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1.
Surface sediments from an anoxic marine environment, the Upper Basin of the Pettaquamscutt River, Rhode Island, were analyzed for volatile organic compounds in the C1C7 range. The compounds identified included methane, ethane, alkenes (C2C5), carbon disulfide, cyclopentane, 3-methylpentane, methylfuran, aldehydes and ketones. Ethane, methylfuran, and most of the aldehydes and ketones showed maxima at the sediment water interface. Methane levels were very high-10–100 times greater than observed in most other surface sediments examined in this laboratory.  相似文献   

2.
A series of even carbon numbered α, ω-dicarboxylic acids ranging from C16 to C24 has been identified in recent sediments from various environments and sampling localities. A lacustrine sediment did not show detectable quantities of diacids. Consideration of quantitative relationships involving the diacids leads us to propose a dual origin for these diacids: deposition by mangroves is their main source in mangal areas while in situ production by sedimentary organisms is the only important source of diacids in a non-mangal marine environment. A fresh water lagoon shows an intermediate situation between these extremes.  相似文献   

3.
Peats in a sediment core from Ruoergai bog, which has a cold and moist plateau climate with major source input from herbaceous plants, have been studied by GC–MS in order to understand the composition and diagenetic processes of lipids in this depositional environment. Long chain components (C21–C35) predominate in the n-alkanes, n-alk-1-enes, n-fatty acids, n-alkan-2-ones and n-alkanols with a maximum of C31, C27, C22 or C24, C23 or C25 and C22, respectively. A herbaceous origin for these long chain compounds is suggested, and this is supported by their stable carbon isotopic compositions. Diterpenoid hydrocarbons with abietane, pimarane and kaurane skeletons, some of which have not been reported often in modern sediments, are prominent and are derived from higher plants. Several triterpenoid ketones and alcohols with oleanane or lupane skeletons, and a series of des-A-triterpenoid hydrocarbons which have not been reported often in modern sediments are also present, and are assigned to a higher plant source. Hopanoids, including their alkanes, alkenes, ketones, alcohols and esters, are abundant and of bacterial origin. Steroid ketones and alkanols are dominated by C29 homologues. C28 and C29 steroids are derived mainly from higher plants, whereas the C27 component is assigned to a microbial source. The presence of short-chain n-alkanes with no odd-even carbon predominance, bacterially derived fatty acids (C14, C15, iso- and unsaturated acids), n-alkan-2-ones, des-A-triterpenoid hydrocarbons, hopanoids and some steroid ketones indicate that intense microbial reworking of the organic matter has taken place in this depositional environment. The chemical and biochemical conversions of some cyclic alkenes to alkanes, such as tricyclic diterpenoids, tetracyclic terpenoids and steroid ketones, are also evident with depth. The dominance of C20 components in the diterpenoid hydrocarbons may reflect an oxidizing or reducing depositional condition.  相似文献   

4.
A 3-m sediment core taken from Lake Suigetsu, in which a shift from fresh to brackish water occurred about three hundred years ago, has been examined for variation with depth of organic carbon and fatty acids. From the difference in total amounts of sulphur between sediments under fresh and brackish water environments, the surface sediments above approximately 35 cm depth were deduced to be accumulated under a brackish water environment. The total contents of organic carbon and fatty acids, and percentage composition of fatty acids gave discontinuous profiles above and below the 35–40 cm sediment layer. At a depth of 12.5 cm, the distribution in chain length of the fatty acids changed from a unimodal (the predominance of C12-C18 over C20-C34) to a bimodal pattern, which was mirrored by the composition diversity index (CDI).Although the fatty acids in the surface sediments (0–40 cm) from Lake Suigetsu seemed to suffer milder degradation through microbial activity than those in a core (0–150 cm) from Lake Suwa, a freshwater eutrophic lake, both lacustrine sediments showed similar trends in the alteration of fatty acid composition with depth.  相似文献   

