Oil-source correlation and the impact of oil-filling process on geochemical composition of the different states of oils in the Upper Triassic Chang 7 Formation,Ordos basin,China

Five crude oil samples from five wells and 33 oil-containing sandstone reservoir rock samples from six wells of Chang 7 sub-unit were systematically studied to determine hydrocarbons in these oil reservoirs whether are the mixtures of oil components derived from different source rocks or from the same source rock during oil filling process over geological times. Sequential extraction was applied to the oil-containing reservoir rocks to deserve the free and adsorbed oils. The distribution of alkanes, hopanes and steranes and the correlation diagram of Pr/n-C₁₇ versus Ph/n-C₁₈ show that these oil components and crude oils have similar parent materials. And on this basis we compared the thermal maturity of the crude oils, the free oils and adsorbed oils and found that the thermal maturity of these oils is different. The cross plot of C₂₉αα-20S/(20S+20R) versus C₂₉ββ/(αα+ ββ) and the correlation diagram of Pr/n-C₁₇ versus Ph/n-C₁₈ both show that the crude oils have highest thermal maturity, followed by the free oils and then the adsorbed oils. The ratios of ∑C₂₁^?/∑C₂₂⁺ for the crude oils and free oils are greater than the adsorbed oils, indicating the crude oils and free oils have suffered more thermal stress and extensive cracking than that of the adsorbed oils. These geochemical data reveal that hydrocarbons in these oil reservoirs and crude oils were derived from the same source rock with different thermal maturity over geological times.     

GEOCHEMISTRY AND ORIGIN OF UPPER CRETACEOUS OILS FROM THE TERMIT BASIN,NIGER

Crude oil samples (n = 16) from Upper Cretaceous reservoir rocks together with cuttings samples of Upper Cretaceous and Paleogene mudstone source rocks (n = 12) from wells in the Termit Basin were characterized by a variety of biomarker parameters using GC and GC‐MS techniques. Organic geochemical analyses of source rock samples from the Upper Cretaceous Yogou Formation demonstrate poor to excellent hydrocarbon generation potential; the samples are characterized by Type II kerogen grading to mixed Types II–III and III kerogen. The oil samples have pristane/phytane (Pr/Ph) ratios ranging from 0.73 to 1.27, low C₂₂/C₂₁ and high C₂₄/C₂₃ tricyclic terpane ratios, and values of the gammacerane index (gammacerane/C₃₀hopane) of 0.29–0.49, suggesting derivation from carbonate‐poor source rocks deposited under suboxic to anoxic and moderate to high salinity conditions. Relatively high C₂₉ sterane concentrations with C₂₉/C₂₇ sterane ratios ranging from 2.18–3.93 and low values of the regular steranes/17α(H)‐hopanes ratio suggest that the oils were mainly derived from kerogen dominated by terrigenous higher plant material. Both aromatic maturity parameters (MPI‐1, MPI‐2 and R_c) and C₂₉ sterane parameters (20S/(20S+20R) and ββ/ (αα + ββ)) suggest that the oils are early‐mature to mature. Oil‐to‐oil correlations suggest that the Upper Cretaceous oils belongs to the same genetic family. Parameters including the Pr/Ph ratio, gammacerane index and C₂₆/C₂₅ tricyclic terpanes, and similar positions on a sterane ternary plot, suggest that the Upper Cretaceous oils originated from Upper Cretaceous source rocks rather than from Paleogene source rocks. The Yogou Formation can therefore be considered as an effective source rock.     

Whole-oil relationship and origin of oil derived from heterogeneous reservoir systems in an offshore field,SE, Niger Delta

Whole-oil (C3–C39) gas chromatograms were obtained for 46 oil samples collected from a reservoirs pool in an oilfield located offshore SE Niger Delta, to investigate the origins and the relationships of the oils, in spite of the discontinuity of the reservoirs from which the oils were produced. All the oils contained hydrocarbons in the range C₃–C₃₉ with prominent pristane and phytane. The plot of pristine: nC17 versus phytane: nC18 shows oils of terrestrial origin that is deposited in an oxidizing environment. However, some of the oils show depletion of n-paraffin in the C₅–C₁₁ range and have abundant n-paraffin in the C₁₂–C₃₅ range suggesting biodegraded oils. The isoprenoid peaks, however, are more prominent than adjacent n-paraffin in some of the other oils. A star plot of the ratios derived from napthenic, aromatic, isoprenoid, and normal alkane compounds of the samples, in addition to the above-mentioned variations, allowed the grouping of the oils into three families. The results infer that the oils from the south eastern Niger delta may be related in some way (in terms of source input) but may have undergone slightly different histories due to reservoir discontinuity.     

