Isotopic Compositions Of Individual N-alkanes Research Articles

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.

NEW INSIGHTS INTO THE ACTIVE PETROLEUM SYSTEMS IN THE COOPER AND EROMANGA BASINS, AUSTRALIA

This paper presents geochemical data—gas chromatography, saturated and aromatic biomarkers, carbon isotopes of bulk fractions and individual n-alkanes—for oils and potential source rocks in the Cooper and Eromanga basins, which show clear evidence for different source-reservoir couplets. The main couplets involve Cooper Basin source and reservoir and Cooper Basin source and Eromanga Basin reservoir. A subordinate couplet involving Eromanga Basin source and Eromanga Basin reservoir is also identified, together with minor inputs from pre-Permian source rocks to reservoirs of the Cooper and Eromanga basins.The source–reservoir relationships are well expressed in the carbon isotopic composition of individual n-alkanes. These data reflect primary controls of source and maturity and are relatively insensitive to secondary alteration through migration fractionation and water washing, processes that have affected the molecular geochemistry of the majority of oils. Accordingly, the principal Gondwanan Petroleum Supersystem originating from a Permian source of the Cooper Basin has been further subdivided into two petroleum systems associated with Lower Permian Patchawarra Formation and Upper Permian Toolachee Formation sources respectively. Both sources are characterised by n-alkane isotope profiles that become progressively lighter with increasing carbon number—negative n-alkane isotope gradient. The Patchawarra source is isotopically lighter than the Toolachee source. Reservoir placement of oil in either the Toolachee or Patchawarra formations is, in general, a good guide to its source and perhaps an indirect measure of seal effectiveness. The subordinate Murta Petroleum Supersystem of the Eromanga Basin is subdivided into the Birkhead Petroleum System and Murta Petroleum System to reflect individual contributions from Birkhead Formation and Murta Formation sources respectively. Both systems are characterised by n-alkane carbon isotope profiles with low to no gradient. The minor Larapintine Petroleum Supersystem has been tentatively identified as involving pre-Permian source rocks in the far eastern YVarburton Basin and western margin of the Warrabin Trough in Queensland.Eromanga source inputs to oil accumulations in the Eromanga Basin can be readily recognised from saturated and aromatic biomarker assemblages. However, biomarkers appear to over-emphasise local Eromanga sources. Hence, we have preferred the semi-quantitative assessment of relative Cooper and Eromanga inputs that can be made using n-alkane isotope data and this appears to be robust provided that Eromanga source input is greater than 25% in oils of mixed origin. Enhanced contributions from Birkhead sources are concentrated in areas of thick and mature Birkhead source rocks in the northeastern Patchawarra Trough. Pre-Permian inputs are readily recognised by n-alkanes more depleted in I3C compared with late Palaeozoic and Mesozoic sources.Long range migration (>50 km) from Permian sources has been established for oil accumulations in the Eromanga Basin. This, together with contributions from local Eromanga sources, highlights petroleum pro- spectivity beyond the Permian edge of the Cooper Basin. Deeper, pre-Permian sources must also be considered in any petroleum system evaluation of the Cooper and Eromanga basins.

Compound-specific carbon isotope analyses of individual long-chain alkanes and alkanoic acids in Harmattan aerosols

The higher molecular weight n-alkane, n-alkanol and n-alkanoic acid series from higher plant wax are ubiquitous components of aerosol particles in remote areas. The carbon isotopic compositions of individual n-alkanes and n-alkanoic acids have been determined in samples of Harmattan aerosol and composited vegetation wax from Nigeria. The data confirm the terrestrial origin of these compounds and support the distinction among the vegetation sources of C 4 plants (savannah) from C 3 and CAM plants (wet climate, mixed vegetation). The superimposed petroleum components from vehicular emissions in urban areas could not be differentiated from C 3 vegetation by compound-specific isotope analysis.

