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1.
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   

2.
《Applied Geochemistry》2006,21(6):1006-1015
We investigated the ability of accelerated solvent extraction (ASE) to extract selected lipid biomarkers (C19–C34 n-alkanes, n-alcohols and n-fatty acids as well as dehydroabietic acid and β-sitosterol) from a sandy soil profile under Corsican pine. Two organic layers (moss and F1) as well as two mineral soil horizons (EA and C1) were sampled and extracted with DCM/MeOH (93:7 v/v) by ASE at 75 °C and a pressure of 6.9 × 106 Pa or 17 × 106 Pa. Soxhlet extractions were used as the established reference method. After clean-up and derivatization with BSTFA, the extracts were analyzed on GC/MS.Using Soxhlet as a reference, we found ASE to extract all compounds adequately. The n-alkanes, especially, were found to be extracted very efficiently from all horizons studied. Only the n-fatty acids and β-sitosterol from the organic layers seemed to be extracted at a slightly lower efficiency by ASE. In all but two instances the relative abundance of extracted lipids within a component class was the same regardless of the extraction method used.Using a higher pressure in the ASE extractions significantly increased the extraction efficiency for all component classes in the moss layer, except β-sitosterol. The effect was most pronounced for the n-alkanes. In the EA horizon, a higher pressure slightly reduced the extraction efficiency for dehydroabietic acid. The observed differences between ASE and Soxhlet extractions as well as the pressure effect can be explained by a decrease in polarity of the extractant due to the elevated pressure and temperature applied during ASE extractions as compared to Soxhlet extractions. This would mainly increase the extraction efficiency of the least polar biomarkers: the n-alkanes as was observed. In addition, a better penetration of still partially water-filled micro pores under elevated pressure and temperature may have played a role.  相似文献   

3.
The Mundaú–Manguaba estuarine–lagoon system (MMELS) constitutes one of the most representative ecosystems in the state of Alagoas, NE Brazil. Approximately 30% or 60,000 ha of the lower surrounding drainage basin of the MMELS are covered by sugar cane and a total of 250,000 inhabitants contribute untreated effluent to the system. Short sediment cores from MMELS were collected in 2007 at three sites: Manguaba Lagoon (C03), Mundaú Lagoon (C07) and Mundaú River (C08) in order to characterize the delivery and deposition of n-alkanes over the past 40 yr. The n-alkanes ranged from C15 to C35, with total aliphatic hydrocarbon (TAH) concentration in the range 27.8–139.5 μg g−1. An unresolved complex mixture (UCM) was observed in all sediments. The terrigenous/aquatic ratio (TAR), carbon preference index (CPI) and average chain length (ACL) showed that the terrigenous input dominated. The (δ13C) values of individual n-alkanes (C16–C33) varied between −22.6‰ and −34.2‰, suggesting a dominance of 12C-enriched n-alkanes that originated from C3 plants and lacustrine algae. The data reflect how anthropogenic input (via sewage, industrial pollution and agriculture) has influenced the organic content of the system through time.  相似文献   

4.
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   

5.
《Applied Geochemistry》1998,13(7):851-859
Emerging acceptance of the limitations of separate phase product recovery has spawned interest in the intrinsic alteration of residual separate phase petroleum products. In this study the geochemical changes in a continuous core through soil containing a separate phase diesel fuel #2 (SPD) in contact with groundwater are investigated. Chemical heterogeneities are shown to exist which can be attributed to weathering, particularly intrinsic biodegradation. The results show that the aliphatic hydrocarbon content is reduced and the δ13C ratio of the aliphatic hydrocarbons increased from top to bottom in the core. Both changes are thought to be due to preferential biodegradation of (isotopically lighter) n-alkanes. A slight increase in the relative abundance of shorter chain n-alkanes (<n-C17) was also observed. The distribution of the dominant aromatic hydrocarbons (C0–C3 alkyl-naphthalenes) is remarkably consistent throughout the core, although naphthalene is depleted below the oil–water interface. In spite of low oil saturation (S0), little or no evidence of biodegradation is noted at the uppermost boundary of the SPD. However, intrinsic biodegradation is evident approximately 0.3 m above the oil–water interface in spite of higher S0. The extent of the chemical changes attributable to biodegradation (described above) gradually increases below the oil–water interface, eventually reaching a maximum at the bottom of the SPD profile (∼1.2 m below the interface) where S0 is again reduced. The relatively higher level of biodegradation observed at and below the oil–water interface may be attributed to the reduced S0 in this zone. An estimate of the mass reduction in diesel fuel between the uppermost and bottommost parts of the core is calculated to be 23% (by weight), due predominantly to the biodegradation of n-alkanes.  相似文献   