Geochemical characteristics of hydrocarbons in different states during oil-filling process of the Upper Triassic Chang 8 formation,Ordos basin,China

Abstract

Four oil-bearing sandstone samples of Chang 8 sub-unit were collected from Ordos basin and geochemical characteristics of hydrocarbon in different states during oil-filling process were determined. The occurrence of hydrocarbon in sandstone can be divided into four types by using sequential extraction. The features of alkanes, the diagram of Pr/nC₁₇ versus Ph/nC₁₈ and the cross plot of MPI-1 versus R_c show that four type hydrocarbons derived from same source rock, the organic matter includes aquatic organisms and higher plants, moreover, the thermal maturity of the free hydrocarbon is the highest, followed by the sealed hydrocarbon and the cement hydrocarbon, and the inclusion hydrocarbon is the lowest. The variation of geochemical features of hydrocarbons in different states may result from continuous oil-charging in geological history.     

GEOCHEMISTRY OF SEEP AND PRODUCED OIL SAMPLES FROM SOUTHERN CAMEROON

Crude oil samples from surface seeps in the Douala Basin (southern Cameroon) and from producing fields in the nearby Rio del Rey and Kribi‐Campo sub‐basins were analysed for bulk and molecular geochemical parameters by inductively coupled plasma – mass spectrometry (ICP‐MS), gas chromatography – mass spectrometry (GC‐MS) and isotope ratio mass spectrometry (IRMS). The aims of the study were to assess the composition of the oils, to evaluate the relationship between the seep oils and the oils from producing fields, and to highlight the significance of the data for oil exploration in the region. Chromatograms of the saturate fractions of the oils exhibit biodegradation ranging from very light (PM1 on the scale of Peters and Moldowan, 1993) in oil from the offshore Lokele field in the Rio del Rey sub‐basin, to severe (PM 6+) for seep oils from the Douala Basin. A plot of Pr/n‐C₁₇ (1.3– 5.0) versus Ph/n‐C₁₈ (0.8–2.6) for the samples further supports mild biodegradation in some samples (Lokele, Kole, Ebome), and demonstrates that the oils from the Lokele and Kole fields (Rio Del Rey sub‐basin) and from Ebome field (Kribi‐Campo sub‐basin) originated from mixed organic matter with a dominant marine contribution. The Pr/Ph ratio (1.8–2.3) for the Lokele, Kole and Ebome oil samples, and the V/(V+Ni) ratios (< 0.5) for the seep oils (Douala Basin) and the oils from the Lokele, Kole and Ebome fields, indicate derivation from source rocks deposited in oxic – dysoxic environments. The CPI (1.0–1.1) demonstrates that the Lokele and Ebome oils originated from mature source rocks, with the ratios of C₃₁ 22S/(S+R) (0.57 to 0.63) and C₃₀‐βαH/C₃₀‐αβH (0.18–0.23) for the Lokele, Kole and Moudi samples indicating early oil window maturity. Both V/(V+Ni) ratios (0.06–0.22) and δ¹³C (‐26.96 to ‐24.89 ‰) were used for correlation of the oils, with the seep oils from the Douala Basin showing the closest relationship to the oil from the Lokele field. The presence of mature Type II / III source rocks in different basins in southern Cameroon suggests significant potential for oil exploration in the region.     

HIGHER LANDPLANT –DERIVED BIOMARKERS IN LIGHT OILS AND CONDENSATES FROM THE COAL-BEARING EOCENE PINGHU FORMATION,XIHU SAG,EAST CHINA SEA SHELF BASIN

The Cenozoic Xihu Sag in the East China Sea Shelf Basin contains large reserves of coals together with liquid petroleum derived from coal-associated sediments. However, the origin of the petroleum is not well understood. In this study, biomarker assemblages in a suite of recently discovered light oils and condensates from the Paleogene succession in the western margin of in the Xihu Sag were investigated using gas chromatography – mass spectrometry. The objectives were to investigate the samples' thermal maturity and the depositional environment of the precursor source rocks which generated the oils. The light oils are believed to have been derived from coaly source rocks in the Eocene Pinghu Formation. Assessment of thermal maturity based on CPI, pristane/n-C₁₇ ratio and isomerisation ratios of C₂₉ steranes and C₃₁ homohopanes suggest that the hydrocarbons have a relatively low maturity in the early to mid oil generation window. The distribution of isoprenoids relative to n-alkanes, the high pristane/phytane ratios (5.1–10.7), the almost complete absence of gammacerane and C₃₃₊ homohopanes, and the low dibenzothiophene/phenanthrene ratios indicate that the source rocks of the hydrocarbons were deposited in a relatively oxic and sulphate-poor fluvio-deltaic environment which was favourable for coal measure development. Abnormally abundant gymnosperm-derived diterpanes including labdane, 19-norisopimarane, fichtelite, rimuane, pimarane, isopimarane, 17-nortetracyclic diterpene, phyllocladanes and abietane were detected in the samples analysed. 16a(H)-Phyllocladane was identified unambiguously and kauranes were confirmed to be absent. In addition, three 19-norisopimarane isomers, 13β(H)-atisane, and 20-normethylatisane were tentatively identified in the studied samples. The distributions of n-alkanes, isoprenoids and regular steranes, the presence of 4β(H)-eudesmane and oleanane, high Pr/Ph ratios and the abundant diterpanes together suggest that the hydrocarbons were derived from a coaly source rock. Gymnosperms of the conifer families Cupressaceae (especially the former Taxodiaceae) and Pinaceae are interpreted to be the major source of the diterpanes and to have made a significant contribution to the coaly source rock. However, the low abundance of oleanane relative to diterpanes may underestimate the contribution from angiosperms relative to gymnosperms. This could be due to differential preservation and alteration of the di- and triterpenoid precursors during diagenesis and the occurrence of non-specific precursors in higher land plants.     