Stable carbon isotope variation of n-alkanes in Central Graben oils

While isotope analysis of bulk fractions is a well-tried and useful tool in oil correlation, use of compound specific isotope ratio mass spectrometry (CS-IRMS) of individual hydrocarbons is still in its infancy. This technique has been developed over the past few years as a useful research tool, but its potential in petroleum exploration has yet to be demonstrated. In this paper both bulk fraction and individual hydrocarbon isotopic data were acquired. Their use was evaluated and compared with traditional geochemical measurements such as gas chromatography and GC-MS. Data on 72 oils from the Norwegian sector of the Central Graben were acquired. Data include δ 13C isotope composition of whole oil and topped oil, as well as saturated and aromatic hydrocarbon, NSO and asphaltene fractions, and δ 13C isotopic composition of individual n-alkanes in the range nC 4 to nC 35. The same samples were also analysed by capillary GC and GC-MS. GC, GC-MS and bulk fraction isotope data suggest that many of the analysed Greater Ekofisk oils (e.g. Valhall, Edlfisk), i.e. within the Lindesnes Ridge Inversion zone have more than one source facies. Outside of this area, particularly towards the northwest, oils are probably mainly from a single source facies. The isotopic compositions of individual hydrocarbon compounds also reveal the same divisions. In addition, several further features were observed. The normal alkanes of many of the Greater Ekofisk oils are more depleted in 12C between nC 20– nC 25 than at higher or lower molecular weight (possibly representative of the original microbial precursors). Other oils have relatively uniform n-alkane isotope profiles, with n-alkanes which are enriched in 12C relative to the n-alkanes of oils with the other type of profile. The two different isotope profiles are interpreted as being separate source facies. The least mature Greater Ekofisk oils also become more enriched in 12C with decreasing molecular weight. Mature oils from this area tend to have very similar n-alkane isotope values throughout the measured n-alkane range. The higher maturity oils and condensates have n-alkanes < nC 8, which are more depleted in 12C than the n-alkanes > nC 8. The tentative interpretation of this is that the highly mature oils/condensates are sourced only from highly mature source rocks, i.e. of a condensate window maturity and are not products of thermal alteration in the reservoir.

Organic matter and copper mineralization at White Pine, Michigan, U.S.A.

Indigenous and exogenous organic matter in sediments of the North American Midcontinent Rift were involved in precipitation of Cu-bearing minerals during main- and second-stage mineralization events at White Pine, Michigan. Samples of the Proterozoic Nonesuch Formation from the White Pine mine and adjacent areas were investigated petrographically and geochemically in order to determine the influence of organic matter on the precipitation of Cu and to determine whether mineralization influenced thermal maturity of organic matter. During main-stage mineralization, introduction of cupriferous fluids into the lower Nonesuch Fm. formed Cu-bearing sulfides by replacement of pyrite. Sulfur may have been added to the system via abiogenic sulfate reduction, with organic matter providing a direct source of reducing potential. In basal ore horizons where all sulfide had been incorporated into chalcocite during main-stage mineralization, native Cu also precipitated locally, with organic matter presumably acting as a direct reductant. Later compressional faulting at White Pine provided conduits for additional cupriferous fluids; these fluids deposited second-stage Cu mineralization. Inclusions of liquid petroleum and solid pyrobitumen in veins filling fractures associated with compressional faults record migration of petroleum into the White Pine district from the deeper, hotter, axis of the rift penecontemporaneous with second-stage fluids. Some of this petroleum may have acted as a reductant during precipitation of native Cu in basal ore horizons. Biomarker compositions of bitumens and isotopic compositions of individual n-alkanes from petroleums and bitumens suggest that these materials were all derived from organic matter deposited during sedimentation of the Nonesuch Fm.. Biomarker data demonstrate that bitumens from the White Pine area have significantly higher levels of thermal maturity than bitumens from unmineralized strata outside the mine area. Therefore, Cu mineralization at White Pine coincides with a thermal anomaly. Seep petroleums from the northeast and southwest domains of the mine contain different n-alkane distributions; we propose that this difference reflects elevated thermal maturity of seep petroleums spatially associated with second-stage mineralization in the southwestern domain of the mine.