生物降解作用对大宛齐油田库车组原油轻烃参数的影响

塔里木盆地大宛齐油田的部分原油经受了不同程度的微生物降解作用,通过对该油田原油中轻烃分布特征的研究, 能更深入地认识微生物降解作用对轻烃的影响。结果表明,微生物优先消耗正构烷烃,其次为异构烷烃和环烷烃;从而导致 C6、C7轻烃三角图发生相应变化。在大宛齐原油中,随微生物降解程度的增加,正庚烷值和异庚烷值逐渐减小;当庚烷值 为0~21,异庚烷值为0~2.6时,为“微生物降解”原油。微生物降解作用亦能使苯/正己烷、甲苯/正庚烷两个比值增大,而 使正庚烷/甲基环己烷比值减小;基于甲苯/正庚烷、正庚烷/甲基环己烷两个比值建立的判别次生蚀变作用的模板,当原油 处于轻微微生物降解作用时,该模板易与蒸发分馏趋势混淆,需谨慎使用。     

The effect of minor to moderate biodegradation on C5 to C9 hydrocarbons in crude oils

A suite of 18 oils from the Barrow Island oilfield, Australia, and a non-biodegraded reference oil have been analysed compositionally in order to detail the effect of minor to moderate biodegradation on C₅ to C₉ hydrocarbons. Carbon isotopic data for individual low molecular weight hydrocarbons were also obtained for six of the oils. The Barrow Island oils came from different production wells, reservoir horizons, and compartments, but have a common source (the Upper Jurassic Dingo Claystone Formation), with some organo-facies differences. Hydrocarbon ratios based on hopanes, steranes, alkylnaphthalenes and alkylphenanthrenes indicate thermal maturities of about 0.8% R_c for most of the oils. The co-occurrence in all the oils of relatively high amounts of 25-norhopanes with C₅ to C₉ hydrocarbons, aromatic hydrocarbons and cyclic alkanes implies that the oils are the result of multiple charging, with a heavily biodegraded charge being overprinted by fresher and more pristine oil. The later oil charge was itself variably biodegraded, leading to significant compositional variations across the oilfield, which help delineate compartmentalisation. Biodegradation resulted in strong depletion of n-alkanes (>95%) from most of the oils. Benzene and toluene were partially or completely removed from the Barrow Island oils by water washing. However, hydrocarbons with lower water solubility were either not affected by water washing, or water washing had only a minor effect. There are three main controls on the susceptibility to biodegradation of cyclic, branched and aromatic low molecular weight hydrocarbons: carbon skeleton, degree of alkylation, and position of alkylation. Firstly, ring preference ratios at C₆ and C₇ show that isoalkanes are retained preferentially relative to alkylcyclohexanes, and to some extent alkylcyclopentanes. Dimethylpentanes are substantially more resistant to biodegradation than most dimethylcyclopentanes, but methylhexanes are depleted faster than methylpentanes and dimethylcyclopentanes. For C₈ and C₉ hydrocarbons, alkylcyclohexanes are more resistant to biodegradation than linear alkanes. Secondly, there is a trend of lower susceptibility to biodegradation with greater alkyl substitution for isoalkanes, alkylcyclohexanes, alkylcyclopentanes and alkylbenzenes. Thirdly, the position of alkylation has a strong control, with adjacent methyl groups reducing the susceptibility of an isomer to biodegradation. 1,2,3-Trimethylbenzene is the most resistant of the C₃ alkylbenzene isomers during moderate biodegradation. 2-Methylalkanes are the most susceptible branched alkanes to biodegradation, 3-methylalkanes are the most resistant and 4-methylalkanes have intermediate resistance. Therefore, terminal methyl groups are more prone to bacterial attack compared to mid-chain isomers, and C₃ carbon chains are more readily utilised than C₂ carbon chains. 1,1-Dimethylcyclopentane and 1,1-dimethylcyclohexane are the most resistant of the alkylcyclohexanes and alkylcyclopentanes to biodegradation. The straight-chained and branched C₅–C₉ alkanes are isotopically light (depleted in ¹³C) relative to cycloalkanes and aromatic hydrocarbons. The effects of biodegradation consistently lead to enrichment in ¹³C for each remaining hydrocarbon, due to preferential removal of ¹²C. Differences in the rates of biodegradation of low molecular weight hydrocarbons shown by compositional data are also reflected in the level of enrichment in ¹³C. The carbon isotopic effects of biodegradation show a decreasing level of isotopic enrichments in ¹³C with increasing molecular weight. This suggests that the kinetic isotope effect associated with biodegradation is site-specific and often related to a terminal carbon, where its impact on the isotopic composition becomes progressively ‘diluted’ with increasing carbon number.     