BIOMARKER CHARACTERISTICS OF CRUDE OILS FROM THE MURZUQ BASIN,SW LIBYA

Twenty crude oil samples from the Murzuq Basin, SW Libya (A‐, R‐ and I‐Fields in Blocks NC115 and NC186) have been investigated by a variety of organic geochemical methods. Based on biomarker distributions (e.g. n‐alkanes, isoprenoids, terpanes and steranes), the source of the oils is interpreted to be composed of mixed marine/terrigenous organic matter. The values of the Pr/Ph ratio (1.36–2.1), C₃₀‐diahopane / C₂₉ Ts ratio and diasterane / sterane ratio, together with the low values of the C₂₉/ C₃₀‐hopane ratio and the cross‐plot of the dibenzothiophene/phenanthrene ratio (DBT/P) versus Pr/Ph ratio in most of oil samples, suggest that the oils were sourced from marine clay‐rich sediments deposited in mild anoxic depositional environments. Assessment of thermal maturity based on phenanthrenes, aromatic steroids (e.g. monoaromatic (MA) and triaromatic (TA) steroid hydrocarbons), together with terpanes, and diasterane/sterane ratios, indicates that crude oils from A‐Field are at high levels of thermal maturity, while oils from Rand I‐Fields are at intermediate levels of thermal maturity. Based on the distributions of n‐alkanes and the absence of 25‐norhopanes in all of the crude oils analysed, none of the oils appear to have been biodegraded. Correlation of the crude oils points to a single genetic family and this is supported by the stable carbon isotope values. The oils can be divided into two sub‐families based on the differences in maturities, as shown in a Pr/nC₁₇ versus Ph/nC₁₈ cross‐plot. Sub‐family‐A is represented by the highly mature oils from A‐Field. Sub‐family‐B comprises the less mature oils from R‐ and I‐Fields. The two sub‐families may represent different source kitchens of different thermal maturity or different migration pathways. In summary, the geochemical characteristics of oil samples from A‐, R‐, and I‐Fields suggest that all the crude oils were generated from similar source rocks. Depositional environment conditions and advanced thermal maturities of these oils are consistent with previously published geochemical interpretations of the Rhuddanian “hot shale” in the Tanezzuft Formation, which is thought to be the main source rock in the Murzuq Basin.     

Biomarkers and isotopic characteristics of crude oils from a central Niger delta depobelt field,Nigeria

Twelve crude oils samples from a field in the central depobelt in the Niger delta, Nigeria were analyzed for their biomarkers and isotopic composition by Gas chromatography–Mass spectrometry and Isotope mass spectrometry. The percentage C_27, C₂₈ and C₂₉ steranes in the oils ranged from 35.80 to 39.9, 28.1 to 30.8 and 29.9 to 35.0, respectively. The distribution of molecular biomarkers and isotopic composition in the oils indicated that they were formed from source rocks of a mixed source (marine and terrestrial kerogen) but with greater input from marine organic matter. The Pr/Ph ratios of the oil samples ranged from 1.2 to 2.3 and this indicated organic matter deposited under suboxic conditions. The vitrinite reflectance (%VRc) values calculated from methylphenanthrene index-1 (MPI-1) parameter ranged from 0.89 to 1.07 indicating oils generated at the peak of oil window.     