6.
The Holocene successions of numerous shallow lakes located along the Coorong coastal plain in South Australia attest to the impact of rising sea level and changing climate on their depositional environment. Old Man Lake is one of the smallest perennial alkaline lakes in the region. Its succession comprises a basal lagoonal sand rich in humic organic matter (OM) overlain by a 3.7 m thick upward shoaling lacustrine mudstone. The latter features three discrete sapropel units deposited between 3270 and 4910 cal yr BP, a time of increasing aridity throughout southeastern Australia. A core taken from the lake’s eastern margin yielded sedimentological, mineralogical, geochronological and micropaleontological data. Coring at five other sites across the lake provided sections of the humic and sapropelic facies (n = 20) for total organic carbon and Rock–Eval analysis; isotopic characterization of their micritic carbonate (δ13Ccarb, δ18Ocarb) and co-existing OM (δ13Corg); and GC–MS and GC–irMS analysis of their free aliphatic hydrocarbons. For each ‘sapropel event’ high productivity of diatoms and green algae was the principal driver of the accumulation and preservation of OM in such high concentrations. The precursor algal blooms were likely triggered by the influx of fresh water following winter rainfall. The combination of kerogen hydrogen index and δ13Ccarbδ13Corg, previously employed to track secular changes in algal productivity and organic preservation, proved useful in identifying synchronous geographic differences in these processes across the lake. Highly branched isoprenoids (HBI: C25:1  C20:0) are prominent components of the aliphatic hydrocarbons in the sapropels, confirming the significant contribution of diatoms to their OM. The C isotopic signatures of the principal C25:1 HBI isomer and the co-occurring C23–C31 odd carbon numbered n-alkanes further document the non-uniformity of biomass preservation within and between the three sapropel units. The evidence from this study suggests that seasonal algal blooms and meromixis, although not necessarily an anoxic hypoliminion, were required for sapropel formation in the Holocene lakes of the Coorong region. Higher resolution sampling, dating and comparative analysis (microfossil, biomarker and isotopic) of these sapropels is required to clarify their potential significance as palaeoclimate proxies.  相似文献   

7.
Hydrogen isotopic composition of n-alkanes was measured in sediments from an excavated profile of the Early Cretaceous Yixian Formation in Liaoning Province, NE China, aiming to assess the significance of the δD value of n-alkanes in ancient lacustrine sediments as the indicator for determining the source inputs of organic matters and paleoclimatic conditions. The δD values of n-alkanes are in the range of − 250‰ to − 85‰ and display an obvious three-stage variation pattern through the profile, which is consistent with the distribution of the dominated n-alkanes and the profile of their δ13C values. The δD and δ13C values of n-alkanes suggest that short-chain n-alkanes are primarily derived from photosynthetic bacteria and algae; n-C29 and n-C31 are mainly originated from terrestrial higher plants; n-C28 and n-C30 may be derived from the same precursor but via the different biological mechanism of hydrogen isotopic fractionation; while the source inputs of medium-chain n-alkanes are more complicated, with n-C23 being derived from some specific algae or biosynthesized by various aquatic organisms. The paleoclimatic conditions are reconstructed via two approaches. The reconstructed hydrogen isotopic values of lake water and meteoric water (expressed as δDLW and δDMW, respectively) were at the intervals of − 51.8‰ to 17.0‰ and − 118.1‰ to − 43.5‰, respectively, indicating a general climate transition from semi-arid to arid. The calculated ΔδDLW-MW values vary from 37.0‰ to 89.1‰ and display a similar but a significant large-scale variation trend with the ΔδDC23  long (− 28.8‰ to 85.0‰; long represents long-chain n-alkanes) and ΔδDmid-long (− 15.4‰ to 43.4‰; mid represents medium-chain n-alkanes) values. The discrepancy may be attributed to the source input overlap for n-alkanes and the uncertainties of εwater/lipid values. The coupling of ΔδDC23  long, ΔδDmid-long and ΔδDLW-MW values with the paleoclimatic evidence indicates that the δD values of n-alkanes could be more sensitive to the change of paleoclimatic conditions.  相似文献   

