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1.
A series of branched alkylbenzene ranging from C15 to C19 with several isomers (2–5) at each carbon number were identified in sediments from the Dongsheng sedimentary uranium ore deposits, Ordos Basin, China. The distribution patterns of the branched alkylbenzenes show significant differences in the sample extracts. The branched alkylbenzenes from organic-rich argillites and coals range from C15 to C19 homologues, in which the C17 or C18 dominated. On the other hand, the C19 branched alkylbenzenes dominated in the sandstone/siltstone extracts. The obvious differences of the branched alkylbenzene distributions between the uranium-host sandstones/siltstones and the interbedded barren organic-rich mudstones/coals probably indicate their potential use as biological markers associated with particular depositional environments and/or maturity diagenetic processes. Possible origins for these branched alkylbenzenes include interaction of simple aromatic compounds with, or cyclization and aromatization reactions of, these linear lipid precursors such as fatty acids, methyl alkanoates, wax esters or alkanes/alkenes that occur naturally in carbonaceous sediments. The possible simple aromatic compounds may include substituted benzenes, functionalized compounds such as phenols that are bound to kerogen at the benzyl position, and phenols that are decomposition products derived from aquatic and terrestrial sources. The distributions of methyl alkanoates and n-alkanes were found to be different between organic-rich mudstone/coal and sandstone/siltstone. From this result, it can be concluded that such differences of the alkylbenzene distributions were mainly resulting from the differences of organic precursors, although maturity effect and radiolytic alteration cannot be completely excluded.  相似文献   

2.
《Applied Geochemistry》2005,20(3):553-568
Seven coal and carbonaceous mudstone samples were collected from outcropping Jurassic coal beds, on the margin of the Dingxi Basin, Northwestern China. The n-alkane distributions in all of the samples are characterised by high concentrations of the C19–C29 homologues, and very much lower amounts outside of this range. C23 or C24 are usually the most abundant n-alkanes. Straight chain n-alkanes from C23 to C29 show moderate odd-to-even C number predominances (CPI range: 1.26–2.70). Long-chain acyclic n-alkan-2-ones, n-alkan-3-ones and n-alkan-4-ones ranging from C15 to C33 with moderate odd-to-even C number predominances, were detected together with one isoprenoid methyl ketone (6,10,14-trimethylpentadecan-2-one) in all of the samples. The C number distributions of the three series of alkanones show a similar distribution to that of the n-alkanes, but the correspondence is not sufficient to substantiate a product–precursor relationship. It can be concluded that the n-alkan-2-ones are a mixture of the products of microbially-mediated β-oxidation of corresponding n-alkanes in the sediments and from the microbial oxidation of higher plant-derived n-alkanes prior to incorporation in the sediments. The n-alkan-3-ones and n-alkan-4-ones were formed from microbially mediated oxidation of the corresponding n-alkanes in the γ and δ positions, respectively. Generation of the ketones from higher plant n-fatty alcohols and n-alkanoic acids could be a possible way to form some of the ketones observed, but it can only play a minor role in the samples analysed.  相似文献   

3.
n-Alkanes in the soluble organic matter extracted from a series of vitrinite and sporinite concentrates have been analysed by gas chromatography. The macerals were isolated from coals ranging in rank from 77.1% to 86.6% carbon (vitrinite: dry, ash-free), and yields of n-alkanes ranged from 10 to 580 ppm for vitrinites and from 20 to 970 ppm for sporinites. The maximum yields were found at a rank of 85.4% C from vitrinites and 86.6% C from sporinites.Distribution maxima of the n-alkanes, as shown by gas chromatography, range from C27 and C29 at lower ranks to as low as C16 at higher ranks. The distributions also show a progressive decrease in the preference of odd-carbon-number homologues with increasing rank. Virtually smooth distributions were attained in high-volatile bituminous A coals. Quantitative data show that the loss of the odd-carbon-number preference occurred, for the most part, while individual long-chain homologues increased in concentration.There is a progressive increase in the amounts of shorter-chain n-alkanes with increasing rank. It is suggested that sequential processes may have occurred whereby the rate of formation of long-chain n-alkanes in high-volatile bituminous A rank macerals becomes slower than their rate of subsequent fragmentation to shorter chain lengths. Consequently, assuming derivation from the insoluble maceral matrices, the chain-length distributions of parent n-alkyl structures within the insoluble material may retain characteristics pertaining more to the nature of the source organic matter at the time of deposition than do the extractable n-alkane patterns, especially at higher ranks.  相似文献   

