Stable sulfur and nitrogen isotopic compositions of crude oil fractions from Southern Germany

Eleven samples of crude oil from the Molasse Basin of Southern Germany were fractionated and their contents of sulfur and nitrogen as well as the stable isotope compositions of these elements (${}^{34}\text{S}{}^{32}\text{S}$ and ${}^{15}\text{N}{}^{14}\text{N}$, resp.) investigated.According to the δ³⁴S determinations, all crude oils from the Tertiary base of the Western and Eastern Molasse belong to one oil family and differ significantly from the Triassic and Liassic oils in the Western Molasse.An enrichment of ³⁴S was observed with increasing polarity of crude oil fractions. The isotope distributions of sulfur in the polar constituents of the biodegraded oils from the sandstones of Ampfing, however, approach a homogeneous distribution.The nitrogen isotope distribution is rather uniform in Southern German oils. A regional differentiation can be recognized, although the overall isotopic variation is small. The δ¹⁵N values of the crudes and asphaltenes do not correlate.     

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.     

The distribution and stable carbon isotopic composition of dissolved organic carbon in estuaries

The distributions of dissolved organic carbon (DOC) and the natural carbon isotope ratio of DOC (DO¹³C) in estuaries reflect the predominant sources and sinks of organic matter from both allochthonous and autochthonous origins. The traditional view is that DOC in land-margin ecosystems reflects mainly the mixing of land-derived and oceanic DOC. However, this view is not consistent with the bulk of our data from a survey of DOC and DO¹³C distributions in estuaries on the East and Gulf coasts of the USA. While it is accurate that the DOC in estuaries includes material derived from land and from the ocean, the distributions of DOC and DO¹³C in several estuaries reflect additional DOC inputs from estuarine phytoplankton and tidal marshes. Even when DOC concentrations were distributed conservatively, the isotopic composition of the DOC revealed the existence of a dynamic cycle of DOC input and removal in some systems.     

Re-Os elemental and isotopic systematics in crude oils

Analysis of 12 worldwide oil samples show that Re and Os abundances are positively correlated with the asphaltene content of oil. Light oils with <1% asphaltene content have basically no measurable Re or Os. Within oil, Re and Os are present dominantly in the asphaltene fraction (>83%), with <14% Re and Os found in the maltene fraction, this distribution is similar to other trace metals such as V and Mo. Rhenium and Os could be present in oil as metalloporphyrin complexes, but given their abundance in the asphaltene component they are also likely bound by heteroatomic ligands. The ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os values in asphaltene calculated at the estimated time of oil generation (Os_i) are similar to those of the whole oil, as expected from the elemental results. This suggests that the asphaltene fraction can be used to approximate the Re-Os isotopic compositions of the whole oil. Os isotopic compositions in oils show a considerable range, from ¹⁸⁷Os/¹⁸⁸Os of 1.9-6.0, and they correlate positively with the age of the proposed source rock. Re/Os ratios also show a large range and overlap the Re/Os ratios found in typical oil source rocks such as organic rich shale.     

Biomarkers and compound-specific stable carbon isotope of n-alkanes in crude oils from Eastern Llanos Basin,Colombia

Representative samples of crude oils from Cusiana, Cupiagua, Apiay, Castilla and Chichimene fields in the Eastern Llanos Basin of Colombia were analyzed to determine its compound-specific stable carbon isotope composition (CSIA) using gas chromatography–isotopic ratio–mass spectrometry (GC–IRMS). GC–IRMS analyses of n-alkanes allowed differentiating between Cretaceous and Cretaceous/Tertiary oil samples. Cretaceous sourced samples have δ¹³C-enriched values than Cretaceous/Tertiary sourced samples; the heavier isotope composition of these samples is due to their major terrigenous organic matter input. Their isotope distribution patterns suggest significant algal and/or bacterial contribution (marine origin). The analysis of the n-alkane fractions by GC–IRMS confirms that the organic matter has marine origin in those samples from Cusiana, Cupiagua and Apiay while Castilla and Chichimene have marine origin with terrestrial inputs. The results were confirmed by gas chromatography/FID and gas chromatography/mass spectrometry (GC/MS). Basic geochemical composition show that samples from Cupiagua/Cusiana fields and Apiay/Castilla/Chichimene fields in the Llanos basin, Colombia present different characteristics reflecting a specific for each depositional environment.     