Effects of Biodegradation on the Distribution of Alkylcarbazoles in Crude Oils

We have investigated the distributions of alkylcarbazoles in a series of crude oils with different biodegradation extents, in combination with biomarker parameters, stable carbon isotopic ratios and viscosities. The analyses showed that slight biodegradation has little effect on alkylcarbazoles. The concentrations of C₀-, C₁-, and C₂-carbazoles seem to display a slight decrease with biodegradation through the moderately biodegraded stage, and an abrupt decrease to the heavily biodegraded stage. The relative concentrations of C₀-, C₁-, and C₂-carbazoles do not show any apparent change in the non-heavily biodegraded stages, but through non-heavily biodegraded to heavily biodegraded stages, the percentages of C₀- and C₁-carbazoles decrease, and those of C₂-carbazoles increase significantly, which may indicate that C₂-carbazoles are more resistant to biodegradation than lower homologous species. As to C₂-carbazole isomers, the relative concentrations of the pyrrolic N-H-shielded, pyrrolic N−H partially shielded and pyrrolic N-H-exposed isomers do not show any obvious variation in the non-heavily biodegraded oil, but there is an abrupt change through the mid-biodegraded stage to the heavily biodegraded stage. This project was financially supported by the Youth Knowledge-Innovation Foundation of CNPC (No. 00Z1304).     

Demethylated hopanes in crude oils and their applications in petroleum geochemistry

Analyses of some Australian crude oils show that many contain varying concentrations of A/ B-ring demethylated hopanes. These range from C₂₆ to C₃₄ and have been identified from their retention times and mass spectral data as 17α(H)-25-norhopanes. Comparison of hopane and demethylated hopane concentrations and distributions in source-related, biodegraded oils suggests that demethylated hopanes are biotransformation products of the hopanes. Further, it appears that the process occurs at a late stage of biodegradation, after partial degradation of steranes has occurred. Demethylated hopanes are proposed as biomarkers for this stage of severe biodegradation. The presence of these compounds in apparently undegraded crude oils is thought to be due to the presence of biodegraded crude oil residues which have been dissolved by the undegraded crude oil during accumulation in the reservoir sands. The timing of hopane demethylation, relative to the degradation of other compounds, has been assessed and the progressive changes in crude oil composition with increasing extent of biodegradation have been identified. The use of demethylated hopanes as maturity parameters for severely biodegraded crude oils, and the applicability of established biomarker maturity parameters to such oils, are also discussed.     

Carbon isotopic composition of individual n-alkanes in asphaltene pyrolysates of biodegraded crude oils from the Liaohe Basin, China

Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C₁₆–C₂₉ range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.     

C24–C27 Degraded triterpanes in Nigerian petroleum: novel molecular markers of source/input or organic maturation?

The analyses, by gas chromatography and gas chromatography/mass spectrometry, of the triterpane concentrate of crude oils sampled from various oil fields of the Tertiary Niger delta have revealed the ubiquitous presence of a series of C₂₄–C₂₇ tetracyclic alkanes likely to be novel degraded triterpanes. The presence in the crude oils of a C₂₅ tricyclic alkane, apparently structurally related to the tetracyclanes, seemed consistent with the hypothesis of sequential cleavages of the terminal rings of precursor pentacyclic triterpenoid derivatives with increasing thermal transformation of the respective petroleums.The degraded triterpanes might be useful for assessing the stages of thermal evolution of petroleum in the reservoir. A possible application, to oil exploration, of the expected variations in the concentration of the polycyclanes in crude oils with different thermal histories would be in distinguishing primary (immature) oils from mature but biodegraded oils.     

Isoprenoid alkanes with irregular “head-to-head” linkages

A lightly biodegraded crude oil from the Tolkinsk field (Upper Jurassic), situated in north-west Siberia, was found to contain a series of C₂₈–C₃₉ isoprenoid alkanes. Most of these components contain a pristane unit linked head-to-head with other isoprenoid units. The structures of these components were elucidated by mass spectral interpretations, comparisons with a synthesised standard and by reference to data published previously in the literature. These results extend the carbon number range, the variety of structural types, and the number of reported occurrences of these compounds in geological samples. These results provide further evidence for a contribution of bacterial cell-wall lipids to crude oils.     