4.
Even-carbon number C22-C28n-alkanes, are present in higher concentrations than their C21-C29 odd-carbon number homologs in an organic-rich rock of Mississippian (ca. 310 × 106-yr-old) age, which contains algae-like remnants. Environmental indicators associated with this organic-rich rock permitted environmental comparison with ancient and modern environments that contain n-alkanes which exhibit similar distributions. The results of these comparisons suggest that even-carbon number n-alkanes are preferentially produced in highly saline, carbonate environments where aerobic and anaerobic bacteria have subsisted on the remains of blue-green algae.  相似文献   

5.
We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO2/g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C27–C31) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are inconsistent with diagenetic degradation of terrigenous OM in oxic depositional environments and cannot be associated with thermal breakdown due to the relatively low thermal maturity of the deposits (Rr = 0.26%). It is assumed that the intimate spatial association of high U concentrations resulted in breakdown via radiolytic cracking of recalcitrant polyaliphatic macromolecules (spores, pollen, cuticles, or algal cysts) yielding medium chain length n-alkanes (C13–C24). Reactions of n-alkenes with OH− radicals from water hydrolysis produced alcohols that dehydrogenated to alkanones or through carbonylation formed alkanones. Rapid reactions with hydroxyl radicals likely decreased the isomerization of n-alkenes and decreased alkanone diversity, such that the alkan-2-one isomer is predominant. This specific distribution of components generated by natural radiolysis enables their application as “radiolytic molecular markers”. Breaking of C–C bonds through radiolytic cracking at temperatures much lower than the oil window (<50 °C) can have profound implications on initiation of petroleum formation, paleoenvironmental reconstructions, mineral exploration and in tracking radiolysis of OM.  相似文献   

6.
The current geochemical study of n-alkanes, steranes, and triterpanes in bitumen from the Late Maastrichtian–Paleocene El Haria organic-rich facies in West of Gafsa, southern Tunisia, was performed in order to characterize with accuracy their geochemical pattern. The type of organic matter as deduced from n-alkanes, steranes, and triterpanes distributions is type II/III mixed oil/gas prone organic matter. Isoprenoids and biomarkers maturity parameters (i.e., T s/T m, 22S/(22S?+?22R) of the C31 αβ-hopanes ratios, 20S/(20R?+?20S) and ββ/(ββ?+?αα) of C29 steranes), revel that the organic-rich facies were deposited during enhanced anoxic conditions in southern Tunisa. The organic matter is placed prior to the peak stage of the conventional oil window (end of diagenesis–beginning of catagenesis). All these result are suggested by total organic carbon analysis, bitumen extraction and liquid chromatography data. Thus, the n-alkanes, triterpane, and steranes study remains valuable and practical for geochemical characterization of sedimentary organic matter.  相似文献   

7.
《Organic Geochemistry》2012,42(12):1277-1284
Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were determined in a greenhouse study. Three Sphagnum species were grown under controlled climate conditions. Stable isotope ratios of cellulose, bulk organic matter (OM) and C21–C25 n-alkanes were measured to explore whether fractionation in Sphagnum is species-specific, as a result of either environmental conditions or genetic variation. The oxygen isotopic composition (δ18O) of cellulose was equal for all species and all treatments. The hydrogen isotopic composition (δD) of the n-alkanes displayed an unexpected variation among the species, with values between −154‰ for Sphagnum rubellum and −184‰ for Sphagnum fallax for the C23 n-alkane, irrespective of groundwater level. The stable carbon isotopic composition (δ13C) of the latter also showed a species-specific pattern. The pattern was similar for the carbon isotope fractionation of bulk OM, although the C23 n-alkane was >10‰ more depleted than the bulk OM. The variation in H fractionation may originate in the lipid biosynthesis, whereas C fractionation is also related to humidity conditions. Our findings clearly emphasize the importance of species identification in palaeoclimate studies based on stable isotopes from peat cores.  相似文献   