ORGANIC GEOCHEMISTRY OF CRUDE OILS AND UPPER CRETACEOUS SOURCE ROCKS FROM CONCESSION 11, WEST SIRTE BASIN,LIBYA

This paper reports the results of Rock‐Eval pyrolysis and total organic carbon analysis of 46 core and cuttings samples from Upper Cretaceous potential source rocks from wells in the West Sirte Basin (Libya), together with stable carbon isotope (δ¹³C) and biomarker analyses of eight oil samples from the Paleocene – Eocene Farrud/Facha Members and of 14 source rock extracts. Oil samples were analysed for bulk (°API gravity and δ¹³C) properties and elemental (sulphur, nickel and vanadium) contents. Molecular compositions were analysed using liquid and gas chromatography, and quantitative biological marker investigations using gas chromatography – mass spectrometry for saturated hydrocarbon fractions, in order to classify the samples and to establish oil‐source correlations. Core and cuttings samples from the Upper Cretaceous Etel, Rachmat, Sirte and Kalash Formations have variable organic content and hydrocarbon generation potential. Based on organofacies variations, samples from the Sirte and Kalash Formations have the potential to generate oil and gas from Type II/III kerogen, whereas samples from the Etel and Rachmat Formations, and some of the Sirte Formation samples, have the potential to generate gas from the abundant Type III kerogen. Carbon isotope compositions for these samples suggest mixed marine and terrigenous organic matter in varying proportions. Consistent with this, the distribution of n‐alkanes, terpanes and steranes indicates source rock organofacies variations from Type II/III to III kerogen. The petroleum generation potential of these source rocks was controlled by variations in redox conditions during deposition together with variations in terrigenous organic matter input. Geochemical analyses suggest that all of the oil samples are of the same genetic type and originated from the same or similar source rock(s). Based on their bulk geochemical characteristics and biomarker compositions, the oil samples are interpreted to be derived from mixed aquatic algal/microbial and terrigenous organic matter. Weak salinity stratification and suboxic bottom‐water conditions which favoured the preservation of organic matter in the sediments are indicated by low sulphur contents and by low V/Ni and Pr/Ph ratios. The characteristics of the oils, including low Pr/Ph ratio, CPI ～l, similar ratios of C₂₇:C₂₈:C₂₉ ααα‐steranes, medium to high proportions of rearranged steranes, C₂₉ <C₃₀‐hopane, low Ts/Tm hopanes, low sulphur content and low V/Ni ratio, suggest a reducing depositional environment for the source rock, which was likely a marine shale. All of the oil samples show thermal maturity in the early phase of oil generation. Based on hierarchical cluster analysis of 16 source‐related biomarker and isotope ratios, four genetic groups of extracts and oils were defined. The relative concentrations of marine algal/microbial input and reducing conditions decrease in the order Group 4 > Group 3 > Group 2 > Group1. Oil – source rock correlation studies show that some of the Sirte and Kalash Formations extracts correlate with oils based on specific parameters such as DBT/P versus Pr/Ph, δ¹³C_saturates versus δ¹³C_aromatics, and gammacerane/hopane versus sterane/hopane.     

MIGRATED PETROLEUM IN OUTCROPPING MESOZOIC SEDIMENTARY ROCKS IN SPITSBERGEN: ORGANIC GEOCHEMICAL CHARACTERIZATION AND IMPLICATIONS FOR REGIONAL EXPLORATION

The presence of migrated petroleum in outcropping rocks on Spitsbergen (Svalbard archipelago) has been known for several decades but the petroleum has not been evaluated by modern geochemical methods. This paper presents detailed organic geochemical observations on bitumen in outcrop samples from central and eastern Spitsbergen. The samples comprise sandstones from the Lower Cretaceous Carolinefjellet Formation, the Upper Triassic – Middle Jurassic Wilhelmøya Subgroup and the Upper Triassic De Geerdalen Formation; a limestone from the De Geerdalen Formation; and carbonates from the Middle Jurassic – Lower Cretaceous Agardhfjellet Formation. In addition a palaeo‐seepage oil was sampled from a vug in the Middle Triassic Botneheia Formation. This data is integrated with the results of analyses of C₁–C₄ hydrocarbon fluid inclusions trapped in quartz and calcite cements in these samples. Organic geochemical data suggest that the petroleum present in the samples analysed can be divided into two compositional groups (Group I and Group II). Group I petroleums have distinctive biomarker characteristics including Pr/Ph ratios of about 1.3–1.5, high tricyclic terpanes relative to pentacyclic terpanes, and relatively high methyl‐dibenzothiophenes compared to methyl‐phenanthrenes. By contrast Group II petroleums have low tricyclic terpanes relative to pentacyclic terpanes and low methyl‐dibenzothiophenes compared to methyl‐phenanthrenes, and most Pr/Ph ratios range from 1.90 to 2.57. The petroleum in both groups was derived from marine shale source rocks deposited in proximal to open marine settings. Group I petroleums, present in the sandstones of the Wilhelmøya Subgroup and the De Geerdalen Formation and as a palaeo‐seepage oil in the vug in the Botneheia Formation, are likely to have been sourced from the Middle Triassic Botneheia Formation. Group II petroleums, found in the sandstone of the Carolinefjellet Formation, the limestone from the De Geerdalen Formation and in carbonates of the Agardhfjellet Formation, are inferred to have been generated from the Jurassic‐Cretaceous Agardhfjellet Formation. The analysis of biomarker and aromatic hydrocarbons in the petroleums indicate three relative maturation levels, equivalent to expulsion at vitrinite reflectances of about 0.7–0.8%R_c, 0.8–0.9%R_c and 1.0–1.6%R_c. On average, Triassic host rocks contain petroleum of higher maturity compared to the Jurassic and Cretaceous host rocks. The fluid inclusion data suggest that gaseous hydrocarbons from the sandstones of the Wilhelmøya Subgroup are thermogenic, and are of similar maturity to the petroleum in extracts from these sandstones, suggesting that the gas was generated together with oil in the oil window. By contrast the inclusion gases from carbonate rocks analysed have a mixed (thermogenic / biogenic) origin. The outcropping rocks in which these oils occur are analogous to offshore reservoirs on the Norwegian Continental Shelf. The study may therefore improve our understanding of the subsurface offshore petroleum systems in the Barents Sea and possibly also in other circum‐Arctic basins.     

