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1.
The triterpenoid hydrocarbons of some West Australian shales have been examined by GC-MS. In addition to the common 17α(H),21β(H)-hopanes, 17β(H),21β(H)-hopanes and 17β(H),21α(H)-moretanes, 28,30-bisnorhopane, 25,28,30-trisnorhopane and 25-norhopanes were identified in the organic extracts. In contrast, pyrolysates of the solvent-extracted sediments contained only the common hopane and moretane series, indicating that 28,30-bisnorhopane, 25,28,30-trisnorhopane and 25-norhopanes are not bonded to kerogen, but rather are present in the sediments as free hydrocarbons.  相似文献   

2.
Earlier studies have shown that an unusual C27 triterpane is abundant in sediments from the Norwegian Continental Shelf and the North Sea. This compound was assigned the tentative structures 24,28,30-trisnormoretane or 25,28,30-trisnormoretane, but we have now shown from detailed retention time measurements and a reinterpretation of the mass spectral data that its correct structure is 17α(H),18α (H),21β(H)-25,28,30-trisnorhopane. Two other triterpanes, 25,28,30-trisnormoretane and 28,30-bisnormoretane, have also been identified as minor constituents of extracts of sediments from the North Sea. Possible origins for these compounds are discussed.  相似文献   

3.
Comparison of biological marker alkanes in the kerogen pyrolyzate and bitumen from a sediment is a useful test for the indigenous nature of sediment extracts. For the pyrolysis conditions used, the bulk of the hydrocarbons is released from the kerogen matrix between 375° and 550°C; and its steriochemistry is almost the same as that observed in the extractable bitumen in a genuine source rock. Examples are given to demonstrate that, during pyrolysis, the sterane/terpane ratio decreases and secondary terpanes are generated at the expense of primary ones.The mechanism of artificial petroleum generation by pyrolysis differs from ‘natural’ diagenesis during geological time and is reflected in the composition of certain C27-C29 steranes, as demonstrated by simulation experiments and C29-C30 moretanes and hopanes. The -sterane ratios, jointly with 17α(H)-hopane17β(H)-moretane ratios, tricyclic terpane concentrations and 17α(H)17β(H)-trisnorhopane ratios, allow the differentiation of kerogens from adjacent stratigraphies.  相似文献   

4.
The thermodynamic stability of selected alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers in the C27, C28, C29, C30 and C31 families were calculated using molecular mechanics (MM2) methods and, where possible, calculated equilibrium ratios of certain isomers were compared with observed ratios of isomers in thermally mature crude oil samples. Those calculated and observed ratios having similar values include: (1) the relative distributions among 17β(H)/17α(H) and 21β(H)/21α(H)-hopanes including the absence of the 17β(H),21β(H)- and 17α(H),21α(H)-hopanes; (2) the 22R/22S ratios in 30-methyl-17α-hopane and 30-methyl-17β-moretane; (3) the relative distributions among 17α(H)/17β(H)- and 21α(H)/21β(H)-28,30-bisnorhopanes and among 25,28,30-trisnorhopanes, including the relatively greater stability of 17β(H) isomers in contrast to the regular hopane series; and (4) the ratios of 28(18−17S)abeo hopanes with respect to their unrearranged counterparts including the C27 compounds, Ts/Tm.  相似文献   

5.
A geochemical method for estimation of the maximum temperature of mudstones is proposed. The extents of epimerization of the sterane and the hopane are used. The temperature function is:
Tmax. (°C) = 606015.0?In(dUdUdV)?273
where U = ln (1 ? α/0.54), V = ln(1 ? β/0.61), α = 20S-/20S- + 20R-24-ethyl-5α(H), 14α(H), 17α(H)-cholestane(C29-sterane) and β = 22S-/22S- + 22R-17α(H), 21β(H)-bishomohopane(C32-hopane). The value of dU/dV can be obtained from the tangent to the evolution curve in the UversusV. This temperature function is applicable to the temperature analysis in the range of 50°C–150°C.  相似文献   