8.
During the last decade, compound-specific hydrogen isotope analysis of plant leaf-wax and sedimentary n-alkyl lipids has become a promising tool for paleohydrological reconstructions. However, with the exception of several previous studies, there is a lack of knowledge regarding possible effects of early diagenesis on the δD values of n-alkanes. We therefore investigated the n-alkane patterns and δD values of long-chain n-alkanes from three different C3 higher plant species (Acer pseudoplatanus L., Fagus sylvatica L. and Sorbus aucuparia L.) that have been degraded in a field leaf litterbag experiment for 27 months.We found that after an initial increase of long-chain n-alkane masses (up to ∼50%), decomposition took place with mean turnover times of 11.7 months. Intermittently, the masses of mid-chain n-alkanes increased significantly during periods of highest total mass losses. Furthermore, initially high odd-over-even predominances (OEP) declined and long-chain n-alkane ratios like n-C31/C27 and n-C31/C29 started to converge to the value of 1. While bulk leaf litter became systematically D-enriched especially during summer seasons (by ∼8‰ on average over 27 months), the δD values of long-chain n-alkanes reveal no systematic overall shifts, but seasonal variations of up to 25‰ (Fagus, n-C27, average ∼13‰).Although a partly contribution by leaf-wax n-alkanes by throughfall cannot be excluded, these findings suggest that a microbial n-alkane pool sensitive to seasonal variations of soil water δD rapidly builds up. We propose a conceptual model based on an isotope mass balance calculation that accounts for the decomposition of plant-derived n-alkanes and the build-up of microbial n-alkanes. Model results are in good agreement with measured n-alkane δD results. Since microbial ‘contamination’ is not necessarily discernible from n-alkane concentration patterns alone, care may have to be taken not to over-interpret δD values of sedimentary n-alkanes. Furthermore, since leaf-water is generally D-enriched compared to soil and lake waters, soil and water microbial n-alkane pools may help explain why soil and sediment n-alkanes are D-depleted compared to leaves.  相似文献   

9.
Future climatic conditions may coincide with an increased potential for wildfires in grassland and forest ecosystems, whereby charred biomass would be incorporated into soils. Molecular changes in biomass upon charring have been frequently analysed with a focus on black carbon. Aliphatic and aromatic hydrocarbons, known to be liberated during incomplete combustion of biomass have been preferentially analysed in soot particles, whereas determinations of these compounds in charred biomass residues are scarce. We discuss the influence of increasing charring temperature on the aliphatic and aromatic hydrocarbon composition of crop grass combustion residues. Straw from rye, representing C3 grasses and maize, representing C4 grasses, was charred in the presence of limited oxygen at 300, 400 and 500 °C. Typical n-alkane distribution patterns with a strong predominance of long chain odd-numbered n-alkanes maximising at C31 were observed in raw straw. Upon combustion at 300 °C aliphatic hydrocarbons in char were dominated by sterenes, whereas at 400 °C sterenes disappeared and medium chain length n-alkanes, maximising around n-C20, with a balanced odd/even distribution were present. At a charring temperature of 500 °C n-alkane chain length shifted to short chain homologues, maximising at C18 with a pronounced predominance of even homologues. Even numbered, short chain n-alkanes in soils may thus serve as a marker for residues of charred biomass. Aromatic hydrocarbons indicate an onset of aromatization of biomass already at 300 °C, followed by severe aromatization upon incomplete combustion at 400–500 °C. The diagnostic composition of aliphatic and aromatic hydrocarbons from charred biomass affords potential for identifying residues from burned vegetation in recent and fossil soils and sediments.  相似文献   

10.
The paper presents the first results of a comparative study of the composition and distribution of organic matter (OM) (Corg, n-alkanes, Pr, Phy) in samples of the ferromanganese nodule–sediment–pore water system taken at a single site in the Clarion–Clipperton Fracture Zone, Pacific Ocean. Samples were taken during Cruise 120 of R/V James Cook in 2015. The results of the comparison of organogeochemical parameters in the lipid fraction of OM in ferromanganese nodules of different size and morphology with the underlying sediment (0–1 cm) and pore water revealed both principle genetic affinity of OM therein and significant discrepancies between the processes of diagenesis during the formation and growth of each individual ore sample.  相似文献   