8.
Based on paleoclimatic reconstructions using various proxies, the Holocene Climate Optimum (10.5–6 ka) has been characterized as a warmer and wetter period in most of East Asia. The summer monsoons associated with the East Asian Monsoon evidently intensified and extended further inland from the Pacific Ocean, a source region of moisture. A notable exception to this general pattern exists in northeast China, where less wet conditions are recorded. We determined molecular compositions of individual plant wax hydrocarbons and their hydrogen isotope compositions (δD values) in a radiocarbon-dated peat core recovered from the Hani marsh in Jilin Province (China) and confirmed that the temperature-dependent effective precipitation in northeast China decreased during the Holocene Climate Optimum. A combination of Paq, an indicator of the relative contribution of aquatic to terrestrial plants, and the difference in δD between low (C23, C25 and C27) and high molecular weight (C31) n-alkanes in the Hani peat bog indicates a dramatic change in vegetation from the deglaciation to the Holocene. No significant differences were observed between the δD values of low and high molecular weight n-alkanes with relatively high δD values and low Paq during the early Holocene, indicating that all n-alkanes were produced by evapotranspiration-sensitive terrestrial plants during that time. However, lower δD values of mid-chain n-alkanes (C23, C25 and C27) relative to the long chain n-alkane (C31), together with higher Paq values during the deglaciation (14–11 ka), suggest an increase in the contribution of aquatic plants and a higher water level during the period. The study demonstrates that northeast China was under a markedly wetter climate condition during the late deglaciation. For the 16 kyr record in the Hani peat sequence, we infer that moisture delivery by the East Asian Monsoon was relatively invariable in northeast China, but increased evaporation during the warmer Holocene Climate Optimum reduced the effective precipitation, defined by the balance between precipitation and evaporation.  相似文献   

9.
In this study, the molecular composition and biomarker distribution of lacustrine sediments from Val-1 drillhole in the central zone of the western part of the Valjevo-Mionica basin were investigated at depth interval of 0–400 m. Former investigations have shown that the core material can be separated into six depth intervals based on bulk geochemical, mineralogical and sedimentological characteristics. Concerning the quality of organic matter, presence of specific minerals, and high salinity and anoxicity, or alkalinity, three zones are of highest interest, defined at depth intervals of 15–75 m (A), 75–200 m (B) and 360–400 m (F). The first aim of the study was to identify which biomarkers characterize these specific intervals. The second aim, addressing the transitions zones of these intervals, was to extend the changes in the characteristics of the organic substance, to reflect the changes of conditions in the depositional environment as well as to define biomarker parameters which are the most sensitive sedimentological indicators.The sediments from the hypersaline anoxic and alkaline environment show high contribution of algal precursor biomass, what is in accordance with the good quality of organic substances in the sediments from these zones. High squalane content and low content of regular isoprenoid C25 are typical for hypersaline anoxic environment, whereas sediments from alkaline environment have high regular isoprenoid C25 content.Transition to specific sedimentation zones is characterized by change in total organic matter content, and of both free and pyrolysis-derived, and change in hydrogen index value. In the biomarker distributions, more significant changes were detected in distributions of n-alkanes and isoprenoids, compared to polycyclic alkanes. The most intensive changes in alkane distribution are reflected in changes in n-C17 content compared to n-C27, and phytane compared to n-C18. In addition, significant sensitivity was seen in ratios between squalane and n-alkane C26 (hypersaline depositional environment), or isoprenoid C25 and n-alkane C22 for high alkalinity environment.This study showed that Sq/n-C26 ratio can be used to assess the quality of organic substance in immature lacustrine sediments.  相似文献   