Assessment of petroleum biodegradation using stable hydrogen isotopes of individual saturated hydrocarbon and polycyclic aromatic hydrocarbon distributions in oils from the Upper Indus Basin,Pakistan

The stable hydrogen isotopic compositions (δD) of selected aliphatic hydrocarbons (n-alkanes and isoprenoids) in eight crude oils of similar source and thermal maturity from the Upper Indus Basin (Pakistan) were measured. The oils are derived from a source rock deposited in a shallow marine environment. The low level of biodegradation under natural reservoir conditions was established on the basis of biomarker and aromatic hydrocarbon distributions. A plot of pristane/n-C₁₇ alkane (Pr/n-C₁₇) and/or phytane/n-C₁₈ alkane (Ph/n-C₁₈) ratios against American Petroleum Institute (API) gravity shows an inverse correlation. High Pr/n-C₁₇ and Ph/n-C₁₈ values and low API gravity values in some of the oils are consistent with relatively low levels of biodegradation. For the same oils, δD values for the n-alkanes relative to the isoprenoids are enriched in deuterium (D). The data are consistent with the removal of D-depleted low molecular weight (LMW) n-alkanes (C₁₄–C₂₂) from the oils. The δD values of isoprenoids do not change with progressive biodegradation and are similar for all the samples. The average D enrichment for n-alkanes with respect to the isoprenoids is found to be as much as 35‰ for the most biodegraded sample. For example, the moderately biodegraded oils show an unresolved complex mixture (UCM), loss of LMW n-alkanes (<C₁₅) and moderate changes in the alkyl naphthalene distributions. The relative susceptibility of alkyl naphthalenes at low levels of biodegradation is discussed. The alkyl naphthalene biodegradation ratios were determined to assess the effect of biodegradation. The dimethyl, trimethyl and tetramethyl naphthalene biodegradation ratios show significant differences with increasing extent of biodegradation.     

Deciphering biodegradation effects on light hydrocarbons in crude oils using their stable carbon isotopic composition: A case study from the Gullfaks oil field, offshore Norway

Compound-specific isotope analysis has become an important tool in environmental studies and is an especially powerful way to evaluate biodegradation of hydrocarbons. Here, carbon isotope ratios of light hydrocarbons were used to characterise in-reservoir biodegradation in the Gullfaks oil field, offshore Norway. Increasing biodegradation, as characterised, for example, by increasing concentration ratios of Pr/n-C₁₇ and Ph/n-C₁₈, and decreasing concentrations of individual light hydrocarbons were correlated to ¹³C-enrichment of the light hydrocarbons. The δ¹³C values of C₄ to C₉n-alkanes increase by 7-3‰ within the six oil samples from the Brent Group of the Gullfaks oil field, slight changes (1-3‰) being observed for several branched alkanes and benzene, whereas no change (<1‰) in δ¹³C occurs for cyclohexane, methylcyclohexane, and toluene. Application of the Rayleigh equation demonstrated high to fair correlation of concentration and isotope data of i- and n-pentane, n-hexane, and n-heptane, documenting that biodegradation in reservoirs can be described by the Rayleigh model. Using the appropriate isotope fractionation factor of n-hexane, derived from laboratory experiments, quantification of the loss of this petroleum constituent due to biodegradation is possible. Toluene, which is known to be highly susceptible to biodegradation, is not degraded within the Gullfaks oil field, implying that the local microbial community exhibits rather pronounced substrate specificities. The evaluation of combined molecular and isotopic data expands our understanding of the anaerobic degradation processes within this oil field and provides insight into the degradative capabilities of the microorganisms. Additionally, isotope analysis of unbiodegraded to slightly biodegraded crude oils from several oil fields surrounding Gullfaks illustrates the heterogeneity in isotopic composition of the light hydrocarbons due to source effects. This indicates that both source and also maturity effects have to be well constrained when using compound-specific isotope analysis for the assessment of biodegradation.     