11.
We characterized the compositions of organic compounds in a Cheremushka bog sediment core (deposited over the last 35 kyr), located at the eastern coast of Lake Baikal, to obtain basic information about the terrestrial organic matter (OM) which contributed to Lake Baikal sediments. The bog sediment was analyzed for the molecular composition of n-alkanes, lignin phenols and n-C24 to C30 alkanoic acids, as well as the carbon isotopic composition of plant wax derived n-C27 to C33 alkanes.Concentrations of lignin phenols [vanillyl (V) plus syringyl (S) phenols] normalized to total organic carbon (TOC) in the Holocene are twice those for the last glacial maximum (LGM), while concentrations of TOC-normalized n-C24 to C30 alkanoic acids do not change markedly in this period. Thus, the ratio of lignin phenols to n-C24 to C30 alkanoic acids increases from the LGM to the Holocene. This result is essentially consistent with pollen analysis indicating an expansion of woody plants in the Holocene and a prevailing herb-abundant environment for the LGM. The δ13C values of n-C27 to C33 alkanes (e.g. ?29‰ to ?33‰ for C31) indicate the presence of C3-dominant plants throughout the core.The contribution of terrestrial OM to Lake Baikal sediments was estimated using the biomarkers, on the assumption that the OM in the bog sediments is a representative of the terrestrial OM around the lake. Hence, the estimation using lignin phenol or n-C24 to C30 alkanoic acid parameters indicates that 11–24% of the TOC in the Academician Ridge sediments is land-derived for both the Holocene and the LGM, which is similar to the estimates from C/N values of bulk OM. However, the estimates for terrestrial OM using the n-C27 to C33 alkane parameter are generally higher than those using lignin phenol or n-C24 to C30 alkanoic acid parameters. The difference is thought to be associated with the difference in source and behavior of these biomarkers.  相似文献   

12.
The carbon isotope composition (δ13C values) of long chain n-alkanes in lake sediments has been considered a reliable means of tracking changes in the terrigenous contribution of plants with C3 and C4 photosynthetic pathways. A key premise is that long chain leaf wax components used for isotope analysis are derived primarily from terrigenous higher plants. The role of aquatic plants in affecting δ13C values of long chain n-alkanes in lacustrine sediments may, however, have long been underestimated. In this study, we found that a large portion of long chain n-alkanes (C27 and C29) in nearshore sediments of the Lake Qinghai catchment was contributed by submerged aquatic plants, which displayed a relatively positive carbon isotope composition (e.g. −26.7‰ to −15.7‰ for C29) similar to that of terrestrial C4 plants. Thus, the use of δ13C values of sedimentary C27 and C29 n-alkanes for tracing terrigenous vegetation composition may create a bias toward significant overestimation/underestimation of the proportion of terrestrial C4 plants. For sedimentary C31, however, the contribution from submerged plants was minor, so that the δ13C values for C31 n-alkane in surface sediments were in accord with those of the modern terrestrial vegetation in the Lake Qinghai region. Moreover, we found that changes in the δ13C values of sedimentary C27 and C29 n-alkanes were closely related to water depth variation. Downcore analysis further demonstrated the significant influence of endogenous lipids in lake sediments for the interpretation of terrestrial C4 vegetation and associated environment/climate reconstruction. In conclusion, our results suggest that the δ13C values of sedimentary long chain n-alkanes (C27, C29 and C31) may carry different environmental signals. While the δ13C values of C31 were a reliable proxy for C4/C3 terrestrial vegetation composition, the δ13C values of C27 and C29 n-alkanes may have recorded lake ecological conditions and sources of organic carbon, which might be affected by lake water depth.  相似文献   

