Contribution of E.S.R. analysis toward diagenic mechanisms in bituminous deposits

The E.S.R. g-values of a variety of bituminous materials have been plotted against a function of their heteroatom content ∑δ_κX_κ, where δ is the splitting coefficient of the given heteroatom κ, and X is its atomic fraction. Three discrete series are evident: two coal series, one exhibiting direct variation of g with ∑δ_κX_κ (Series I), the other exhibiting an inverse relationship (Series II). The petroleum asphaltenes, as well as most asphaltites and asphaltoids (Series III), lie above and roughly parallel to Series I. Sulfur-treated asphaltics approach Series I, whereas heated asphaltenes and resins are situated around the intersection of Series II and III.Bituminous deposits may transform through diagenesis to their mature forms, as evidenced by their increase in the delocalization (increased aromaticity) with a decrease in heteroatom content. The diagenesis of coal is reliant on oxygen whose elimination may result in aromatization (Series I), and further transformations may increase active peripheral oxygen function groups (Series II). The intersection of Series I and II contains the delocalization states. There exist major differences in the precursors and mode of transformation between members of the coal and asphaltene series.     

Comparative studies on compounds occluded inside asphaltenes hierarchically released by increasing amounts of H2O2/CH3COOH

Being the heaviest fraction of crude oils, asphaltenes are liable to aggregate, and other molecules in the oils can be steadily adsorbed onto, and even occluded inside the macromolecular structures of the asphaltenes. These occluded compounds inside the asphaltenes can survive over geological time in oil reservoirs owing to effective protection by the macromolecular structures of the asphaltenes. The asphaltenes of a crude oil (ZG31) from the central Tarim Basin, NW China, were hierarchically degraded by increasing the amount of H₂O₂/CH₃COOH to release the occluded compounds. Besides the common components, series of even numbered n-alk-1-enes and 3-ethylalkanes were detected among the occluded compounds. Comparison of the biomarker distributions and the compound-specific C isotopic results between the compounds from the maltenes and those from the occluded fraction, the ZG31 reservoir was suggested to have been charged multiple times, with different charges being derived from different strata of source rocks.     

Petrological, organic geochemical and geochemical characteristics of coal from the Soko mine, Serbia

A petrological, organic geochemical and geochemical study was performed on coal samples from the Soko Mine, Soko Banja basin, Serbia. Ten coal and two carbonaceous clay samples were collected from fresh, working faces in the underground brown coal mine from different parts of the main coal seam. The Lower Miocene, low-rank coal of the Soko Mine is a typical humic coal with huminite concentrations of up to 76.2 vol.%, liptinite less than 14 vol.% and inertinite less than 11 vol.%. Ulminite is the most abundant maceral with variable amounts of densinite and clay minerals. Sporinite and resinite are the most common macerals of the liptinite group. Inertodetrinite is the most abundant maceral of the inertinite group. The mineral-bituminous groundmass identified in some coal samples, and carbonaceous marly clay, indicate sub-aquatic origin and strong bacterial decomposition. The mean random huminite reflectance (ulminite B) for the main coal seam is 0.40 ± 0.05% Rr, which is typical for an immature to early mature stage of organic matter.The extract yields from the coal of the Soko Banja basin ranges from 9413 to 14,096 ppm, in which alkanes constituted 1.0–20.1%, aromatics 1.3–14.7%, asphaltenes 28.1–76.2% and resins 20.2–43.5%. The saturated hydrocarbon fractions included n-C₁₅ to n-C₃₂, with an odd carbon number that predominate in almost all the samples. The contents of n-C₂₇ and n-C₂₉ alkanes are extremely high in some samples, as a contribution of epicuticular waxes from higher plants. Acyclic isoprenoid hydrocarbons are minor constituents in the aliphatic fraction, and the pristane/phytane (Pr/Ph) ratio varies between 0.56 and 3.13, which implies anaerobic to oxic conditions during sedimentation. The most abundant diterpanes were abietane, dehydroabietane and 16α(H)-phyllocladane. In samples from the upper part of the coal seam, diterpanes are the dominant constituents of the alkane fraction. Polycyclic alkanes of the triterpane type are important constituents of alkane fractions. The occurrence of ββ- and αβ-type hopanes from C₂₇ to C₃₁, but without C₂₈, is typical for the Soko Banja coals.The major and trace elements in the coal were analysed using X-ray fluorescence (XRF), and inductively coupled plasma-mass spectrometry (ICP-MS). In comparison with world lignites, using the geometric mean value, the coal from the Soko Banja Basin has a high content of strontium (306.953 mg/kg). Higher values than the world lignites were obtained for Mo (3.614 mg/kg), Ni (8.119 mg/kg), Se (0.884 mg/kg), U (2.642 mg/kg) and W (0.148 mg/kg). Correlation analysis shows inorganic affinity for almost all the major and trace elements, except for S, which has an organic affinity.     