辽河原油好氧生物降解模拟过程中化学组成及其碳同位素值的变化

对辽河盆地中央凸起南部潜山原油进行了好氧生物降解模拟实验,分析了辽河原油在轻度至中度(PM 1~4级)的好氧生物降解过程中化学组分的变化,以及在此过程中原油族组分和正构烷烃单体的稳定碳同位素值的变化。结果显示,饱和烃组分的消耗速率最快,正构烷烃的消耗速率高于异构烷烃,低碳数正构烷烃的消耗速率高于高碳数正构烷烃。正构烷烃的疏水性及其在原油中的相对浓度可能是影响微生物选择性地消耗正构烷烃的主导因素,即低碳数的正构烷烃由于在油水界面上的表面张力较小而更容易被微生物降解。正构烷烃单体(C_(14)~C_(30))稳定碳同位素值在生物降解过程中较稳定,未产生明显的碳同位素分馏效应。正构烷烃的好氧降解产物主要是脂肪酸、醇和CO_2。辽河原油中正构烷烃组分的δ~(13)C值较饱和烃、芳烃、胶质和沥青质组分都要偏重,降解产物中水溶性较低的高碳数脂肪酸和醇大部分进入胶质中,少部分通过氢键缔合和形成酯键等方式进入到沥青质组分中,造成沥青质组分的δ~(13)C值发生相应的变化,即对沥青质的δ~(13)C值产生"拉动效应";而降解产物中高水溶性的低碳数烷基酸和醇会进入水相而脱离原油,导致残余油的整体δ~(13)C值相应变轻。因此,假如易受生物降解的烃类如正构烷烃等的δ~(13)C值与原油的δ~(13)C值差别比较大,那么生物降解过程中随着原油化学组成的改变,原油本身及其族组分的δ~(13)C值均可能发生明显的变化。     

Metabolic effects on stable carbon isotopic composition of freshwater bivalve shell Corbicula fluminea

The stable isotopic composition of the bivalve shell has been widely used to reconstruct the pa-laeo-climate and palaeo-environment. The climatic and environmental significance of carbon isotopic composition of the bivalve shell is still in dispute, and incorporation of metabolic carbon can obscure carbon isotope records of dis-solved inorganic carbon. This study deals with freshwater bivalve, Corbicula fluminea aragonite shell. The results indicated that the δ13C values of bivalve shells deposited out of equilibrium with the host water and showed an onto-genic decrease, indicating that there are metabolic effects and more metabolic carbon is incorporated into larger shells. The proportion of metabolic carbon of shells varies between 19.8% and 26.8%. However, δ13CS can still be used as qualitative indicators of δ13CDIC and environmental processes that occurred during shell growth.     

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.     

Chemical and Os isotopic study of Cretaceous potassic rocks from Southern Brazil

During the late Mesozoic, an unusually broad range of alkalic magma compositions was erupted along the southern border of the São Francisco craton of Brazil. This magmatic activity includes carbonatite, kimberlite, lamprophyre, lamproite, syenite and the largest known example of extrusive kamafugite, the Mata da Corda formation. To determine the nature of the sources of this magmatism, and their geochemical history, an Os isotope study along with major and trace element and Sr, Nd and Pb isotope analyses of kimberlitic, lamproitic and kamafugitic rocks from the Alto Paranaíba province of Brazil was undertaken. This complements recent geochemical and isotopic studies of these magmas. The Os isotope data for Alto Paranaíba samples point to a peridotitic lithospheric mantle source for the kimberlites and lamproites that was variably depleted in Re, presumably by melt removal at some time between the late Archean and mid-Proterozoic. These lithospheric peridotites experienced LIL-element enrichment by fluid/melt metasomatism at roughly 1 Ga, most likely during mobile belt formation along the western border of the São Francisco craton. Kamafugitic samples have very radiogenic Os, suggestive of mafic (e.g. pyroxenite, websterite, eclogite) source materials that again appear to have been stabilized in the lithospheric mantle of Brazil in the mid to late Proterozoic. The Os isotope evidence for lithospheric sources for the Alto Paranaíba activity, coupled with Sr, Nd and Pb isotopic characteristics that overlap those of the Walvis Ridge hot-spot trace indicate that the EM1 component in South Atlantic ocean island basalts most likely represents the influence of delaminated Brazilian lithospheric mantle mixed into mantle circulation beneath the South Atlantic and is not related to the plume(s) commonly associated with this ocean island magmatism.     