金湖凹陷原油轻烃的地球化学特征及意义

对金湖凹陷40个原油样品进行轻烃组分、Mango参数和成熟度等研究。甲基环己烷指数指示出该凹陷原油的干酪根类型为Ⅰ-Ⅱ型;C₅轻烃特征显示有机质来源既有腐泥型也有腐殖型;Mango轻烃参数K₁值基本符合轻烃稳态催化动力学轻烃成因模式,暗示着该凹陷原油有着相似的沉积环境;C₅-C₇轻烃三环优势大于五环和六环优势,表明该地区原油主要来源于湖相沉积环境的烃源岩;原油轻烃组分中的庚烷值和异庚烷指数都较低,原油成熟度低,原油形成温度在120~128℃之间。为进一步认识金湖凹陷原油和烃源岩的地球化学特征提供科学依据。     

ORGANIC FACIES VARIATIONS AND HYDROCARBON GENERATION POTENTIAL OF PERMIAN GONDWANA GROUP COALS AND ASSOCIATED SEDIMENTS,BARAPUKURIA AND DIGHIPARA BASINS,NW BANGLADESH

In the Barapukuria and Dighipara coal basins, NW Bangladesh, the Basement Complex is overlain by the coal‐bearing Permian Gondwana Group. In the present study, 36 core samples collected from five boreholes in these two basins were analysed using organic geochemical and organic petrological methods. Based on the results of biomarker analyses (TIC, m/z 191 and m/z 217 fragmentograms) and maceral composition (proportions of vitrinite, liptinite, inertinite), three organic facies were identified: coals, carbargillites and mudstones. Together with other evidence, cross‐plots of HI versus T_max and Pr/nC₁₇ versus Ph/nC₁₈ indicate that the coals, as expected, were dominated by terrestrial organic matter (OM). The carbargillites contained a mixture of terrestrial and probable Type II aquatic OM, and the mudstones contained mostly terrestrial OM. Accordingly the coals, carbargillites and mudstones are interpreted to have been deposited in swamp‐dominated environments in a delta‐plain setting which was subject, in the case of carbargillites, to periodic flooding. Suboxic conditions were indicated by very high Pr/Ph ratios and a high content of inertinite macerals. All the samples analysed were immature or early mature for hydrocarbon generation, as indicated by mean vitrinite reflectance (%R_o) of 0.60–0.81%, Rock‐Eval T_max of 430–439°C, and biomarker ratios (hopane C₃₂ 22S/(22S+22R)) of 0.57–0.60. Carbargillites showed potential for both liquid and gaseous hydrocarbon generation; coals were mainly gas‐prone with minor liquid hydrocarbon potential; and mudstones were dominantly gas‐prone. The oil‐prone nature of the samples was attributed to the presence of resinite, cutinite, bituminite and fluorescent vitrinite. The presence of exsudatinite within crack networks, solid bitumen and oil droplets as well as bituminite at early oil‐window maturities suggests that the organic matter may have expelled some hydrocarbons.     

Distribution and geochemical significance of phenylphenanthrenes and their isomers in selected oils and rock extracts from the Tarim Basin,NW China

Twenty-two oil samples and eight source rock samples collected from the Tarim Basin,NW China were geochemically analyzed to investigate the occurrence and distribution of phenylphenanthrene(PhP),phenylanthracene(PhA),and binaphthyl(BiN) isomers and methylphenanthrene(MP) isomers in oils and rock extracts with different depositional environments.Phenylphenanthrenes are present in significant abundance in Mesozoic lacustrine mudstones and related oils.The relative concentrations of PhPs are quite low or below detection limit by routine gas chromatography-mass spectrometry(GC-MS) in Ordovician oils derived from marine carbonates.The ratio of 3-PhP/3-MP was used in this study to describe the relative abundance of phenylphenanthrenes to their alkylated counterparts-methylphenanthrenes.The Ordovician oils in the Tabei Uplifthave quite low 3-PhP/3-MP ratios(0.10),indicating their marine carbonate origin,associating with low Pr/Ph ratios(pristane/phytane),high ADBT/ADBF values(relative abundance of alkylated dibenzothiophenes to alkylated dibenzofurans),low C_(30) diahopane/C_(30)hopane ratios,and low Ts/(Ts+Tm)(18α-22,29,30-trisnorneohopane/(18α-22,29,30-trisnorneohopane+17α-22,29,30-trisnorhopane)) values.In contrast,the oils from Mesozoic and Paleogene sandstone reservoirs and related Mesozoic lacustrine mudstones have relatively higher 3-PhP/3-MP ratios(0.10),associating with high Pr/Pli,low ADBT/ADBF.high Ts/(Ts + Tm).and C_(30) diahopane/C_(30) hopane ratios.Therefore,the occuirence of significant amounts of phenylphenanthreiies in oils typically indicates that the organic matter of the source rocks was deposited in a suboxic environment with mudstone deposition.The phenylphenanthreiies may be effective molecular markers,indicating depositional environment and lithology of source rocks.     