10.
Calcite veins with fluid and solid bitumen inclusions have been discovered in the south-western shoulder of the Dead Sea rift within the Masada-Zohar block, where hydrocarbons exist in small commercial gas fields and non-commercial fields of heavy and light oils. The gas–liquid inclusions in calcite are dominated either by methane or CO2, and aqueous inclusions sometimes bear minor dissolved hydrocarbons. The enclosed flake-like solid bitumen matter is a residue of degraded oil, which may be interpreted as “dead carbon”. About 2/3 of this matter is soot-like amorphous carbon and 1/3 consists of n-C8C18 carboxylic acids and traces of n-alkanes, light dicarboxylic acids, and higher molecular weight (>C20) branched and/or cyclic carboxylic acids. Both bitumen and the host calcites show genetic relationship with mature Maastrichtian chalky source rocks (MCSRs) evident in isotopic compositions (δ13C, δ34S, and δ18O) and in REE + Y patterns. The bitumen precursor may have been heavy sulfur-rich oil which was generated during the burial compaction of the MCSR strata within the subsided blocks of the Dead Sea graben. The δ18O and δ13C values and REE + Y signatures in calcites indicate mixing of deep buried fluids equilibrated with post-mature sediments and meteoric waters. The temperatures of fluid generation according to Mg–Li-geothermometer data range from 55 °С to 90 °С corresponding to the 2.5–4.0 km depths, and largely overlap with the oil window range (60–90 °С) in the Dead Sea rift (Hunt, 1996; Gvirtzman and Stanislavsky, 2000; Buryakovsky et al., 2005). The bitumen-rich vein calcites originated in the course of Late Cenozoic rifting and related deformation, when tectonic stress triggers damaged small hydrocarbon reservoirs in the area, produced pathways, and caused hydrocarbon-bearing fluids to rise to the subsurface; the fluids filled open fractures and crystallized to calcite with entrapped bitumen. The reported results are in good agreement with the existing views of maturation, migration, and accumulation of hydrocarbons, as well as basin fluid transport processes in the Dead Sea area.  相似文献   

11.
Novel ecosystem development is occurring within the western boreal forest of Canada due to land reclamation following oil sand surface mining. Sphagnum peat is the primary organic amendment used to reconstruct soil in these novel ecosystems. We hypothesised that ecosystem recovery would be indicated by an increasing similarity in the biomolecular characteristics of novel soil organic matter (SOM) derived from peat to those of natural boreal ecosystems. We evaluated the use of the homologous series of long chain (⩾ C21) n-alkanes with odd/even predominance to monitor the re-establishment of boreal forest on these anthropogenic soils. The lipids were extracted from dominant vegetation inputs and SOM from a series of natural and novel ecosystem reference plots. Twice the concentration of n-alkanes was extracted from natural than from novel ecosystem SOM (p < 0.01). We observed unique n-alkane signatures for the source vegetation, e.g. peat material was dominated by C31, and aspen (Populus tremuloides Michx.) leaves by C25. The n-alkane distribution differed between the two systems (p < 0.001) and reflected the dominant vegetation input, i.e. peat or tree species. Our results indicate that further research is required to clarify the influence of vegetation or disturbance on the signature of n-alkanes in SOM; however, the use of n-alkanes as biomarkers of novel ecosystem development is a promising application.  相似文献   

12.
Lake sediments generally contain a mixture of terrestrial and aquatic source inputs, and determining the major inputs is important for understanding geological records in paleoenvironment and paleoclimate research. In this study we describe the distribution of n-alkanes and n-fatty acids (FAs) in representative modern plants from around Lake Qinghai. We found a significant difference in the average length of n-FA carbon chains (ACL Fa16–32) in terrestrial (23.3) and aquatic plants (18.6). The results reveal that ACL Fa16–32 may essentially serve as a proxy for evaluating the major source inputs to lake sediments. Assessment of surface sediments from the lake showed that the FAs originated from a mixture of inputs, with the aquatic source input predominant at most sites. Additionally, the δD values of sediment mid-chain n-acids (C22) showed a relationship with the ACL Fa16–32 proxy: an increased Fa ACL corresponded to more negative hydrogen isotope ratio values. We suggest that different sources should be considered and ACL Fa16–32 could be a potential calibration proxy before using δD values to extract reliable isotopic information from lake water. More attention should be paid to source inputs and their relationship to other geochemical proxies in future studies of lake sediments.  相似文献   