Sterane isomerisation and moretane/hopane ratios in crude oils derived from Tertiary source rocks

The extent of sterane isomerisation reactions and the moretane/hopane ratios of 234 crude oils, taken world wide, from a wide variety of source rocks of differing geological ages, have been measured.This data indicates that in 78 crude oils derived from Tertiary source rocks, sterane isomerisation reactions as determined by the 20S/(20S + 20R) ration of the C₂₉ 5α(H), 14α(H), 17α(H) normal-steranes and the C₂₉ iso/(iso + normal) ratio [iso = 5α (H), 14β(H), 17β(H)] are mainly incomplete and sometimes considerably so. In addition, the same crude oils have 17β(H), 21α(H)-moretane/17α(H), 21β(H)-hopane ratios which are significantly greater (predominantly in the range 0.10–0.30) than those of crude oils derived from older, mature source rocks (mainly less than 0.1).This data, for crude oils, lends support to the hypothesis, proposed by Mackenzie and McKenzie (1983) for source rock extracts, that the time/temperature constraints of sterane isomerisation reactions are such that the time available for isomerisation in Tertiary sediments is generally insufficient, despite generation of crude oil at relatively high temperatures.An alternative hypothesis is that the incomplete sterane isomerisation of Tertiary crude oils may be due to generation of these crude oils from their deltaic, land plant-containing source rocks under low heating conditions.A third hypothesis proposes that the Tertiary crude oils may have picked up the incompletely isomerised steranes from immature sediments during migration. Although possible in particular instances, such a mechanism does not appear to be generally applicable since, in that case, the phenomenon would then appear to be restricted to the Tertiary.The higher moretane/hopane ratios of the Tertiary crude oils could suggest that constraints, similar to those applying in sterane isomerisation, also operate in the conversion of moretane to 17α(H)-hopane.     

Geochemical and stable carbon isotopic composition of coal-related gases from the SW Upper Silesian Coal Basin,Czech Republic

Gas associated with Carboniferous coal seams and younger Miocene sediments in the SW Upper Silesian Basin in Czech Republic shows wide compositional variation. Coal-related gas extracted from cross-measure degassing boreholes, as well as gas released during canister desorption of coal samples from three different mines was analyzed to evaluate the genetic origin and the influence of sorption/desorption processes on the gas composition. Analyses comprised the compositional and stable carbon and isotope composition of coal-related gases. The isotopic composition of gas from cross-measure boreholes indicates thermogenic origin in the southern part of the basin and microbial CO₂ reduction and mixed type origin in the northern part. Gas from canister desorption shows similar origins, but larger compositional and isotopic variation. No consistent isotopic fractionation due to desorption could be observed. Differences in geochemical composition of thermogenic gases could indicate a contribution of gas migrated from deeper formations below the Carpathian overthrust.     

Chemical and stable isotope composition of the high grade metamorphic rocks from the Arendal area,Southern Norway

A group of high grade metamorphic rocks from the Arendal area in Southern Norway has been analyzed for bulk geochemistry, and carbon and sulfur isotopic composition. A good correspondence between the composition of the Arendal rocks and common unmetamorphosed sedimentary and magmatic rocks suggests that except for some volatile compounds no mass transport took place during metamorphism. The high grade mafic rocks interlayered with the metasediments originate from basaltic tuffs and/or intrusives.Carbon occurs as graphite and also in small amounts in a still unidentified form. The carbon of the silicic metasedimentary rocks is isotopically light with an average ¹³C of –20.2, but significantly heavier than carbonaceous matter from unmetamorphosed Precambrian sediments. This is probably due to thermal pyrolysis of the original sedimentary organic matter and to the escape of a gas phase enriched in light carbon by reactions with the graphitic substance during metamorphism.Both the metasediments and the high grade mafic rocks have relatively high sulfur contents. The mean ³⁴S values are 3.3 and 1.8, respectively. This can be explained by isotopically heavy sulfur in the original sediment. Some migration of sulfur probably has occurred from the metasediments into the metamafic rocks.No influence of the hypersthene isograd on the chemical and stable isotope composition could be detected.     

Bulk stable light isotopic ratios in archaeological birch bark tars

The authors report a preliminary study of the light stable isotopic (δD, δ¹³C and δ¹⁸O) values for bulk archaeological birch bark tars, over a geographical (e.g. Greece to Norway) and chronological (9500–3000 BP) range. For δ¹³C an increase in fractionation with increase in latitude is observed in samples from Greece which are less depleted than those from northern Europe. There is no clear difference between the samples from northern Europe. There is no apparent trend in δ¹³C value with the ¹⁴C age of the sample. Due to biosynthetic fractionation all the samples are significantly depleted in ²H and enriched in ¹⁸O relative to the global meteoric water line. This study indicates that archaeological birch bark tar from Greece can be distinguished from those of northern Europe; this separation is probably based on the extreme geographical range of the samples examined here. But this does provide evidence that the birch bark tars were probably made locally rather than traded.     