6.
Hydrocarbon distributions and stable isotope ratios of carbonates (δ13Ccar, δ18Ocar), kerogen (δ13Cker), extractable organic matter (δ13CEOM) and individual hydrocarbons of Liassic black shale samples from a prograde metamorphic sequence in the Swiss Alps were used to identify the major organic reactions with increasing metamorphic grade. The studied samples range from the diagenetic zone (<100°C) to amphibolite facies (∼550°C). The samples within the diagenetic zones (<100 and 150°C) are characterized by the dominance of C<20n-alkanes, suggesting an origin related with marine and/or bacterial inputs. The metamorphic samples (200 to 550°C) have distributions significantly dominated by C12 and C13n-alkanes, C14, C16 and C18n-alkylcyclopentanes and to a lesser extend C15, C17 and C21n-alkylcyclohexanes. The progressive 13C-enrichment (up to 3.9‰) with metamorphism of the C>17n-alkanes suggests the occurrence of cracking reactions of high molecular weight compounds. The isotopically heavier (up to 5.6) C<17n-alkanes in metamorphic samples are likely originated by thermal degradation of long-chain homologous with preferential release of isotopically light C1 and C2 radicals. The dominance of specific even C-number n-alkylcyclopentanes suggests an origin related to direct cyclization mechanism (without decarboxylation step) of algal or bacterial fatty acids occurring in reducing aqueous metamorphic fluid conditions. The regular increase of the concentrations of n-alkylcycloalkanes vs. C>13n-alkanes with metamorphism suggests progressive thermal release of kerogen-linked fatty acid precursors and degradation of n-alkanes. Changes of the steroid and terpenoid distributions are clearly related to increasing metamorphic temperatures. The absence of 18α(H)-22,29,30-trisnorneohopane (Ts), the occurrence of 17β(H)-trisnorhopane, 17β(H), 21α(H)-hopanes in the C29 to C31 range and 5α(H),14α(H),17α(H)-20R C27, C29 steranes in the low diagenetic samples (<100°C) are characteristic of immature bitumens. The higher thermal stress within the upper diagenetic zone (150°C) is marked by the presence of Ts, the disappearance of 17β(H)-trisnorhopane and thermodynamic equilibrium of the 22S/(22S + 22R) homohopane ratios. The increase of the ααα-sterane 20S/(20S + 20R) and 20R ββ/(ββ + αα) ratios (from 0.0 to 0.55 and from 0.0 to 0.40, respectively) in the upper diagenetic zone indicates the occurrence of isomerization reactions already at <150°C. However, the isomerization at C-20 (R → S) reaches thermodynamic equilibrium values already at the upper diagenesis (∼150°C) whereas the epimerisation at C-14 and C-17 (αα → ββ) arrives to constant values in the lower anchizone (∼200°C). The ratios Ts vs. 17α(H)-22,29,30-trisnorneohopane [(Ts/(Ts + Tm)] and 18α(H)-30-norneohopane (C29Ts) vs. 17α(H),21β(H)-30-norhopane [C29Ts/(C29Ts + C29)] increase until the medium anchizone (200 to 250°C) from 0.0 to 0.96 and from 0.0 to 0.44, respectively. An opposite trend towards lower values is observed in the higher metamorphic samples.The occurrence of specific hydrocarbons (e.g., n-alkylcyclopentanes, cadalene, hydrogenated aromatic compounds) in metamorphic samples points to kerogen degradation reactions most probably occurring in the presence of water and under reducing conditions. The changes of hydrocarbon distributions and carbon isotopic compositions of n-alkanes related to metamorphism suggest that the organic geochemistry may help to evaluate the lowest grades of prograde metamorphism.  相似文献   

7.
8.
Novel biological marker parameters are applied to problems of geochemical correlation of crude oils in the McKittrick Field, California. An attempt is described to distinguish four diagenetic parameters; namely, source input, source maturation, migration and ‘in reservoir’ maturation. The tools include the absolute concentration of steranes, terpanes and paraffins (n + iso) in combination with internal ratios of individual biomarkers such as primary/secondary terpanes, 17α(H)-trisnorhopane/18α(H)-trisnorhopane II (both maturation specific), 5β/5α-steranes, 5β-steranes/17α(H)-hopanes and rearranged steranes/5α-steranes (all migration oriented), 5α/5α-steranes and a number of terpane ratios of partially unknown chemical structure (source input specific).Among other new correlation parameters are: two series of mass chromatograms (m/e 253 and 239), signaling monoaromatized steranes, a series of presumably rearranged steranes (m/e 259), and a series of methylhopanes (m/e 205).The results obtained on the molecular level exceed the degree of information obtainable from organic geochemical ‘bulk’ parameters such as yields of saturates, aromatics, sulfur compounds and C13/C12 ratios by far; however, both types of parameters are mutually supporting. All conclusions are consistent with subtle stratigraphie and overall geologic prerequisites.  相似文献   