The influence of biodegradation on resins and asphaltenes in the Liaohe Basin

Asphaltenes are traditionally considered to be recalcitrant to microbial alteration. Resins and asphaltenes of seven biodegraded oils extracted from reservoir cores of two columns (Es3 and Es1) of the Lengdong oilfield in the Liaohe Basin, NE China, were studied to test this hypothesis. Elemental (C, H, N, O, S) and isotopic compositions (δ¹³C and δ¹⁵N) were measured, FT-IR was used to study the oxygenated functionalities of both resins and asphaltenes, and Py–GC–MS was used to elucidate how alkyl side chains of asphaltenes were altered during biodegradation. We conclude that the products of biodegradation, such as carboxylic acids, phenol and alcohols, may not only contribute to the resin fraction of crude oils, but also are linked with functionalities of resins and asphaltenes. The amount of asphaltenes increases because some resin molecules are enlarged and their polarity increased such that they can be precipitated by hexane as newly generated asphaltenes. Thus, the hydrocarbons that are progressively consumed during biodegradation can pull the δ¹³C of asphaltene fraction closer to the δ¹³C of the altered resins and hydrocarbons that were consumed.     

9 and 34 GHz EPR study of the free radicals in various asphaltenes: Statistical correlation of the g-values with heteroatom content

The 9 and 34 GHz EPR spectra of eight asphaltenes from different locations have been studied at 294 K in an attempt to correlate the observed g-values with the heteroatom content. It is found that the EPR linewidths are larger and the g-values are smaller at 34 GHz than at 9 GHz. Quantitative statistical analysis of the g-values observed in those asphaltenes derived from tar sand bitumens and crude oils shows that they are uncorrelated with the heteroatom content, unlike those from coal. It is concluded that g-values may not be a good analytical tool for elucidating the structure of those asphaltenes not derived from coal.     

Oxidation inhibitors occuring in bioproducers, recent sediments, ancient rocks and oils

Native antioxidants (AO) are involved in the transformation of organic matter (OM) in different stages of diagenesis. In the early stages, the geochemical significance of AO can be estimated by using AO consumption index (I). The positive I values suggest that the OM fossilization proceeded under reducing conditions which favoured the formation of oil-source rocks, while the negative I values indicate oxidizing conditions which are characterized by the formation of rocks having a low oil-generation potential. In the late stages of diagenesis, the AO content is indicative of the degree of catagenic (thermal) or biodegradation (oxidative) transformation of oils. The AO contents of Paleogenic, Mesozoic and Paleozoic oils have been found to differ approximately by one order of magnitude. A major portion of AO is concentrated in oil resins and asphaltenes. The ratio of AO to resins and asphaltenes can be used as criterion of catagenic transformation of OM.     