13.
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   

14.
The organic geochemical methods of hydrocarbon prospecting involve the characterization of sedimentary organic matter in terms of its abundance, source and thermal maturity, which are essential prerequisites for a hydrocarbon source rock. In the present study, evaluation of organic matter in the outcrop shale samples from the Semri and Kaimur Groups of Vindhyan basin was carried out using Rock Eval pyrolysis. Also, the adsorbed low molecular weight hydrocarbons, methane, ethane, propane and butane, were investigated in the near surface soils to infer the generation of hydrocarbons in the Vindhyan basin. The Total Organic Carbon (TOC) content in shales ranges between 0.04% and 1.43%. The S1 (thermally liberated free hydrocarbons) values range between 0.01–0.09 mgHC/gRock (milligram hydrocarbon per gram of rock sample), whereas the S2 (hydrocarbons from cracking of kerogen) show the values between 0.01 and 0.14 mgHC/gRock. Based on the Tmax (temperature at highest yield of S2) and the hydrogen index (HI) correlations, the organic matter is characterized by Type III kerogen. The adsorbed soil gas, CH4 (C1), C2H6 (C2), C3H8 (C3) and nC4H10, (nC4), concentrations measured in the soil samples from the eastern part of Vindhyan basin (Son Valley) vary from 0 to 186 ppb, 0 to 4 ppb, 0 to 5 ppb, and 0 to 1 ppb, respectively. The stable carbon isotope values for the desorbed methane (δ13C1) and ethane (δ13C2) range between −45.7‰ to −25.2‰ and −35.3‰ to −20.19‰ (VPDB), respectively suggesting a thermogenic source for these hydrocarbons. High concentrations of thermogenic hydrocarbons are characteristic of areas around Sagar, Narsinghpur, Katni and Satna in the Son Valley. The light hydrocarbon concentrations (C1–C4) in near surface soils of the western Vindhyan basin around Chambal Valley have been reported to vary between 1–2547 ppb, 1–558 ppb, 1–181 ppb, 1–37 ppb and 1–32 ppb, respectively with high concentrations around Baran-Jhalawar-Bhanpur-Garot regions (Kumar et al., 2006). The light gaseous hydrocarbon anomalies are coincident with the wrench faults (Kota – Dholpur, Ratlam – Shivpuri, Kannod – Damoh, Son Banspur – Rewa wrench) in the Vindhyan basin, which may provide conducive pathways for the migration of the hydrocarbons towards the near surface soils.  相似文献   

15.
Hydrocarbon results from gas chromatography of 60 recent sediment and 10 benthic algae samples delineate two distinct shelf environments in the northeastern Gulf of Mexico.Sediments off Florida (shell hashes and sands) have moderate amounts of lipids/total sediment (average 113ppm ± 80%) but low hydrocarbon levels (average 3.06 ppm ± 41%). Aliphatic hydrocarbons are dominated by a series of branched or cyclic, unsaturated C25 isomers. The major n-alkane is n-C17. The n-alkane and isoprenoid patterns are consistent with a marine hydrocarbon source.Sediments closer to the Mississippi River (silts and clays) contain large amounts of lipids (average 232 ppm ± 53%) and hydrocarbons (average 11.7 ppm ± 55%) to total sediment. Aliphatic hydrocarbons are mainly odd carbon number high molecular weight n-alkanes, indicating a terrigenous hydrocarbon source. Isoprenoids are present in greater abundance than in sediments off Florida (n-C17/ pristane and n-C18/phytane ratios ~2to 3). Relatively large amounts of n-C16, together with an even distribution of n-alkanes in the range C14–C20 and a substantial unresolved envelope all point to a fossil fuel input to the Mississippi samples.Samples off the Alabama coast show intermediate characteristics.  相似文献   