9.
The distributions of polycyclic alkanes were monitored in a Neocomian sequence (well 1-ESS-34) from the Espirito Santo Basin, southeast Brazil. The profiles included, apart from regular hopanes, significant concentrations of 18α(H), 28,30-bisnorhopane and subordinate amounts of gammacerane. Sterane concentrations, normally with hopane/sterane <5, were compatible with other geochemical data indicating a predominantly planktonic/microbial source of the deposited organic matter. Sample maturities ranged from very immature to the onset of oil generation, allowing biomarker distributions to be followed along a broad maturation range. The ability of certain molecular ratios (e.g. C27 17α(H)/17β(H)hopanes) to reflect a maturity sequence with depth in the closely-spaced strata of the immature upper levels (Jiquiá Stage) showed the value of molecular techniques over classical geochemical methods (e.g. vitrinite reflectance) for the study of immature sequences. The presence in the oils of southern Espirito Santo of 28,30-bisnorhopane, gammacerane and methyl steranes in similar concentrations as in extracts of the deepest levels of the 1-ESS-34 well qualify the Jiquia Stage as the probable source rock of oils accumulated in the basin.  相似文献   

10.
《Organic Geochemistry》1999,30(8):985-1010
The Buller Coalfield (South Island, New Zealand) is an inverted late Paleogene Basin that contains middle Eocene bituminous coals which exhibit considerable variation in both coal rank (across-basin), and coal type (in-seam). Twenty-two fractionated bitumen extracts of Brunner Coal Measures coal samples from 12 drillholes were analyzed by GC and GC–MS to characterize the effect of coal rank and type on conventional hydrocarbon maturity indices at the beginning and end of the oil window (0.56–1.26% Romax).The Carbon Preference Index, pristane/phytane and isoprenoid/n-alkane ratios evolve throughout the high volatile bituminous B rank stage, while other biomarker ratios [18α(H)-22,29,30-trisnorneohopane/17α(H)-22,29,30-trisnorhopane (Ts/Tm), 18α(H),21β(H)-30-norneohopane (C29 Ts)/17α(H),21β(H)-30-norhopane and C30 diahopane/hopane] do not show appreciable change in value until medium volatile bituminous rank. Various aromatic based ratios appear to be more effective in delineating rank throughout the entire oil window; in particular the Methylphenanthrene Index and vitrinite reflectance are positively correlated over the entire bituminous rank range. However, subtle changes in depositional conditions (variable coal type) complicate these rank estimates. Within a given coal seam, variation in CPI, isoprenoid/n-alkane and hopane/sterane ratios appear to be related to the hydrogen content of the coal, while the homohopane index and the oleanane/hopane ratio covary with sulfur content. As with depressed vitrinite reflectance values, MPI is similarly lowered in the perhydrous samples. The mechanisms that control these hydrocarbon parameters during deposition and diagenesis are complex and convoluted, however, changes in bacterial activity and community (with marine incursion) appear to play an important role. Due to these anomalies, none of the hydrocarbon maturity indices calculated can be singularly used to constrain coal rank.  相似文献   

11.
Gel permeation chromatography (GPC) using a high performance liquid chromatography (HPLC) system was studied for the separation and enrichment of steroid and hopanoid hydrocarbons from crude oil for stable carbon isotope analysis. A crude oil sample was pretreated using silica gel chromatography and 5A molecular sieve to remove polycyclic aromatic hydrocarbons and n-alkanes. The GPC behavior of both the pretreated saturated hydrocarbon fraction of the oil and standard steroid [5α(H), 14α(H), 17α(H) C27–C29 steranes], hopanoid [17α(H) C27 trisnorhopane, 17α(H), 21β(H) C29–C32 hopanes] and triterpenoid [18α(H)-oleanane, gammacerane] mixtures were examined. The results indicate that 17α(H), 21β(H) hopanes as well as steranes could be enriched efficiently using GPC and that they could be obtained without removing n-alkanes from the oil saturated hydrocarbon fraction. The GPC behavior of steroid and triterpenoid hydrocarbons was controlled by molecular size and shape.  相似文献   