13.
The Namoi Formation in the Werrie Syncline, north and west of Tamworth, is part of the well-preserved Devonian–Carboniferous fore arc in the New England Fold Belt. The formation is between 640–914 m thick and consists of dominant olive-green mudstones with lenses of sandstone and oolitic limestone. To assess shale gas prospectivity, we analysed five outcrop samples from the Namoi Formation in the Keepit area. Well-preserved aliphatic and aromatic hydrocarbon fractions do not show evidence of weathering or biodegradation. n-Alkanes in all samples have a unimodal distribution maximising at C26 to C28. Little odd-to-even n-alkane carbon number predominance and relatively low Pr/n-C17 and Ph/n-C18 ratios are consistent with a high thermal maturity. Based on the distribution of alkylnaphthalenes and alkylphenanthrenes, the Namoi Formation is in the gas window. Calibration of the methylphenanthrene index and ratio with vitrinite reflectance suggests a calculated reflectance around 2.1%, which given a normal geothermal gradient is equivalent to a maximum temperature of 205°C for the deepest burial of the formation. There is a dominance of parent polycyclic aromatic hydrocarbons (PAH) over alkylated PAHs, supporting a high thermal maturity. Some samples contain biomarkers suggestive of a marine depositional environment, including the C30 sterane index and the C31/C30 hopane ratio. The Namoi Formation is a prospective shale-gas source, as it has been buried sufficiently to be well within the gas window. Where it is exposed at the surface gas will have been lost, but elsewhere it will be buried beneath other sediments and may still retain gas. Key exploration uncertainties include information on organic richness, lateral variation in thermal maturity, mineralogy, and porosity–permeability relationships.  相似文献   

14.
The most widely accepted origin of n-alkan-2-ones in peats is the microbial oxidation of the related n-alkanes and/or oxidative decarboxylation of fatty acids derived from plant input. The distributions of n-alkanes and n-alkan-2-ones in 48 samples from the Roñanzas 6000 cal. yr BP peat bog profile (N Spain) do not justify a single source. The n-alkan-2-ones typically dominate the n-alkanes, maximizing at C19 or C25/C27, whereas the n-alkanes maximized either at C23 or at C31/C33. The averaged δ13C values of the n-alkanes ranged from −32.3‰ to −33.1‰, but those of the n-alkan-2-ones were consistently higher (−29.2‰ to −29.9‰), suggesting a different, probably bacterial, source for the ketones.  相似文献   

15.
Geochemical analysis of dump materials from the opencast Maritsa Iztok mines, Bulgaria, was carried out based on biomarker assemblages of hydrocarbon fractions. Organic matter (OM) and secondary transformations in three representative samples (massive black claystones and materials from the Iztok and Staroselets dump sites) were studied using geochemical proxies.A number of differences were recognised in the respective OM compositions of the samples compared to both published data and between the individual dump samples themselves. The ОM of the studied samples was found to be polar, but also contains some apolar compounds. It consists mainly of resins and asphalthenes. Claystone OM is of the dispersed type, with intense oxidative-reductive interactions in a lacustrine environment resulting in its transformation into an inert material. Dump sample kerogen is of Type II and mixed Type II/III. In all samples, “odd” numbered n-alkanes are found in higher amounts. Diterpenoids (С19, С20) with pimarane, abietane and phyllocladane skeletons are preponderant. Tri- and tetracyclic terpenoids and steranes have been identified in the black claystones OM only. Hopanes are present in low amounts in extractable OM from all three samples. Biomarkers indicate that black claystone OM is formed from aqueous flora, with a minor supply of gymnosperms (mainly G. Sequoia). Iztok Dump OM is structured by higher plants with an aqueous vegetation input. The Staroselets Dump OM formation is assigned to an active microbial reworking of aqueous vegetation and bacteria with a minor coniferous supply. Different geochemical parameters admit anoxic stratified bottom waters for the black claystones with an addition of deep water stagnation for Staroselets sample in a Maritsa Iztok Basin (MIB) aqueous environment.An attempt was also made to track the effect of secondary processes (oxidation, destruction, dearomatisation), temperature, water drainage and wash-out on dump materials. Leaching and weak degradation processes in the MIB dump environment are likely for a time span of ca. 40–50 years, considering the low percentage of short-chain n-alkanes, long-chain prevalence and low Pr/nC17 and Ph/nC18 ratios, with the Iztok Dump sample experiencing more advanced transformations.  相似文献   