Biomarker distributions in asphaltenes and kerogens analysed by flash pyrolysis-gas chromatography-mass spectrometry

Biomarker distributions in a suite of asphaltenes and kerogens have been analysed by flash pyrolysis directly coupled to a GCMS system. Attention has been focussed on biomarkers of the sterane and triterpane types. The sample suite under investigation consists of sediments with different kerogen types and some crude oils. Biomarker distributions in the pyrolysates have been compared with the “free” biomarkers in the corresponding saturated hydrocarbon fractions.The analyses show significant differences between the distributions of the free biomarkers and those in the pyrolysates. The latter have lower amounts of steranes while diasteranes are absent or present at low concentrations only. In the triterpane traces a shift of maximum intensity from C₃₀ (free compounds) to C₂₇/C₂₉ is observed. Furthermore, the pyrolysates contain a set of triterpenes (not present among the free compounds), and there is a selective loss of “non-regular” triterpanes that are present in the saturated hydrocarbon fractions. The observed differences between pyrolysates and free hydrocarbons can be explained partly by the processes occurring during pyrolysis such as bond rupture and subsequent stabilisation of primary pyrolysis products. To a certain extent these differences also show that maturation processes occurring in sediments have effects on free biomarker molecules different from those on molecules that are enclosed in a macromolecular matrix (kerogen or asphaltenes).Differences between biomarker distributions of asphaltene and kerogen pyrolysates are relatively small. A comparison with the pyrolysates from extracted whole sediments suggests that these differences are mainly caused by interactions between the organic material and the mineral matrix during pyrolysis.Oil asphaltenes behave differently from sediment asphaltenes as their pyrolysates are more similar to the corresponding saturated hydrocarbon fractions, i.e. the differences described above are observed to a much smaller extent. This different behaviour appears to be the result of coprecipitation of a part of the maltene fraction with the oil asphaltenes.     

The use of model compounds to investigate the release of covalently bound biomarkers via hydropyrolysis

This study describes the reduction of functionalised model compounds to their corresponding hydrocarbons by catalytic hydropyrolysis to provide information on the release of biomarkers from kerogens and asphaltenes covalently bound through the functional groups investigated. Five model compounds were investigated, the n-C₁₈ carboxylic acids, stearic and oleic acids; the C₂₄ steroidal acid, 5β-cholanic acid; and the saturated and unsaturated C₂₇ sterols, 5α-cholestanol and cholesterol. The yield and distribution of the hydrocarbons generated were assessed for the model compounds adsorbed to silica and carbon substrates, and unsupported on a bed of catalyst. The n-C₁₈ acids are shown to be reduced to the n-C₁₈ alkane, with a selectivity of >95% for stearic acid, although due to its unsaturated structure, oleic acid is prone to cracking, with shorter chained n-alkanes also being formed. The conversion of these compounds, adsorbed to either silica or carbon is relatively low, even at hydropyrolysis temperatures significantly above their boiling point, suggesting that interactions between the acids and substrate leading to the formation of stable entities (Si–O–C linkages in the case of silica) significantly retard volatilisation. The yield can be increased by placing the compounds directly onto a bed of catalyst, but for low boiling compounds such as stearic acid this can result in volatilisation and cracking at temperatures below that of the activation point of the catalyst. This method produced improved yields of >95% pure product for higher boiling compounds such as 5β-cholanic acid. The presence of the functional group attached to the ring system of compounds such as 5α-cholestanol does not diminish the selectivity of the technique. The double bond in cholesterol resulted in more incomplete hydrogenation with sterenes being generated, and in addition to 5α and 5β-cholestane, diasteranes were also generated via migration of the double bond.     

Evaluating the timing of oil expulsion: about the inverse behaviour of light hydrocarbons and oil asphaltene kinetics

This paper deals with natural temperature records in the heavy (asphaltenes) and the light fractions (C₇—light hydrocarbons) of petroleum. Two sets of marine oils formed from different source rocks and petroleum systems were studied using asphaltene kinetics and light hydrocarbon analysis. Both fractions have been reported to contain information about the temperature the respective oils have been exposed to in the subsurface. These indicated temperatures generally correspond to the conditions in the source rock when expulsion occurred. Bulk kinetic analysis of reservoir oil asphaltenes as well as light hydrocarbon (LH) analysis (of dimethylpentanes) were used here in order to evaluate the expulsion temperatures. Surprisingly, when considering information coming from both fractions, an inverse trend between LHs expulsion temperatures (Ctemp) and asphaltenes (Tasph.) can be observed—high T_asph (asphaltene temperatures) occur with low LH C_temp (light hydrocarbon expulsion temperatures) and low T_asph can be observed when Ctemp is high. These differences are of fundamental importance for the use of such geochemical data in calibrating numerical basin models. The reason for this inverse behaviour is possibly due to the different expulsion behaviour of light hydrocarbons and the heavy fraction of oils, especially when the source rocks contain only moderate amounts of organic matter. In addition it has to be considered that the temperature predictions obtained using asphaltene kinetic analysis are related to the onset temperature of petroleum expulsion, while light hydrocarbons provide, at best, average expulsion temperatures.     