12.
The lipid biomarkers of hopanoids in cold seep carbonates from the South China Sea continental slope were investigated by gas chromatography–mass spectrometer (GC–MS) and gas chromatography-isotope ratio-mass spectrometer (GC-ir-MS). The distribution of hopanes/hopenes shows a preference for the ‘biological’ 17β(H), 21β(H)-over the ‘geological’ 17α(H), 21β(H)-configuration. This interpretation is in agreement with the strong odd–even preference of long-chain n-alkanes in those samples, suggesting that the ββ hopanes may be the early diagenetic products of biohopanoids and the αβ, βα configurations of hopanes were mainly derived from allochthonous sources contributing to the organic matter of the carbonates. In terms of hopanoid acids, the C30 to C33 17β(H), 21β(H)-hopanoid acids were detected with C32 17β(H), 21β(H)-hopanoid acid being the most abundant. However, there is a significant difference in stable carbon isotopic compostions of the C32 17β(H), 21β(H)-hopanoic acid among samples (−30.7‰ to −69.8‰). The δ13C values match well with the carbon isotopic compositions of SRB-derived iso-/anteiso-C15:0 fatty acids in the samples, which strongly depend on the carbon utilization types by microbe. The most abundant compound of hopanols detected in the samples, C30-17β(H), 21β(H)-hopanol, may be a good indicator of diagenetic product of type I methanotrophs. The molecular and carbon isotopic compositions of hopanoids demonstrate clearly that there is a combination contribution of both SRB and type I or type X methanotrophs to the source organism in the seep carbonates from the South China Sea continental slope.  相似文献   

13.
14.
Mass absorption coefficients (A2) for a series of standard rocks, have been calculated in the wavelength region 0.492–3.03 a?. Plots of these data against the intensity of the Compton scattered peak [(I) Compton] give an excellent correlation for the wavelengths 0.429 a? to the Fe-absorption edge (1.74 a?); the data confirm the observations of Reynolds. Hence, routine measurement of one peak will give the mass absorption coefficient of a sample in an analytically important region (Sn/1bKα to Ni/1bKα). A2 has also been directly measured on three of the samples and systematic differences between calculated and measured are attributed to the measuring technique. At wavelengths longer than the Fe-absorption edge, (up to 3.03 a?) A2 can be estimated using a combination of (I) Compton and Fe/1bKα c.p.s. This technique enables meaningful matrix corrections to be carried out on the elements Co, Mn, Cr, V, Ti, Sc (K spectra) and Ba (L spectra). Cr and Ba results are presented for some standard rocks.  相似文献   

15.
The degradation of acyclic petroleum hydrocarbons was studied during a 24-month experiment in Mediterranean coastal sediments (Gulf of Fos). Sediment cores entirely contaminated with oil (Arabian Light Crude Oil) were incubated in situ. The use of conservative tracers of sediment's particles reworking (luminophores) allowed the distinction of the reworked layer from the anoxic deeper sediments. Using the 17α,21βC30 hopane (C30H) as an inert internal reference, we could demonstrate that, after 24 months of experiment, acyclic petroleum hydrocarbons can be degraded under natural anaerobic conditions. The reactivity of individual alkanes appeared to depend on their chemical structure. To cite this article: D. Massias et al., C. R. Geoscience 335 (2003).To cite this article: D. Massias et al., C. R. Geoscience 335 (2003).  相似文献   

16.
Results of the analyses of twenty-three samples from the Middle Miocene to Lower Pliocene strata from DSDP Site 467, offshore California, are presented. The analyses were performed with the aim of determining the origin of the organic matter, the stratigraphic section's hydrocarbon generation potential and extent of organic diagenesis. Organic carbon contents are an order of magnitude greater than those typically found in deep sea sediments, suggesting an anoxic depositional environment and elevated levels of primary productivity. Hydrocarbon generation potentials are above average for most samples. The results of elemental analyses indicate that the kerogens are primarily composed of type II organic matter and are thermally immature. Analysis of the bitumen fractions confirms that the samples are immature. In cores from 541 to 614 meters, the gas chromatograms of the C15+ non-aromatic hydrocarbon fractions are dominated by a single peak which was identified as 17α(H), 18α(H), 21β(H)-28, 30-bisnorhopane. This interval is the same area in which the highest degrees of anoxia are observed as reflected by the lowest pristane/phytane ratios. This correlation may have some implications with regard to the origin of the bisnorhopane and its possible use as an indicator of anoxic depositional conditions within thermally immature sediments.  相似文献   

17.
The textural study of a sizable number of samples from the various microenvironments of the Thar Desert reveals that the overall size of the desert sediments corresponds to fine sand (2–3 φ); the crests of the dunes are coarser than the flanks; the sediments have bimodal and/or polymodal population, they show a high sand/silt ratio, are well sorted, and are fine-skewed to strongly-fine-skewed; most of the sediments show platykurtic and very platykurtic curves, exhibit subangular to subrounded outlines, and show a moderate to high degree of sphericity.It is concluded that the scatter plots between moment mean (χ) and moment skewness (α3), moment mean (χ) and first percentile, graphic mean (Mz) and inclusive graphic skewness (SkI), moment standard deviation (σ) and moment mean (χ), moment standard deviation (σ) and first percentile, cubed standard deviation and mean cubed deviation (α3σ3), moment standard deviation (σ) and moment skewness (α3), and moment standard deviation (σ) and mean cubed deviation (α3σ3), can safely be used to distinguished the desert sediments from those accumulated in river and beach environments.  相似文献   