Bicyclic sesquiterpenoids and diterpenoids in Australian crude oils

Bicyclanes previously reported only in heavily biodegraded Texas Gulf Coast crudes have been found to be ubiquitous in Australian crude oils of non-marine origin from four different basins. The compounds are present in oils, thought to be derived from the same or similar sources, that have undergone varying degrees of biodegradation. They are also found to be present in oils of different geological age. In addition a series of tricyclic diterpenoid hydrocarbons was common to four oils from the Gippsland Basin. Four of these compounds had the molecular formula C₂₀H₃₄ and mass spectral fragmentation patterns suggested they were mono-unsaturated diterpenoids. The presence of unsaturated diterpenoids in crude oils appears to be a unique observation. It is proposed that the diterpenoids may be the source of the bicyclanes also observed in these oils.     

Biodegradation of petroleum by <Emphasis Type="Italic">Klebsiella pneumoniae</Emphasis> isolated from drilling fluid

The removal of petroleum and petroleum-based products from the environment is of great importance. The objectives of this study were to investigate the most suitable physiological conditions and the effects of additional carbon, nitrogen and surfactant sources on petroleum biodegradation by Klebsiella pneumoniae ATCC13883 isolated from drilling fluid and to evaluate petroleum biodegradation with detailed hydrocarbon analysis by GC–MS. The results indicated that the highest biodegradation rate of 66.5% for K. pneumoniae was obtained under the conditions of pH 7, petroleum concentration 1% (v/v) and 7-day incubation at 150 rpm and 25 °C, proving to be the most effective physical conditions for petroleum biodegradation in this present study. Additional sources such as Triton X: 100, glucose and yeast extract significantly enhanced the petroleum biodegradation of K. pneumoniae to 68, 71 and 72.5%, respectively. In the last stage of this study, biodegradation rates were above 90% for hydrocarbons ranging from C₁₀ and C₂₀, above 70% for hydrocarbons ranging from C₂₁ and C₂₂ and above 40% for hydrocarbons ranging from C₃₁ and C₃₂. In conclusion, oil field adapted K. pneumoniae could efficiently degrade short-, medium- and long-chain alkanes in petroleum and thus is a potential source for advanced petroleum treatment.     

生物降解原油地球化学研究新进展

生物降解作用是原油的一种重要的蚀变作用,对原油的物性和经济价值有着负面的影响。全球石油大多遭受过生物降解。生物降解作用对常见生物标志物的影响得以较好的描述,综述了近年来高分子量正构烷烃、三环萜烷、25 降藿烷生物降解的新进展。目前对生物降解作用的细节、发生机理尚不十分清楚,讨论了原油喜氧和厌氧降解机制,认为厌氧作用可能起主导作用,降解速率很慢。温度是控制生物降解作用的重要因素,储层温度大于80℃不会发生生物降解作用。生物降解原油多为混源油,介绍了研究生物降解原油的多期成藏方法。沥青质不易生物降解,其热解产物及钌离子催化氧化产物在生物降解原油对比、油源对比中具有重要的作用;最后指出了今后的发展方向。     

Tracing sources of carbon in urban groundwater using δ<Superscript>13</Superscript>C<Subscript>TDIC</Subscript> ratios

Total dissolved inorganic carbon (TDIC) and its stable isotope ratio δ¹³C_TDIC are used to trace the evolution of the carbon system of groundwater in three UK Permo-Triassic sandstone aquifers. Samples were collected from multilevel piezometers, open boreholes and sewer sampling points in the British Midlands (Nottingham, Birmingham and Doncaster) to evaluate both local and regional variations in δ¹³C_TDIC. δ¹³C samples of matrix and pore water have also been analysed in each aquifer to further constrain the interpretations. Combining δ¹³C_TDIC ratios with measurements of TDIC and pH clearly distinguishes the principal processes underlying the geochemical evolution of groundwater in Triassic sandstone aquifers, where processes can be both natural (e.g. carbonate dissolution) and anthropogenic (sewer-derived recharge). The paper shows that δ¹³C_TDIC resolves ambiguities that arise from the interpretation of TDIC and pH measurements in isolation. Field measurements demonstrate that, under natural conditions, the carbonate system evolves similarly in each aquifer. An open-system evolution during recharge largely saturates the groundwater with carbonate depending upon its availability in the sandstone matrix. The contribution of sewer exfiltration to urban recharge is readily distinguished by lower pH and higher TDIC values without significant changes in δ¹³C_TDIC.     