16.
The Jurassic–Lower Cretaceous aged carbonate sequence is widely exposed in the southern zone of Eastern Pontides. Aptian black bituminous limestone is found in the upper part of this sequence in the Kale area (Gümüşhane). This limestone contains faunal remains (e.g., gastropod, ostracod, characean stems and miliolid type benthic foraminifera) that indicate a freshwater, lacustrine depositional environment.The total organic carbon (TOC) values of the bituminous limestone samples range from 0.11–1.30% with an average TOC value of 0.54%. The hydrogen index (HI) varies from 119–448 mg HC/g TOC (average HI 298 mg HC/g TOC) indicating that the limestone contains gas prone as well as oil prone organic matter. Pyrolysis data prove that the organic matter content in the bituminous limestone consists of Type II kerogen. The average Tmax value for bituminous limestone samples is 438 °C (434–448 °C). Bitumen/TOC ratios for bituminous limestone are 0.05 and 0.04. The Tmax values and the ratios indicate that the bituminous limestone samples contain early mature to mature organic matter.Analysis of solvent extracts from the two richest bituminous limestones show a predominance of high carbon number (C26–C30) n-alkanes. The Pr/Ph ratio and CPI value are 1.34 and 0.96, respectively. C29 is the dominant sterane, with C29 > C27 > C28. The bituminous limestone samples have low C22/C21 ratios, high C24/C23 tricyclic terpane ratios and very low C31R/C30 hopane ratios (<0.25). These data are consistent with the bituminous limestones being deposited in a lacustrine environment.  相似文献   

17.
Previously studied thermosequences of wood (chestnut) and grass (rice straw) biochar were subjected to hydrogen pyrolysis (hypy) to evaluate the efficacy of the technique for determining pyrogenic carbon (CP) abundance. As expected, biochar from both wood and grass produced at higher temperature had higher CP amount. However, the trend was not linear, but more sigmoidal. CP/CT ratio values (CT = total organic carbon) for the wood thermosequence were ⩽0.03 at biochar production temperature (TCHAR)  300 °C. They increased dramatically until 600 °C and remained relatively constant and near unity at higher biochar production temperature. Grass biochar was similar in profile, but CP/CT values rose dramatically after 400 °C. The findings are consistent with the hypothesis that hypy residues contain polycyclic aromatic hydrocarbons (PAHs) with a degree of condensation above at least 7–14 fused rings, with labile organic matter and pyrogenic PAHs below this degree of condensation removed by hypy.Both wood and grass thermosequences displayed δ13CP values that decreased with increased TCHAR, indicating that recalcitrant carbon compounds (pyrogenic aromatic PAHs with a relatively high degree of condensation) were first formed from structural components with relatively high δ13C values (e.g. cellulose). Relatively constant δ13C values at TCHAR  500 °C suggested the dominant pyrolysis reaction was condensation of PAHs with no additional fractionation. Comparison of hypy with benzene polycarboxylic acid (BPCA), ‘ring current’ NMR and pyrolysis gas chromatography–mass spectrometry (GC–MS) results from the same suite of samples indicated a consistent overview of the structure of CP, but provided unique and complimentary information.  相似文献   

