from sedimentary facies and paleontology. It was found that carbon isotope ratios (δ¹³C) of kerogen macerals increased from ?28‰ to ?25‰ from the Sakainomiya to the lower part of the Lower Shigarami Formations. The cause of that increase was presumably the expansion of C₄ plants into southwest Japan. The timing was concordant with that of the expansion of C₄ plant grasslands in East Asia. The oxicity (oxic to anoxic) conditions of sea bottoms evaluated from pristane/phytane ratios varied. Particularly, in the lower part of the Senmi Formation, layers in which no steroid biomarkers could be detected were found, and had presumably formed under oxic conditions when strong biodegradation had occurred. Concentrations of regular (C₂₇–C₂₉) steranes and dinosteranes were higher in the Sakainomiya and Lower Shigarami Formations. This indicates that dinoflagellates‐dominant primary productions were higher at those stages. In addition, concentrations of diatomaceous biomarkers such as C₂₆ norsterane increased from the Lower Shigarami Formation, thus adding diatoms to the major producers. Furthermore, similar associations between the increases of δ¹³C values of kerogen macerals and concentrations of diatomaceous biomarkers were observed in the Takafu syncline area. Thus, the expansion of C₄ plants was possibly associated with the high production of diatom in the shallow‐marine areas of the paleo‐Japan Sea during the Neogene Period.     

Biodegradability of the Anti-tumour Agents 5-Fluorouracil,Cytarabine, and Gemcitabine: Impact of the Chemical Structure and Synergistic Toxicity with Hospital Effluent

Most anti-tumour agents are known to be carcinogenic, mutagenic, teratogenic, embryotoxic or fetotoxic. Only little is known about the environmental impact of pharmaceuticals. Unmetabolized active substances are excreted and will show up in municipal wastewater. Therefore, we examined the biodegradability of the widely used anti-tumour agent 5-fluorouracil (5-FU), also as an example for assessing the impact of hospital effluent on the biodegradation of a test compound. The biodegradability of the structurally similar anti-tumour agents cytarabine and gemcitabine was also examined. Test systems used were the closed bottle test (OECD 301 D) and the modified Zahn-Wellens test (OECD 302 B). 5-FU was not biodegradable in the closed bottle test (CBT) nor in the Zahn-Wellens test (ZWT). At the highest concentration of 5-FU, with hospital effluent an inhibition of the degradation of substances present in hospital effluent was observed, probably as a result of a synergistic effect by 5-FU with antibiotics present in hospital sewage. Gemcitabine was biodegraded 42% in the CBT. The prolongation of the test period to 40 days only improved the result to 45%. In the ZWT, the biodegradation of gemcitabine was 50%. Cytarabine was partially biodegraded in the CBT (50%), but only after an adaptation period of 20 days. After a test prolongation to 40 days, the degree of biodegradation was 80%. In the ZWT, the biodegradability was > 95% after only a few days.     

Stability relation of (Mg,Fe)SiO3 garnets, major constituents in the Earth's interior

High-pressure and high temperature experiments at 20 GPa on (Mg,Fe)SiO₃ have revealed stability fields of two types of aluminium-free ferromagnesian garnets; non-cubic garnet and cubic garnet (majorite). Majorite garnet is stable only within a limited compositional variation, 0.2 < Fe/(Mg + Fe)< 0.4, and in the narrow temperature interval of 200°C around 2000°C, while the stability of non-cubic garnet with more iron-deficient compositions persists up to higher temperatures. These two garnets show fractional melting into iron-deficient garnet and iron-rich liquid, and the crystallization field of cubic garnet extends over Fe/(Mg + Fe)= 0.5. The assemblage silicate spinel and stishovite is a low-temperature phase, which also occurs in the iron-rich portion of the MgSiO₃—FeSiO₃ system. The sequence as given by the Fe/(Mg + Fe) value for the coexisting phases with the two garnets at 2000°C and 20 GPa is: silicate modified spinel aluminium-free garnets silicate spinel.Natural majorite in shock-metamorphosed chondrites is clarified to be produced at pressures above 20 GPa and temperatures around 2000°C. Similar shock events may cause the occurrence of non-cubic garnet in iron-deficient meteorites. Non-cubic garnet could be a stable phase in the Earth's mantle if a sufficiently low concentration of aluminium is present in the layer corresponding to the stable pressure range of non-cubic garnet. The chemical differentiation by melting in the deep mantle is also discussed on the basis of the present experimental results and the observed coexistence of majorite garnet with magnesiowüstite in chondrites.     