16.
Carbon isotopic compositions were determined by GC–IRMS for individual n-alkanes in crude oils and the free, adsorbed and inclusion oils recovered by sequential extraction from reservoir rocks in the Tazhong Uplift and Tahe oilfield in the Tabei Uplift of Tarim Basin as well as extracts of the Cambrian–Ordovician source rocks in the basin. The variations of the δ13C values of individual n-alkanes among the 15 oils from the Tazhong Uplift and among the 15 oils from the Triassic and Carboniferous sandstone reservoirs and the 21 oils from the Ordovician carbonate reservoirs in the Tahe oilfield demonstrate that these marine oils are derived from two end member source rocks. The major proportion of these marine oils is derived from the type A source rocks with low δ13C values while a minor proportion is derived from the type B source rocks with high δ13C values. Type A source rocks are within either the Cambrian–Lower Ordovician or the Middle–Upper Ordovician strata (not drilled so far) while type B source rocks are within the Cambrian–Lower Ordovician strata, as found in boreholes TD2 and Fang 1. In addition, the three oils from the Cretaceous sandstone reservoirs in the Tahe oilfield with exceptionally high Pr/Ph ratio and δ13C values of individual n-alkanes are derived, or mainly derived, from the Triassic–Jurassic terrigenous source rocks located in Quka Depression.The difference of the δ13C values of individual n-alkanes among the free, adsorbed and inclusion oils in the reservoir rocks and corresponding crude oils reflects source variation during the reservoir filling process. In general, the initial oil charge is derived from the type B source rocks with high δ13C values while the later oil charge is derived from the type A source rocks with low δ13C values.The δ13C values of individual n-alkanes do not simply correlate with the biomarker parameters for the marine oils in the Tazhong Uplift and Tahe oilfield, suggesting that molecular parameters alone are not adequate for reliable oil-source correlation for high maturity oils with complex mixing.  相似文献   

17.
European settlement and drought have significantly impacted the hydrology of the Coorong, a shallow coastal lagoon complex in South Australia, which is part of a terminal wetland at the mouth of the River Murray. An increased salinity associated with lower water levels and progressive isolation from ocean flushes contributed to a severe decline in ecological diversity over the past decades. Here we have conducted a molecular and stable isotopic study of a sedimentary core from the northern Coorong Lagoon spanning more than 5000 years to investigate the recent palaeoenvironmental history of the ecosystem. Major alterations were evident in many biogeochemical parameters in sediments deposited after the 1950s coinciding with the beginning of intensified water regulations. The most prominent shift occurred in δ13C profiles of C21–C33 n-alkanes from average values of −23.5‰ to an average of −28.2‰. Further changes included decreases in carbon preference index (CPI) and average chain length (ACL) of the n-alkane series as well as significant increases in algal (e.g. C20 HBI, long chain alkenes and C29-alkadiene) and bacterial (e.g. 13C depleted short chain n-alkanes and hopanoids, δ13C: −35.9‰ to −30.1‰) derived hydrocarbons. Long chain n-alkanes with a strong odd/even predominance as observed here are typically attributed to terrigenous plants. In the Coorong however, terrigenous input to sedimentary OM is only minor. Therefore changes in the before mentioned parameters were attributed to a source transition from a major contribution of macrophytes towards predominantly microalgae and bacteria.δD values of C21–C33 n-alkanes showed a general trend towards more enriched values in younger sediments, indicating an overall rising salinity. However, the most pronounced positive shift in these profiles again occurred after the 1950s. Altogether this study demonstrates that the recent human induced changes of the Coorong hydrology, compounded by a severe drought led to an increase in salinity and alterations of primary production which have been much more significant than natural variations occurring throughout the Holocene over several thousands of years.  相似文献   

18.
The chemical composition of organic matter (Corg, Norg, δ13C, δ15N, and n-alkanes) was studied in the top layer of bottom sediments of the East Siberian Sea. Possible ways were proposed to estimate the amount of the terrigenous component in their organic matter (OM). The fraction of terrigenous OM estimated by the combined use of genetic indicators varied from 15% in the eastern part of the sea, near the Long Strait, to 95% in the estuaries of the Indigirka and Kolyma rivers, averaging 62% over the sea area.  相似文献   

19.
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   

20.
We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ13C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ13C values of odd carbon numbered C23-C33n-alkanes ranged from −37.2‰ to −31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from −244‰ to −180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ13C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C25-C31n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment.  相似文献   

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