18.
The stable carbon isotopic compositions of light hydrocarbon gases adsorbed in near-surface soil and sediments from the Saurashtra basin were characterized for their origin and maturity. Saurashtra is considered geologically prospective for oil and gas reserves; however, a major part of the basin is covered by the Deccan Traps, hindering the exploration of Mesozoic hydrocarbon targets. Surface geochemical prospecting, based on micro-seepage of hydrocarbons from subsurface accumulations, could be advantageous in such areas. In light of this, 150 soil samples were collected from the northwestern part of Saurashtra, around the Jamnagar area, where a thick sedimentary sequence of about 2–3 km exists under 1–1.5 km of Deccan basalt. The concentration of acid desorbed alkane gases from soil samples was found to vary (in ppb) as: methane (C1) = 3–518; ethane (C2) = 0–430; propane (C3) = 0–331; i-butane (iC4) = 0–297; n-butane (nC4) = 2–116; i-pentane (iC5) = 0–31 and n-pentane (nC5) = 0–23, respectively.Fifteen samples with high concentrations of alkane gases were measured for their δ13C1; δ13C2 and δ13C3 compositions using gas chromatography–combustion-isotope ratio mass spectrometry (GC–C-IRMS). The values for methane varied from ? 27 to ? 45.4‰, ethane from ? 20.9 to ? 27.6‰, and propane from ? 20.4 to ? 29.1‰ versus the Vienna PeeDee Belemnite (VPDB). The carbon isotope ratio distribution pattern represents isotopic characteristics pertaining to hydrocarbon gases derived from thermogenic sources. Comparisons of carbon isotopic signatures and compositional variations with the standard carbon isotopic models suggest that hydrocarbon gases found in the shallow depths of the study area are not of bacterial origin but are formed thermally from deeply buried organic matter, likely to be mainly a terrestrial source rock with a partial contribution from a marine source. These gases may have migrated to the near-surface environment, where they represent an admixture of thermally generated hydrocarbon gases from mixed sources and maturity. The maturity scale (δ13C versus Log Ro %) applied to the surface sediment samples of the Jamnagar area indicated the source material to be capable of generating oil and gas. The detection of thermogenic alkane gases in near-surface sediments offers the possibility of hydrocarbons at depth in Saurashtra.  相似文献   

19.
We investigated the molecular inventory of River Danube sediments and identified wax esters with 28–36 carbons, with C30, C31 and C32 homologs the most abundant. They consist of various combinations of n-, iso- and anteiso-aliphatic acid and alcohol moieties, with different isomer distributions for the esters with odd and even carbon numbers. The short chain length (C28–C36), high proportion of methyl moieties and presence of monounsaturated esters together suggest a bacterial origin for the wax esters. The concentration in surface sediments varied from 0 to 741 μg/kg, being significantly enriched at locations with high nutrient concentration and high primary productivity. Cluster analysis of denaturing gradient gel electrophoresis (DGGE) band patterns revealed different bacterial communities in surface sediments from the stream and surface sediments from the reservoir. The concentration in a 70 cm core of rapidly deposited sediments decreased significantly with depth, following first order kinetics, suggesting a loss of the esters within ca. 3 years following burial and hence a low probability for preservation in the geological record. Wax esters in rivers have rarely been investigated; our results suggest that they represent a bacterial response to enhanced primary production, triggered by higher nutrient supply.  相似文献   

20.
The Bulonggoer paleo-oil reservoir (BPR) on the northwest Junggar Basin is the first Devonian paleo-oil reservoir discovered in North Xinjiang, China. Solid bitumens occur within sandstone pores and as veins filling fractures. Samples of both types were analyzed using stable carbon isotope and reflectance measurements, as well as molecular biomarker parameters.The extremely positive δ13C values and biomarker indicators of depositional environment/lithology, such as pristane/phytane (Pr/Ph), C29/C30 hopane, diasteranes/regular steranes and dibenzothiophene/phenanthrene ratios, indicate a siliciclastic source for the BPR and their deposition in a highly reducing hypersaline environment. The presence of long chain n-alkanes and abundant tetracyclic diterpanes, C20–C21 tricyclic terpanes and perylene are indicators of higher plant organic matter input. Moreover, the bimodal distribution of C27 > C28 < C29 regular steranes and abundant methyltriaromatic steroids also support a contribution of microalgae as well as higher plants organic matter. The similar molecular composition and thermal maturity parameters indicate that the reservoir and veined solid bitumens were altered from a common paleo-petroleum, which originated from peak oil window matured source rocks.All solid bitumens from the BPR are characterized by relatively low bitumen reflectance values (Rb% < 0.7), suggesting that they were generated from low temperature processes rather than oil thermal cracking. Comparatively, the Rb% values for veined bitumens are higher than reservoir bitumens, indicating that the veined bitumens occurred earlier and experienced higher thermal conditions.  相似文献   

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