REE distribution in the resin-asphaltene fractions as a geochemical criterion for identification of sources of trace elements in oil

This paper reports REE data on resin-asphaltene components of oil from six oil-gas-bearing provinces and on bitumoids from inferred oil-source rocks (domanikites and bazhenites). It was shown that, regardless of geological-tectonic structure of the regions, oil composition, depth of reservoirs, and host lithologies, oil exhibits significant REE fractionation, and, unlike bitumoids, positive Eu anomaly. The (Eu/Sm)_n ratio increases from asphaltenes to resins and further to oils. Based on REE distribution in oil, source rocks, and bitumoids, it was concluded that deep-seated fluids were one of the possible sources that defined the trace element composition of oil.     

Identification and geochemical significance of polarized macromolecular compounds in lacustrine and marine oils

Polarized macromolecular compounds in typical lacustrine and marine shale oils collected from the Ordos Basin and Tarim Basin of China were analyzed by FT-ICR-MS. Maturity was taken into consideration by diagenesis physical simulation experiments on shale oils, which had been collected at various temperature and pressure stages. The results showed that similar components existed in non-hydrocarbon and asphaltenes and the main peak compound classes of Nl and 02 were potential parameters for identifying typical marine oil and lacustrine oil in China. Nitrogen compounds/（nitrogen compounds and oxygen compounds）, such as Nl/（O2＋Nt）, NL/（Oa＋Nt）, Ni/（NiO1＋N1O2） are the maturity indicators, which are related with C-N and C-O bond energy. Differences in molecular components and weights between marine and lacustrine oils are the effective index to identify source maturity and sedimentary environment.     

Characterisation of the non-asphaltene products of mild chemical degradation of asphaltenes

The major steranes of the non-asphaltene fraction of Nigerian tar sand bitumen (maltene) are the c₂₇-c₂₉ diasteranes [13β(H),17α(H); 20R + S] and C₂₈-C₂₉ regular steranes [14β (H),17β (H); 20S]. The reducing metal reaction products of the corresponding asphaltenes (maltene-I) contain mainly C₂₇-C₂₉ regular steranes with the 14β(H),17β(H); 20R + S and 14α(H),17α(H); 20R + S configurations as well as the corresponding diasteranes having the 13β(H),17α(H); 20R + S configuration. These sterane distributions suggest that maltene-I corresponds to an unaltered oil whilst the maltene is equivalent to the product of severe biodegradation of maltene-I. This is consistent with maltene-I being the remnant of “original oil” trapped within the asphaltene matrix and protected from the effect of in-reservior biodégradation.Degradation of Nigerian asphaltenes by refluxing with ferric chloride-acetic anhydride or methanolic potassium hydroxide also releases soluble reaction products having the characteristics of unaltered oil such as the presence of n-alkanes having an unbiased distribution. These methods appear to be milder and more suitable than reducing metal reactions for releasing hydrocarbons occluded by asphaltenes.     

Hydrocarbon products of coals as revealed by pyrolysis-gas chromatography

The hydrocarbon products generated and released from coals continue to be debated. The Mesozoic and Cenozoic southern hemisphere coals have been described as being capable of generating significant quantities of heavy hydrocarbons (oil-like material) when compared to the Paleozoic coals of the northern hemisphere because of changes in the coal forming community. This hypothesis was examined by comparing the pyrolysis-gas chromatography results of a collection of coals. Preliminary results indicate that the most significant difference in pyrolytic products is in the less than nC₁₅ fraction. The data further indicate that coals generate similar types of hydrocarbons independent of age or geographic position if they contain similar bulk maceral content. Coals rich in vitrinite generate predominately aromatic hydrocarbons with lesser amounts of n-paraffins. Coals rich in algae and other exinites generate largely paraffinic hydrocarbons. Coals rich in resins generate naphthenic and aromatic hydrocarbons. The petroleum generating potential of coals also depends on the coal's expulsion efficiency, which is not addressed by this study.     