5.
Steroids with unconventional side chains have increasingly been applied as diagnostic markers for geological source and age assessments. However, one of the most distinctive characteristics, the abnormal abundance of pregnane and homopregnane in ancient sediments and petroleum, remains unresolved. Higher pregnane and homopregnane, as well as C23–C26 20-n-alkylpregnanes, relative to the regular steranes were observed in samples collected from different petroleum basins in China. These included Precambrian marine carbonate-derived petroleum (NW Sichuan Basin), Lower Paleozoic marine marl derived crude oils (Tarim Basin), and Eocene hypersaline lacustrine carbonate source rocks and associated petroleum (Bohai Bay Basin). However, all of the samples have many common biomarker characteristics, such as pristane/phytane ratios < 1, low amounts of diasteranes and high C29/C30 hopane (∼0.6–1), C35/C34 hopane (mostly ⩾ 1) and dibenzothiophene/phenanthrene (DBT/PHEN, mostly 0.5–1) ratios revealing a contribution from anoxic carbonate/marl source rocks deposited in restricted, clastic-starved settings. We suggest that 5α,l4β,l7β-pregnane and homopregnane, as well as their higher C23–C26 homologues, are geological products derived from steroids bound to the kerogen by a sulfurized side chain. Carbon or carbonate minerals are considered to be natural catalysts for this cracking reaction via preferential cleavage of the bond between C-20 and C-22. Similar distributions occur in the short chain analogues of 4-methylsterane, triaromatic steroid and methyltriaromatic steroid hydrocarbons, providing circumstantial evidence for this proposal. The ratio of pregnane and homopregnane to the total regular steranes and the ratio of C27 diasteranes to cholestanes can be sensitive indicators of sedimentary environments and facies. In general, high diasteranes and low pregnanes (with homologues) indicate an oxic water column or significant input of terrigenous organic matter in clay rich source rocks and some organic lean carbonate rocks. Low diasteranes with high pregnanes implies restricted, sulfur rich conditions, typical of anoxic carbonate source rocks. Furthermore, the two ratios may be useful to assess the variation of mineralogy and openness of source rock depositional settings.  相似文献   

6.
Steryl alkyl ethers (SAEs) have been reported from marine sediments ranging from Holocene to Lower Cretaceous and their production has been linked to upwelling of cold, nutrient-rich water. However, the lack of continuous stratigraphic records for them has complicated validation of the precise connection of their production, sedimentary distribution and survival to climatic conditions. Here, we report an SAE record that spans the last ca. 135 ka from a core taken offshore southeastern Australia in the Murray Canyons Group region. The SAEs are composed predominantly of C27–C30 steroid moieties with one or two double bonds, ether-bound to C10–C11 alkyl moieties. Some of the SAEs are identical to those reported in marine sediments, whereas others have not been identified previously. They do not exhibit any systematic change in distribution over the past 110 ka but sediments older than 110 ka possess a different assemblage, with a higher amount of constituents containing a C11 alkyl moiety. The SAE accumulation rate increases rapidly during glacial episodes and for intervals characterized by a sharp decline in sea-surface temperature. The results suggest that SAEs may be related to marine eukaryotes that thrive when there is an influx of cold, deep waters in the Murray Canyons Group region, likely triggered by stronger westerlies over southeastern Australia forcing deeper water to reach the surface during glacials.  相似文献   

7.
《Applied Geochemistry》2005,20(10):1875-1889
Based on the systematic analyses of light hydrocarbon, saturate, aromatic fractions and C isotopes of over 40 oil samples along with related Tertiary source rocks collected from the western Qaidam basin, the geochemical characteristics of the Tertiary saline lacustrine oils in this region was investigated. The oils are characterized by bimodal n-alkane distributions with odd-to-even (C11–C17) and even-to-odd (C18–C28) predominance, low Pr/Ph (mostly lower than 0.6), high concentration of gammacerane, C35 hopane and methylated MTTCs, reflecting the high salinity and anoxic setting typical of a saline lacustrine depositional environment. Mango’s K1 values in the saline oils are highly variable (0.99–1.63), and could be associated with the facies-dependent parameters such as Pr/Ph and gammacerane indexes. Compared with other Tertiary oils, the studied Tertiary saline oils are marked by enhanced C28 sterane abundance (30% or more of C27–C29 homologues), possibly derived from halophilic algae. It is noted that the geochemical parameters of the oils in various oilfields exhibit regular spatial changes, which are consistent with the depositional phase variations of the source rocks. The oils have uncommon heavy C isotopic ratios (−24‰ to −26‰) and a flat shape of the individual n-alkane isotope profile, and show isotopic characteristics similar to marine organic matter. The appearance of oleanane and high 24/(24 + 27)-norcholestane ratios (0.57–0.87) in the saline oils and source rocks confirm a Tertiary organic source.  相似文献   