LOWER CARBONIFEROUS SHALES IN THE EASTERN TAURIDE BELT,SOUTHERN TURKEY: SOURCE ROCK CHARACTERISTICS

Lower Carboniferous (Tournaisian‐Visean) shales, sandstones and limestones are exposed at the surface in autochthonous units in the Eastern Taurides, southern Turkey. This study investigates the organic geochemical characteristics, thermal maturity and depositional environments of shale samples from two outcrop locations in this area (Belen and Naltas). The total organic carbon (TOC) contents range from 0.11 to 5.61 wt % for the Belen samples and 0.04 to 1.74 wt % for the Naltas samples. T_max values ranging from 432–467 °C indicate that the samples are in the oil generation window T_max and are thermally mature. Rock‐Eval pyrolysis data indicate that the organic matter in the shales is composed mainly of Type II and III kerogen. Solvent extract analyses of the samples show a unimodal n‐alkane distribution with a predominance of low carbon number (C₁₃‐C₂₀) n‐alkanes. Pr/Ph ratios and CPI values range from 1.57–1.66 and 1.08–1.11, respectively Pr/n‐C₁₇ and Ph/n‐C₁₈ ratios also indicate that the shales consist of mixed Type II/III organic matter. Sterane distributions are C₂₇>C₂₉>C₂₈ as determined by the sum of normal and isosteranes, suggesting marine depositional conditions 20S/(20S+20R) and ββ (ββ+αα) C₂₉ sterane ratios range from 0.51–0.54 and 0.53–0.57, respectively. These values are high and 20S/(20S+20R) sterane isomerisation has reached equilibrium values. Tricyclic terpanes are abundant on m/z 191 mass chromatograms and C₂₃ tricyclic terpanes are the dominant peak, which indicates a marine depositional setting. C₂₉ norhopane has a higher concentration than C₃₀ hopane, and C₃₀ diahopane and C₂₉Ts are present in all the samples. Ts and Tm were recorded in similar abundances. Moretane/hopane ratios are very low. 22S homohopanes are dominant over 22R homohopanes, and the C₃₂ 22S/(22R + 22S) C₃₂ homohopane ratios are between 0.58 and 0.59, indicating that homohopane isomerisation has reached equilibrium. C₃₁ homohopanes are dominant and the abundance of homohopanes decreases towards higher numbers. Although regional variations in the level of thermal maturity of Upper Palaeozoic sediments throughout the Taurus Belt region largely depend on burial depth, organic geochemical data indicate that the Lower Carboniferous shales in the eastern Taurus region (Naltas and Belen locations) have potential to generate hydrocarbons. These shales are thermally mature and have entered the oil generation window.     

Geochemistry,generation and maturation of the hydrocarbons at Wadi Al-Rayan oil field,Western Desert of Egypt

`The present work aims to study the organic chemistry, the generation and maturation of the hydrocarbons encountered at Abu Roash Formation, Wadi El Rayan oil field. The analysis of source rocks indicates the presence of two organic facies. The first is characterized by high total organic carbon of 0.93–3.39%, strongly oil-prone (Type II), and good potential for oil generation (pyrolysis S2 yields 4.54–23.26 mg HC/g rock and HI 488–705 mg HC/g TOC). The second attains good range of organic carbon from 0.90% to 1.57%, which is a mixed oil and gas (Type II–Type III) of fair hydrocarbon generation (pyrolysis S2 yield of 1.98–5.33 mg HC/g). The kerogen type consists of unstructured lipids and some terrestrial material. Plot of Pr/n-C17 versus Ph/n-C18 indicates that the crude oil was derived from mixed source rock, while the maturity profile assigns oil windows (0.6 R_o%) matching topmost of Abu Roash G Member.     

ORGANIC GEOCHEMISTRY OF BARENTS SEA PETROLEUM: THERMAL MATURITY AND ALTERATION AND MIXING PROCESSES IN OILS AND CONDENSATES