Organic geochemistry and petrography of Tertiary coals and carbonaceous shales from Argentina

A series of eight Tertiary coal and carbonaceous shale samples with vitrinite reflectance values between 0.50 and 0.58% were extracted, fractionated and the saturated and aromatic hydrocarbons analysed for characteristic components by GC and GC-MS. Additionally, a microscopical study was undertaken in order to obtain a more precise picture of the samples under investigation.The saturated hydrocarbon fractions displayed the typical n-alkane distribution for coals of this rank, with CPI values between 2.0 and 3.1. Among the branched/cyclic compounds, pristane and α, β-homohopane were recognised as relevant components pointing to an oxic depositional environment. Detection of benzohopanes (C₃₂–C₃₅) in the aromatic hydrocarbon fractions suggests that bacteriohopanetetrol was a significant constituent of the coal biomass. Taking into consideration the Pr/Ph ratios, ash contents and microscopical characteristics of the samples, aspects of the possible degradation of hopanetetrol to homohopane are discussed. Resin-derived diterpenoids with the phyllocladane and kaurane skeleton were tentatively identified and, although minor compounds, they are interpreted to be a sign of the contribution of Podocarpaceae and Araucareaceae to the coal swamp.Aromatic compounds were dominated by alkylnaphthalene derivatives, presumably formed by C-ring cleavage and aromatisation of higher plant-derived pentacyclic triterpenois, which were main components in the high-boiling range of the fractions investigated. Angiosperms (especially Fagaceae) are postulated as source for these polycyclic compounds and, hence, for some of the polyalkylated aromatic bicyclics detected.     

Role of coal type and rank on methane sorption characteristics of Bowen Basin, Australia coals

The effect of coal composition, particularly the organic fraction, upon gas sorption has been investigated for Bowen Basin and Sydney Basin, Australia coals. Maceral composition influences on gas retention and release were investigated using isorank pairs of hand-picked bright and dull coal in the rank range of high volatile bituminous (0.78% R_{o max}) to anthracite (3.01% R_{o max}). Adsorption isotherm results of dry coals indicated that Langmuir volume (V_L) for bright and dull coal types followed discrete, second-order polynomial trends with increasing rank. Bright coals had a minimum V_L at 1.72% R_{o max} and dull coals had a minimum V_L at 1.17% R_{o max}. At low rank, V_L was greater in bright coal by about 10 cm³/g, but as rank increased, the bright and dull trends converged and crossed at 1.65% R_{o max}. At ranks higher than 1.65% R_{o max}, both bright and dull coals followed similar trends. These competing trends mean that the importance of maceral composition on V_L varies according to rank. In high volatile bituminous coals, increases in vitrinite content are associated with increases in adsorption capacity. At ranks higher than medium to low volatile bituminous, changes in maceral composition may exert relatively little influence on adsorption capacity. The Langmuir pressure (P_L) showed a strong relationship of decreasing P_L with increasing rank, which was not related to coal type. It is suggested that the observed trend is related to a decrease in the heterogeneity of the pore surfaces, and subsequent increased coverage by the adsorbate, as coal rank increases. Desorption rate studies on crushed samples show that dull coals desorb more rapidly than bright coals and that desorption rate is also a function of rank. Coals of lower rank have higher effective diffusivities. Mineral matter was found to have no influence on desorption rate of these finely crushed samples. The evolution of the coal pore structure with changing rank is implicated in diffusion rate differences.     