Terrestrial and marine biomarker estimates of organic matter sources and distributions in surface sediments from the East China Sea shelf

Revealing of the sources and distributions of sedimentary organic matter in the East China Sea (ECS) is important for understanding its carbon cycle, which has significant temporal and spatial variability due to the influences of recent climate changes and anthropogenic activities. In this study, we report the contents of both terrestrial and marine biomarkers including ∑C₂₇+C₂₉+C₃₁n-alkanes (38.6-580 ng/g), C₃₇ alkenones (5.6-124.6 ng/g), brassicasterol (98-913 ng/g) and dinosterol (125-1521 ng/g) from the surface sediments in the Changjiang River Estuary (CRE) and shelf areas of the ECS. Several indices based on biomarker contents and ratios are calculated to assess the spatial distributions of both terrestrial and marine organic matter in the ECS surface sediments, and these results are compared with organic matter distribution patterns revealed by the δ¹³C (−20.1‰ to −22.7‰) and C/N ratio (5-7.5) of total organic matter. The contents of terrestrial biomarkers in the ECS surface sediments decrease seaward, controlled mostly by Changjiang River (CR) inputs and surface currents; while higher contents of the two marine biomarkers (brassicasterol and dinosterol) occur in upwelling areas outside the CRE and in the Zhejiang-Fujian coastal zone, controlled mostly by marine productivity. Four proxies, f_Terr(δ¹³C) (the fraction of terrestrial organic matter in TOC estimated by TOC δ¹³C), odd-alkanes (∑C₂₇+C₂₉+C₃₁n-alkanes), 1/P_mar-aq ((C₂₃+C₂₅+C₂₉+C₃₁)/(C₂₃+C₂₅) n-alkanes) and TMBR (terrestrial and marine biomarker ratio) (C₂₇+C₂₉₊C₃₁n-alkanes)/((C₂₇+C₂₉+C₃₁) n-alkanes+(brassicasterol+dinosterol+alkenones)), reveal a consistent pattern showing the relative contribution of terrestrial organic matter (TOM) is higher in the CRE and along the Zhejiang-Fujian coastline, controlled mostly by CR inputs and currents, but the TOM contribution decreases seaward, as the influences of the CR discharge decrease.     

Biodegradability and Toxicity of Anionic Surfactants

Alkyl sulphates of the general formula CH_{2n + 1}-O-SO₃Na and alkyl sulphonates of the general formula C_nH_{2n + 1}-SO₃Na, where n = 8, 10, 12, 14 in each series have been tested for biodegradability with the modified OECD screening test No. 301 E, and for toxicity with Daphnia magna and with Photobacterium phosphoreum (the Microtox^TM test). The results show that both alkyl sulphates and alkyl sulphonates are biodegraded with the alkyl sulphates degrading more rapidly under the test conditions. The alkyl sulphates also have higher toxicity to both test species and for both alkyl sulphates and sulphonates the toxicity increases linearly with increasing molecular weight of the surfactant.     

Novel C15 sesquiterpanes and their origin in different crude oils from the Pearl River Mouth Basin of China