Heterogeneous C<Subscript>16</Subscript>Zn<Subscript>8</Subscript>O<Subscript>8</Subscript> nanocluster as a selective CO/NO nanosensor: computational investigation

Density functional theory (DFT) calculations were employed to investigate the effects of adsorption of toxic carbon monoxide (CO) and nitrogen monoxide (NO) molecules on heterogeneous C₁₆Zn₈O₈ nanocage. A detailed analysis of the energetic, geometry, and electronic structure of various CO and NO adsorptions on the cluster surface was performed. It has been shown that CO molecule was adsorbed on the surface of the cluster resulting in more stable complex system, while NO molecule adsorption led to less stable system. These processes also changed the electronic properties of the cluster by reducing the HOMO/LUMO energy gap after adsorption process. Since this phenomenon led to an increment in the electrical conductivity of the cluster at a definite temperature, the C₁₆Zn₈O₈ was transformed to a stronger semiconductor substance upon the CO and NO adsorption. We believe that this research may be helpful in the several fields study such as sensor and catalyst investigation.     

Organic geochemistry of the oils from the southern geological Province of Cuba

The aliphatic hydrocarbon composition (acyclic isoprenoids, hopanoids and steroids) of oils from the most productive fields in the southern geological Province of Cuba have been studied. This province is defined by its position with respect to the Cretaceous overthrust belt generated during the formation of oceanic crust along the axis of the proto-Caribbean Basin. The relative abundances of 18α(H)-22,29,30-trisnorneohopane, gammacerane and diasteranes suggest that Pina oils are related to the carbonate oils from the Placetas Unit in the northern province (low T_s/(T_s+T_m) and C_27,29 rr/(rr+sd) ratios). The Cristales and Jatibonico oils exhibit some differentiating features such as higher T_s/(T_s+T_m) and absence of gammacerane. The oils from this province do not exhibit significant differences in either hopane, C₃₂ 22S/(S+R) and C₃₀ αβ/(αβ+βα), or sterane, C₂₉ αα 20S/(S+R), maturity ratios. However, the relative content of 5α(H),14β(H),17β(H)-cholestanes (C₂₉ ββ/(ββ+αα) ratio) indicates that Pina oils are more mature than Cristales and Jatibonico oils. Several of these oils (Cristales, Jatibonico and Pina 26) are heavily biodegraded, lacking n-alkanes, norpristane, pristane and phytane (the two former oils do not contain acyclic isoprenoid hydrocarbons). Other biodegradation products, the 25-norhopanes, are found in all the oils. Their occurrence is probably due to mixing of severely biodegraded oil residues with undegraded crude oils during accumulation in the reservoir.     

Novel side chain methylated and hexacyclic hopanes: Identification by synthesis, distribution in a worldwide set of coals and crude oils and use as markers for oxic depositional environments

Novel side chain methylated and hexacyclic hopanes have been identified in coals and oils from around the world. Extended hopanes (>C₃₂) with an additional methyl in the side chain (“isohopanes”) were identified by comparison with synthetic standards. The major C₃₃-C₃₅ isohopanes are 31-methylbishomohopanes, 32-methyltrishomohopanes and 33-methyltetrakishomohopanes. Extended hopanes methylated at C-29 were not detected. The 17α(H),21β(H)-31-methyltrishomohopanes show four peaks on gas chromatography because of the extra asymmetric carbon at C-31. Like regular hopanes, the isohopanes extend beyond C₃₅. Low concentrations of novel hexacyclic hopanes having 35 or more carbons were also detected in oils and coal extracts. The C₃₅ hexacyclic hopanes were identified as 29-cyclopentylhopanes. Isohopanes are released from the kerogen by hydrous pyrolysis and hydropyrolysis. The 22S/(22S + 22R) ratio for 31-methylbishomohopanes and other isohopanes is around 0.60 at equilibrium in geological samples. They isomerize slightly more slowly than regular C₃₃ hopanes. Isohop-17(21)-enes, 2α-methylisohopanes and two series of rearranged isohopanes were tentatively identified. Isohopanes can be biodegraded to form the corresponding 25-norhopanes. When 25-norhopanes are not formed, the isohopanes are much more resistant to biodegradation than regular hopanes. In biodegraded oil seeps from Greece, 30-norisohopanes were tentatively assigned. The composition and relative abundance of C₃₃ and C₃₄ isohopanes in a worldwide set of coals and crude oils was determined. Isohopanes are abundant in coal and coal-generated oils, where they can account for more than 5% of all extended hopanes, and low in abundance in oils from source rocks deposited under anoxic conditions.     