The petroleum system in the Barents Sea is complex with numerous source rocks and multiple uplift events resulting in the remigration and mixing of petroleum. In order to investigate the degree of mixing, 50 oil and condensate samples from 30 wells in the SW Barents Sea were geochemically analysed by GC‐FID and GC‐MS to evaluate their thermal maturity and secondary alteration signatures. Saturated and aromatic compounds from C₁₄–C₁₈ and biomarker range (C₂₀₊) hydrocarbons were compared with light (C₄‐C₈) hydrocarbon alteration and maturity signatures from a previous study. The geochemical data demonstrate that petroleum generation occurred from the early‐ to late‐oil/condensate window, correlating to calculated vitrinite reflection values of between 0.7%R_c and 1.9%R_c. Two maturation traits are in general present in the oil samples analysed and indicate mixing of petroleum phases: a C₂₀₊ fraction which represents a possible “black‐oil ‐related” signature; and a C_20‐ fraction, which is probably a more recent oil charge. However, maturity variations are less pronounced in condensates, which in general exhibit higher generation temperatures than oils but are influenced by severe phase fractionation effects. The samples are characterised by diverse biodegradation signatures including depletion of C_15‐ saturated compounds, almost complete removal of n‐alkanes, elevated Pr/n‐C₁₇ values, high 17α(H), 25‐norhopane content, and a reverse trend in methylated naphthalene distribution. However, the presence of the more recent, unaltered light hydrocarbon charge together with the oil with a palaeo‐biodegraded signature is clear evidence that mixing has occurred. A cross‐plot of C₂₄‐tetracyclic terpane/C₃₀αβ‐hopane versus C₂₃‐C₂₉‐tricyclic terpane/C₃₀αβ‐hopane can be used to discriminate between Palaeozoic/Triassic and Jurassic‐generated petroleums in the Barents Sea region, since it appears to be maturity independent.     

HYDROCARBON GENERATION POTENTIAL AND DEPOSITIONAL ENVIRONMENT OF SHALES IN THE CRETACEOUS NAPO FORMATION,EASTERN ORIENTE BASIN,ECUADOR

Marine shale samples from the Cretaceous (Albian‐Campanian) Napo Formation (n = 26) from six wells in the eastern Oriente Basin of Ecuador were analysed to evaluate their organic geochemical characteristics and petroleum generation potential. Geochemical analyses included measurements of total organic carbon (TOC) content, Rock‐Eval pyrolysis, pyrolysis — gas chromatography (Py—GC), gas chromatography — mass‐spectrometry (GC—MS), biomarker distributions and kerogen analysis by optical microscopy. Hydrocarbon accumulations in the eastern Oriente Basin are attributable to a single petroleum system, and oil and gas generated by Upper Cretaceous source rocks is trapped in reservoirs ranging in age from Early Cretaceous to Eocene. The shale samples analysed for this study came from the upper part of the Napo Formation T member (“Upper T”), the overlying B limestone, and the lower part of the U member (“Lower U”).The samples are rich in amorphous organic matter with TOC contents in the range 0.71–5.97 wt% and Rock‐Eval T_max values of 427–446°C. Kerogen in the B Limestone shales is oil‐prone Type II with δ¹³C of ?27.19 to ?27.45‰; whereas the Upper T and Lower U member samples contain Type II–III kerogen mixed with Type III (δ¹³C > ?26.30‰). The hydrocarbon yield (S₂) ranges from 0.68 to 40.92 mg HC/g rock (average: 12.61 mg HC/g rock). Hydrogen index (HI) values are 427–693 mg HC/g TOC for the B limestone samples, and 68–448 mg HC/g TOC for the Lower U and Upper T samples. The mean vitrinite reflectance is 0.56–0.79% R₀ for the B limestone samples and 0.40–0.60% R₀ for the Lower U and Upper T samples, indicating early to mid oil window maturity for the former and immature to early maturity for the latter. Microscopy shows that the shales studied contain abundant organic matter which is mainly amorphous or alginite of marine origin. Extracts of shale samples from the B limestone are characterized by low to medium molecular weight compounds (n‐C₁₄ to n‐C₂₀) and have a low Pr/Ph ratio (≈ 1.0), high phytane/n‐C₁₈ ratio (1.01–1.29), and dominant C₂₇ regular steranes. These biomarker parameters and the abundant amorphous organic matter indicate that the organic matter was derived from marine algal material and was deposited under anoxic conditions. By contrast, the extracts from the Lower U and Upper T shales contain medium to high molecular weight compounds (n‐C₂₅ to n‐C₃₁) and have a high Pr/ Ph ratio (>3.0), low phytane/n‐C₁₈ ratio (0.45–0.80) with dominant C₂₉ regular steranes, consistent with an origin from terrigenous higher plant material mixed with marine algae deposited under suboxic conditions. This is also indicated by the presence of mixed amorphous and structured organic matter. This new geochemical data suggests that the analysed shales from the Napo Formation, especially the shales from the B limestone which contain Type II kerogen, have significant hydrocarbon potential in the eastern part of the Oriente Basin. The data may help to explain the distribution of hydrocarbon reserves in the east of the Oriente Basin, and also assist with the prediction of non‐structural traps.     