In the saturate fractions of crude oils from the Zhu1 and Zhu2 depressions of the Pearl River Mouth Basin,two novel C_(15) sesquiterpanes have been detected except for drimanes and rearranged drimanes.By comparison with spectra and retention times in previous studies,they have been identified as 2,2,4α,7,8-pentamethyl-trans-decalin and 2,2,4α,7,8-pentamethyl-cis-decalin,respectively,which are related to the D/Eringsof18α(H)-and18β(H)-oleanane.ResultsshowthatthenovelC15sesquiterpanesarerelativelyabundantincondensateoilsthathavehighPr/PhratiosandarerichinterrigenoustriterpanessuchasoleananeandbicadinanesfromtheZhu2depression,butevidentlylowinlacustrineoilsthathavelowPr/Phratiosandarerichin4-methylsteranesfromtheZhu1depression.ThissuggeststhatthenovelC15sesquiterpanescouldberelatedtoterrigenousorganicmatterinoriginandcanhelpdistinguishtheoriginandsourceofcrudeoilsinthestudyarea.Inaddition,thereexistcompletelydifferentcorrelationsbetweentherelativeabundancesofdifferentC15sesquiterpanesthathavedifferentsourcesandthePr/Phratio,whichindicatesredoxconditionsinthecrudeoils.Forexample,thenovelC15sesquiterpanesandcadinanethatindicateterrigenousinputarepositivelycorrelatedwiththePr/Phratio,butdrimanesandrearrangeddrimaneshavingmicrobialoriginarenegativelycorrelatedwiththePr/Phratio.ThisimpliesthattheformationofthenovelC15sesquiterpanesrequiresrelativelyoxicconditions.ThenovelC15sesquiterpanesaremuchmoreabundantincarbonaceousmudstone(Pr/Ph=7.39)thanindarkmudstone(Pr/Ph=2.19)fromtheEnpingformation,althoughtheirorganicmatterishumic.However,theyarenotcommoninsapropeliclacustrinesourcerocks(Pr/Ph=2.29)fromtheWenchangFormation.Thissuggeststhatterrigenousorganicmatterisonlyasufficientcondition,butanoxicenvironmentduringdepositionanddiagenesismaybeaprerequisitefortheformationofnovelC15sesquiterpanes.     

The effect of volatile components in oil on evolutionary characteristics of diamondoids during oil thermal pyrolysis

On the basis of the results of simulation experiments, now we better understand the contribution of high carbon number hydrocarbons to diamondoid generation during thermal pyrolysis of crude oil and its sub-fractions(saturated, aromatic, resin, and asphalene fractions). However, little is known about the effect of volatile components in oil on diamondoid generation and diamondoid indices due to the lack of attention to these components in experiments. In this study, the effect of volatile components in oil on diamondoid generation and maturity indices was investigated by the pyrolysis simulation experiments on a normal crude oil from the HD23 well of the Tarim Basin and its residual oil after artificial volatilization, combined with quantitative analysis of diamondoids. The results indicate that the volatile components(≤n C12) in oil have an obvious contribution to the generation of adamantanes, which occurs mainly in the early stage of oil cracking(Easy Ro1.0%), and influences the variations in maturity indices of adamantanes; but they have no obvious effect on the generation and maturity indices of diamantanes. Therefore, some secondary alterations e.g., migration, gas washing, and biodegradation, which may result in the loss of light hydrocarbons in oil under actual geological conditions, could affect the identification of adamantanes generated during the late-stage cracking of crude oil, and further influence the practical application of adamantane indices.     

Geochemical study on oil-cracked gases and kerogen-cracked gases (II)—Discrimination methods between oil-cracked gases and kerogen-cracked gases

In the processes of discrimination between oil-cracked gases and kerogen-cracked gases, Behar and Pinzgofer et al.’s results were adopted in the former researches, in which the ratio of C₂/C₃ is basically a constant while the ratio of C₁/C₂ gradually increases in the course of primary cracking of kerogen. Otherwise in the course of secondary cracking of oil, the ratio of C₂/C₃ increases rapidly while C₁/C₂ keeps relatively stable. Our study on analogue experiment shows that, whether it is oil or kerogen, in its process of gas generating by cracking, the ratios of C₂/C₃, C₁/C₂ or C₁/C₃ will all be increased with the growth of thermal conditions. In comparison, the ratio of C₂/C₃, which is affected by genetic type to some comparatively less extent, mainly responds to the maturity of gases, while the value of C₂/C₃ is about 2, and that of C₂/iC₄ is about 10, and the corresponding value of R _o is about 1.5%–1.6%. The influence of gas source on C₂/C₃ is less than that of gas maturity, otherwise C₁/C₂ (or C₁/C₃) is obviously affected by cracking matrices. The ratios of C₁/C₂, C₁/C₃ of oil-cracked gases are less than that of kerogen-cracked gases, under the condition that the ratios of C₂/C₃ are similar in value, so are the value of dryness indexes. There exists wide diffidence between this view and the former discrimination method in theory. The analysis of the spot sample indicates that we can apply the above basic view to dealing efficiently with the problem of the discrimination between oil-cracked gas and kerogen-cracked gas.