本源微生物降解辽河原油的非烃分子结构变化

利用高效本源降解菌在不同时间范围内对辽河油样进行了微生物降解模拟实验,以研究不同降解程度原油分子结构的变化规律。微生物作用前后原油样品做族组分分离及进一步的中性氮化合物和酸性化合物分离,然后对其不同组分进行色谱质谱分析和红外光谱分析。结果表明,辽河油样中的非烃化合物经微生物作用以后,正构一元酸含量随降解时间的增加而增加,且变化幅度逐渐增大;五环三萜类羧酸中C28组分和莫烷酸系列随着降解时间的增加含量上升;轻度的微生物降解作用对咔唑、甲基咔唑、二甲基咔唑等化合物没有明显影响,中等强度降解具有一定的影响;从胶质、沥青质红外光谱图看出,微生物能够降解该原油胶质、沥青质。侧链长度随降解程度增加而变短;芳香环结构抗微生物降解能力强,缩合程度变化不大;而取代基上的烷烃易被微生物氧化,氧化程度随降解程度增加而增加,产生酸类、醚类物质。探讨原油微生物降解中非烃化合物结构及其地球化学特征对石油勘探开发都有重要指导作用。     

Tmax of asphaltenes: a parameter for oil maturity assessment

A new maturity parameter determined on both oil and bitumen samples, the asphaltene T_max, is proposed and discussed. This parameter could be very useful to address the maturity of the source rock. The asphaltene T_max is measured by programmed Rock-Eval pyrolysis, using a modified temperature program. Some phases of the experimental procedure, such as the asphaltene preparation and the Rock-Eval measurement substratum choice, are crucial in order to achieve reliable data. Laboratory simulations were carried out in order to assess the possible effects of both primary and secondary migration on asphaltene T_maxin the expelled oil: the original value of the asphaltene T_max in the bitumen is not substantially modified and it is very close to that measured on kerogen. Examples of the determination of asphaltene T_max on many samples, collected from different areas and with different organic matter composition, are given. Results show that T_max values from oil asphaltenes are reasonable indicators of source rock maturity.     

Classification of torbanite and cannel coal: II. Insights from pyrolysis-GC/MS and multivariate statistical analysis

Petrographic and megascopic criteria have traditionally been used as the basis for the classification of torbanite and cannel coal. For this study, it was hypothesized that modern analytical organic geochemical and multivariate statistical techniques could provide an alternative approach. Towards this end, the demineralized residues of 14 torbanite (rich in Botryococcus-related alginite) and cannel (essentially, rich in organic groundmass and/or sporinite) coal samples were analyzed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Cluster analysis performed on the Py-GC/MS data clearly distinguished the torbanite from the cannel coal, demonstrating a consistency between the chemical properties and the petrographic composition. All the torbanite samples group into one cluster, their pyrolyzates having an overwhelming predominance of straight chain hydrocarbons, a characteristic typical of Botryococcus. The presence of the C₉–C₂₆ n-α,ω-alkadiene series is the key feature distinguishing the torbanites from the other samples. The cannel coals exhibit more chemical diversity, reflecting their greater variability in petrographic composition. The Breckinridge cannel, dominated by a highly aliphatic lamalginitic groundmass, chemically fits the torbanite category. The bituminitic groundmass-dominated cannel coals fall into a cannel sub-cluster, their pyrolyzates having a characteristic predominance of n-alk-1-enes and n-alkanes (particularly the long-chain homologues), with no detectable alkadienes. The vitrinitic groundmass-dominated Ohio Linton cannel and the sporinite-rich Canadian Melville Island cannel are readily distinguishable from the other cannels by the relatively abundant aromatic and phenolic compounds in their pyrolyzates. The internal distribution patterns of alkylaromatic and alkylphenolic isomers are shown to be less significant in the classification of this sample set. Multivariate statistical analysis of the pyrolysis data not only successfully discriminated torbanites from cannel coals, but recognized subtler differences between the examples of these two coal types, in substantial agreement with the petrographic characterization. As such, these methods can substitute for or supplement the traditional microscope-based approach.     

The use of 18O/16O ratios to study the formation and chemical origin of coal

The ${}^{18}\text{O}{}^{16}\text{O}$ ratios of some New Zealand peat, lignite and coal samples were measured and compared with those of various coal precursors (cellulose, lignin and plant resins). The results showed that the major source of oxygen in all cases (except that of high rank coal) was from cellulose with the contribution from lignin and plant resins being insignificant.