The formation of the composition of unrecovered oils in producing oil fields of Tatarstan

Analysis of the composition of unrecovered and produced oils of Tatarstan shows that the adsorption-chromatographic process upon oil motion in the reservoir during recovery is manifested in an increase in the density and viscosity of unrecovered oils. They do not contain light hydrocarbons of the IBP ?200°C fraction and have dramatically smaller concentrations of both the least polar lube oil hydrocarbons and alcohol-benzene-extractable resins exhibiting the highest polarity. According to GLC data, unrecovered and produced oils are classified with different subtypes of chemical type A1 of nonbiodegraded oils: produced oils are grouped with subtype 1 and unrecovered oils are attributed to subtype 2. The dynamics of the development of areas of produced oils with the use of a technique based on the activation of reservoir microflora showed that the process of the microbiological oxidation manifests itself in the preferential ability of reservoir microflora to digest C₁₂-C₃₄ n-alkane hydrocarbons as compared to cyclic hydrocarbons. Normal C₁₂-C₂₀ alkanes are consumed by bacteria before hydrocarbons with a greater number of carbon atoms C₂₀-C₃₄ of this series. An analysis of extracts from aqueous infusions of oils showed that the dissolution process leads to the transfer of 0.04–0.07 wt % hydrocarbons and heteroatomic components from oil to water.     

THE MIDDLE CAMBRIAN SUCCESSION IN THE CENTRAL BALTIC BASIN: GEOCHEMISTRY OF OILS AND SANDSTONE RESERVOIR CHARACTERISTICS

Some 36 oilfields, all producing from Middle Cambrian (Deimena Group) sandstones, are located in the central Baltic Basin in an area covering onshore Lithuania and Kaliningrad (Russia) and the adjacent offshore. This paper presents new data on the composition of crude oils from fields in this area and reviews the reservoir properties of the Deimena Group sandstones. Twenty‐one crude oil samples from fields in Lithuania and Kaliningrad were analysed by standard techniques including GC and GC‐MS. The oils had densities of 790.5 to 870.0 kg/m³, and had low asphaltene (<2.2%) and sulphur (<0.44%) contents. The gasoline fraction (b.p. >200°C) ranged from 12–34%. The saturated hydrocarbon content was 35.3 to 77.8%, and the ratio of saturate to aromatic hydrocarbons was 2.1–5.2, indicating long‐distance migration or high thermal maturities. GC analyses of saturate fractions indicated a composition dominated by n‐alkanes with a maximum at C₁₃–C₁₅ and reduced abundance in the C₂₀–C₃₅ range. The analysed crude oil samples are characterized by relatively low concentrations of steranes and triterpanes. Biomarker data indicated an algal origin for the precursor organic matter and a clastic‐dominated source rock. Sterane isomerization ratios imply that the oils are in general relatively mature. Exceptions are samples from the Juzno Olempijskoye and Deiminskoye fields, Kaliningrad, which were early mature. Oil from well Gondinga‐l (Lithuania) was lightly fractionally evaporated and has a relatively higher density, higher viscosity, higher asphaltene content and lower content of saturated fractions. Stable carbon isotope ratios of crude oils and saturated and aromatic fractions were analysed. Whole oils showed little carbon isotope variation, but there were significant differences in δ¹³C ratios for saturated and aromatic fractions. The geochemical data show differences in oil sourcing and indicate the possible existence of different kitchen areas in the Kaliningrad region. Vertical and lateral variations in Deimena Group reservoir properties are controlled by variations in quartz cementation. In fields in western Lithuania, sandstone porosity ranges from 0.7 to 20% and permeability from 20 mD to 300 mD; in fields onshore Kaliningrad, porosity is up to 34% and gas permeability up to 4.8 D. Wide variations in porosity and permeability occur at a field scale.     

Geochemical studies of the Silurian oil reservoir in the Well Shun-9 prospect area, Tarim Basin, NW China

Commercial oil flow has been obtained from the sandstone reservoir of the Lower Silurian Kelpintag Formation in the Well Shun-9 prospect area.In the present studies,10 Silurian oil and oil sand samples from six wells in the area were analyzed for their molecular and carbon isotopic compositions,oil alteration（biodegradation）,oil source rock correlation and oil reservoir filling direction.All the Silurian oils and oil sands are characterized by low Pr/Ph and C21/C23 tricyclic terpane（〈1.0） ratios,＂V＂-pattern C27-C29 steranes distribution,low C28-sterane and triaromatic dinosterane abundances and light δ13C values,which can be correlated well with the carbonate source rock of the O3 l Lianglitage Formation.Different oil biodegradation levels have also been confirmed for the different oils/oil sands intervals.With the S1k2 seal,oils and oil sands from the S1k1 interval of the Kelpintag Formation have only suffered light biodegradation as confirmed by the presence of ＂UCM＂ and absence of 25-norhopanes,whereas the S1k3-1 oil sands were heavily biodegraded（proved by the presence of 25-norhopanes） due to the lack of the S1k2 seal,which suggests a significant role of the S1k2 seal in the protection of the Silurian oil reservoir.Based on the Ts/（Ts＋Tm） and 4-/1-MDBT ratios as reservoir filling tracers,a general oil filling direction from NW to SE has been also estimated for the Silurian oil reservoir in the Well Shun-9 prospect area.