18.
A thermodynamic model for concentrated brines has been developed which is capable of predicting the solubilities of many of the common evaporite minerals in chloro-sulfate brines at 25°C and 1 atm. The model assumes that the behaviour of the mean stoichiometric ionic activity coefficient in mixtures of aqueous electrolytes can be described by the Scatchard deviation function and Harned's Rule. In solutions consisting of one salt and H2O, the activity coefficient is described by the expression logλ4plusm;=-|z+z? √ 1/c1+a?B √ I) + 2(V+V?/v)Bi?l where a? and B? salt specific parameters obtained from data regression. In a mixture of n electrolytes and H2O, B? for the ith component is given by Bi?i=B i?i+σ αijyj where αij is a (constant) mixing parameter characterizing the interaction of the i and j components and yj is the ionic strength fraction of the jth component. The activity of H2O is obtained from a Gibbs-Duhem integration and does not require any additional parameters or assumptions. In this study, parameters have been obtained for the systems NaCl-KCl-MgCl2-CaCl2-H2O and NaCl-MgSO4-H2O at 25°C and 1 atm. Computed solubility curves and solution compositions predicted for invariant points in these systems agree well with the experimental data. The model is flexible and easily extended to other systems and to higher temperatures.  相似文献   

19.
Al26 and noble gas contents of 6 ordinary chondrites with He3Ne21 ratios above 6.0 or below 4.0 are used to infer the variability of the production rates of He3 and Ne21 (PHe3 and PNe21). The ratio of the observed Al26 content to a calculated, normal value is taken as a measure of the change of PNe21 from its normal value. The corresponding change in PHe3 is then computed from the observed He3Ne21 ratio and an average value of PHe3.According to these calculations which exclude orbital effects, PHe3 will be near the average value in meteorites with high He3Ne21 ratios, while PNe21 will be about 30 per cent below normal. In meteorites with low He3Ne21 ratios, PHe3 may be depressed by as much as 25 per cent from normal while PNe21 may be 15–20 per cent above the average.  相似文献   

20.
Major and rare earth element (REE) data for basalts from Holes 483, 483B, and 485A of DSDP Leg 65, East Pacific Rise, mouth of the Gulf of California, support a simple fractional crystallization model for the genesis of rocks from this suite. The petrography and mineral chemistry (presented in detail elsewhere) provide no evidence for magma mixing, but rather a simple multistage cooling process. Based on its lowest TiO2 content (0.88%), FeO1MgO ratio (0.95 with total Fe as FeO), and Mg# (100 MgMg + Fe″ = 70), sample 483-17-2-(78–83) has been selected as the most primitive primary magma of the samples analyzed. This is supported by the REE data which show this sample has the lowest total REE content, a LaSmcn (chondrite-normalized) = 0.36, and EuSmcn = 1.05. Because other samples analyzed have higher SiO2, lower Mg#, and a negative Eu anomaly (EuSmcn as low as 0.89), they are most likely derivative magmas. Wright-Doherty and trace element modelling support fractional crystallization of 14.1% plagioclase (An88), 6.7% olivine (Fo86), and 4.7% clinopyroxene (Wo41En49Fs10) from 483-17-2-(78–83) to form the least differentiated sample with Mg# = 63. The LaSmcn of this derivative magma is almost identical to the parent magma (0.35 to 0.36), but the other samples have higher LaSmcn (0.45 to 0.51), more total REE, and lower Mg# (60 to 56). Both Wright-Doherty and trace element modelling indicate that the primary magma chosen cannot produce these more evolved samples. For the major elements, the TiO2 and P2O5 are too low in the calculated versus the observed (1.38 to 1.90; 0.11 to 0.17, respectively, for example). Rayleigh fractionation calculates a lower LaSmcn and requires about 60% crystal removal versus 40% for the Wright-Doherty. These more evolved samples must be derived from a parent magma different from the one selected here and, unfortunately, not sampled in this study. A magma formed by a smaller degree of partial melting with slightly more residual clinopyroxene left in the mantle than for sample 483-17-2-(78–83) is required.  相似文献   

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