Adsorption of H<Subscript>2</Subscript>O,NH<Subscript>3</Subscript> and C<Subscript>6</Subscript>H<Subscript>6</Subscript> on alkali metal cations in internal surface of mordenite and in external surface of smectite: a DFT study

Adsorption of H₂O, NH₃ and C₆H₆ on H- and alkali metal-exchanged structures of mordenite and on corresponding cations on the smectite layer is investigated by ab initio density-functional calculations. Proton or an alkali metal cation compensates one Al/Si framework substitution and resides in the extra-framework position of zeolite or above flat smectite layer close to the Al/Si substitution. Pronounced similarities between zeolite and smectite are observed in changes of the adsorption energies and location of the external cation with changing character of the external cation. Calculated adsorption energies exhibit the following trend: E(NH₃) > E(H₂O) > E(C₆H₆). Because of looser contact with the framework, zeolitic cations are stronger adsorption centers and calculated adsorption energies of zeolites are by ~20–30% larger than cations of smectites. The highest adsorption energy is calculated for H-exchanged structures and down the group of alkali metal cations a decrease of the adsorption energy is observed. Deviations from the smooth variation of the adsorption energy are caused by: (1) formation of strong hydrogen bonds in H-exchanged structures, (2) adsorption induced migration of the external Li⁺ cation, and (3) steric hindrances of the flat C₆H₆ molecule adsorbed on the cation in the cage of zeolite.     

LiFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> and NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript> at low temperatures: an infrared spectroscopic study

 Synthetic aegirine LiFeSi₂O₆ and NaFeSi₂O₆ were characterized using infrared spectroscopy in the frequency range 50–2000 cm⁻¹, and at temperatures between 20 and 300 K. For the C2/c phase of LiFeSi₂O₆, 25 of the 27 predicted infrared bands and 26 of 30 predicted Raman bands are recorded at room temperature. NaFeSi₂O₆ (with symmetry C2/c) shows 25 infrared and 26 Raman bands. On cooling, the C2/c–P2₁/c structural phase transition of LiFeSi₂O₆ is characterized by the appearance of 13 additional recorded peaks. This observation indicates the enlargement of the unit cell at the transition point. The appearance of an extra band near 688 cm⁻¹ in the monoclinic P2₁/c phase, which is due to the Si–O–Si vibration in the Si₂O₆ chains, indicates that there are two non-equivalent Si sites with different Si–O bond lengths. Most significant spectral changes appear in the far-infrared region, where Li–O and Fe–O vibrations are mainly located. Infrared bands between 300 and 330 cm⁻¹ show unusually dramatic changes at temperatures far below the transition. Compared with the infrared data of NaFeSi₂O₆ measured at low temperatures, the change in LiFeSi₂O₆ is interpreted as the consequence of mode crossing in the frequency region. A generalized Landau theory was used to analyze the order parameter of the C2/c–P2₁/c phase transition, and the results suggest that the transition is close to tricritical. Received: 21 January 2002 / Accepted: 22 July 2002     

Correlation of crude oils with their oil source formation,using high resolution GLC C6-C7 component analyses

A new method has been devised, based on high resolution GLC component analyses of the C₆-C₇ hydrocarbons from shales and from crude oils, whereby composition parameters in an oil are compared with the corresponding parameters in a shale. Ideally, a given composition parameter should have the same value for a crude oil and the source rock which generated and expelled that crude oil. A Similarity Coefficient has been devised, to measure the degree of correlation between crude oil and source rock hydrocarbons or between the hydrocarbons from different groups of crude oils. The maximum value of the Similarity Coefficient is 1.00, and the theoretical minimum is a positive fraction close to zero. Based on the natural variation in composition of primary (not biodegraded) crude oils of the same basin and origin, it was found that if the Similarity Coefficient is about 0.80 or higher, correlation between the natural hydrocarbons considered is good. If the Similarity Coefficient is less than 0.73, correlation is poor.Based on strict rules for sample selection (e.g. maturity of shales and lack of biodegradation in the oils), ten presumed crude oil-source formation pairs were selected. Most of these pairs have high Similarity Coefficients of 0.80 or more. Erroneous crude oil-source rock combinations from areas with more than one source formation, as in West Texas, have low Similarity Coefficients. This indicates that the crude oil-source formation correlation method based on the Similarity Coefficient generally is functioning properly.     

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.