松辽盆地南部上白垩统烃源岩和原油中正构烷烃的氢同位素组成研究

以松辽盆地南部上白垩统的烃源岩及原油为研究对象,对烃源岩抽提物和原油中正构烷烃的单体氢同位素组成进行了测定。生物标志化合物和正构烷烃的碳氢同位素组成特征表明,在未成熟—成熟阶段正构烷烃的单体氢同位素组成受热成熟度的影响不明显,可以作为油源对比的一个有用的辅助指标。氢同位素组成在母源判识以及重建古沉积环境方面可以提供更多的信息,与碳同位素组成结合应用具有一定的优势。     

Problems of migration of Polish crude oils on the basis of geochemical correlation data and carbon isotope composition

A method for the correlation of crude oils has been worked out on the basis of analyses of 120 crude oils from 4 geological regions of Poland.     

Origin and depositional environments of source rocks and crude oils from Niger Delta Basin: Carbon isotopic evidence

Thirty-nine crude oils and twenty-one rock samples from Niger Delta Basin, Nigeria have been characterized based on their isotope compositions by elemental analysis-isotope ratio mass spectrometry and gas chromatography-isotope ratio mass spectrometry. The bulk carbon isotopic values of the whole rock extracts, saturate and aromatic fractions range from –28.7‰ to –26.8‰, –29.2‰ to –27.2 ‰ and –28.5 ‰ to –26.7 ‰, respectively while the bulk carbon isotopic values of the whole oils, saturate and aromatic fractions range from –25.4 ‰ to –27.8 ‰, –25.9 ‰ to –28.4 ‰ and –23.5 ‰ to –26.9 ‰, respectively. The average carbon isotopic compositions of individual alkanes (nC₁₂-nC₃₃) in the rock samples range from –34.9‰ to –28.2‰ whereas the average isotopic values of individual n-alkanes in the oils range from –31.1‰ to –23.8‰. The δ¹³C isotope ratios of pristane and phytane in the rock samples range from –29.2 ‰ to –28.2 ‰ and –30.2 ‰ to –27.4 ‰ respectively while the pristane and phytane isotopic values range from –32.1‰ to –21.9‰ and –30.5‰ to –26.9‰, respectively. The isotopic values recorded for the samples indicated that the crude oils were formed from the mixed input of terrigenous and marine organic matter and deposited under oxic to sub-oxic condition in lacustrine-fluvial/deltaic environments. The stable carbon isotopic compositions were found to be effective in assessing the origin and depositional environments of crude oils in the Niger Delta Basin.     

A contribution to geochemical correlation between crude oils and potential source rocks in the eastern Molasse Basin (Southern Germany)

Nineteen core samples of potential source rocks for crude oils in the Eastern Molasse Basin were investigated with respect to their isotopic composition of stable carbon in organic extracts and kerogens. p] Some of the chemical and isotopic results give positive or negative indications for the relationship between crude oils and the selected core samples. The analytical data point to the clayish sediments of the Rupelian and Sannoisian as probable source rocks, but further sampling and methodological research will be necessary to confirm the preliminary results on these samples which proved to be of low maturity by their elementary composition.     

Nitrogen and carbon isotopic composition of bone collagen from marine and terrestrial animals

The stable nitrogen and carbon isotope ratios of bone collagen prepared from more than 100 animals representing 66 species of birds, fish, and mammals are presented. The δ¹⁵N values of bone collagen from animals that fed exclusively in the marine environment are, on average, 9%. more positive than those from animals that fed exclusively in the terrestrial environment; ranges for the two groups overlap by less than 1%. Bone collagen δ¹⁵N values also serve to separate marine fish from the small number of freshwater fish we analyzed. The bone collagen δ¹⁵N values of birds and fish that spent part of their life cycles feeding in the marine environment and part in the freshwater environment are intermediate between those of animals that fed exclusively in one or the other system. Further, animals that fed at successive trophic levels in the marine and terrestrial environment are separated, on average, by a 3%. difference in the δ¹⁵N values of their bone collagen. Specifically, carnivorous and herbivorous terrestrial animals have mean δ¹⁵N values for bone collagen of + 8.0 and + 5.3%., respectively. Among marine animals, those that fed on fish have a mean δ¹⁵N value for bone collagen of + 16.5%., whereas those that fed on invertebrates have a mean δ¹⁵N value of + 13.3%. These results support previous suggestions of a 3%. enrichment in δ¹⁵N values at each successively higher trophic level. In contrast to the results for δ¹⁵N values, the ranges of bone collagen δ¹³C values from marine and terrestrial feeders overlap to a great extent. Additionally, bone collagen δ¹³C values do not reflect the trophic levels at which the animals fed. These results indicate that bone collagen δ¹⁵N values will be useful in determining relative dependence on marine and terrestrial food sources and in investigating trophic level relationships among different animal species within an ecosystem. This approach should be applicable to animals represented by prehistoric or fossilized bone in which collagen is preserved.