8.
The distributions of a series of structurally related C25 and C30 biogenic alkenes in sediments of the Narragansett Bay estuary have been determined. The suite of alkenes detected differs both quantitatively and qualitatively from those previously reported in other estuanne and coastal regions. Four C25 mono- and dienes and one C30 diene comprise 73–91% of the total alkenes in all surface (upper 2.5–5 cm) sediments analyzed. However, significant geographic variations exist in the relative abundance of these five compounds throughout the estuary. A comparison of alkene concentrations with δ13C of the bulk sedimentary organic matter has shown that the geographic variations of some alkenes reflect the distribution of marine organic matter, suggesting a marine source for these compounds. The distributions of other alkenes are not similarly correlated. In particular, concentrations of the C30 diene are relatively constant and exhibit no dependence on the origin of organic matter in these sediments. This distribution implies an in situ production of this alkene throughout the estuary. Analysis of several sediment cores reveals that alkene concentrations are generally highest at the surface and decrease to low, constant values within the upper 25 cm. An exception is the subsurface concentration of one C25 diene, which exhibits an increase at the same depth in two separate upper bay cores.  相似文献   

9.
Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C15+ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C15+ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C15+ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m3/m3 during bitumen generation and remain essentially constant (81–84 m3/m3) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C17 and phytane/n-C18) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.  相似文献   

10.
The distributions of eight tricyclic and eight pentacyclic terpanes were determined for 216 crude oils located worldwide with subsequent simultaneous RQ-mode factor analysis and stepwise discriminate analysis for the purpose of predicting source rock features or depositional environments. Five categories of source rocks are evident: nearshore marine (i.e., paralic/deltaic); deeper-water marine; lacustrine; phosphaticrich source beds; and Ordovician age source rocks. The first two factors of the RQ-mode factor analysis describe 45 percent of the variation in the data set; the tricyclic terpanes appear to be twice as significant as pentacyclic terpanes in determining the variation among samples. Lacustrine oils are characterized by greater relative abundances of C21 diterpane and gammacerane; nearshore marine sources by C19 and C20 diterpanes and oleanane; deeper-water marine facies by C24 and C25 tricyclic and C31 plus C32 extended hopanes; and Ordovician age oils by C27 and C29 pentacyclic terpanes. Although thermal maturity trends can be observed in factor space, the trends do not necessarily obscure the source rock interpretations. Also, since bacterial degradation of crude oils rarely affects tricyclic terpanes, biodegraded oils can be used in predicting source rock features. The precision to which source rock depositional environments are determined might be increased with the addition of other biomarker (e.g., steranes) and stable isotope data using multivariate statistical techniques.  相似文献   

11.
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   

12.
The unique KMnO4 degradation products of β-carotene, previously identified as 2,2-dimethyl succinic acid (C6) and 2,2-dimethyl glutaric acid (C7) have been found in the oxidation products of Green River shale (Eocene, 52 × 106yr) and Tasmanian Tasmanite (Permian, 220−274 × 106yr) kerogens. These two compounds were also detected in KMnO4 degradation products of young kerogens from lacustrine and marine sediments. The results indicate that kerogens incorporated carotenoids (possibly β-carotene) at the time of kerogen formation in surface sediments. Both acids are useful markers to obtain information on biological precursors contributing to the formation of fossil kerogens.  相似文献   

13.
Lake Kinneret, a relict lake from the Neogene, is characterised by the dominance among its phytoplankton of the dinoflagellate Peridinium cinctum. The lipid geochemistry of Lake Kinneret is discussed herein in terms of the biology, chemistry and hydrology of the lake. Lipids isolated from two sediment sections (surface and 15 cm deep), obtained from the deepest point of Lake Kinneret, include: (1) 4α-methyl-5α (H)-stanols and related derivatives characteristic of P. cinctum, the novel sterol 4a-methylgorgosterol, and peridinosterol and 4α-methylgorgostanol, not previously reported to occur in lacustrine sediments; (2) C30 and C32 alkane-1,15-diols, not previously reported to occur in contemporary lacustrine deposits, and (3) products of early diagenesis. Many similarities were observed with the more widely studied marine dinoflagellates and marine sediments with dinoflagellate input.  相似文献   

14.
This paper consists of two interrelated parts. In the first part, the influence of the composition of sediment organic matter on crude oil composition is discussed. The second part deals with the origin of normal paraffins in petroleum.Source beds with abundant terrestrial plant matter generate heavy hydrocarbons rich in five-ring naphthenes. Unless such source beds are exposed to a high temperature for a prolonged time, the oils released are also rich in five-ring naphthenes. Such oils are rare; thus far the only examples found are some Eocene Wilcox oils from the Texas Gulf Coast and some Eocene Green River oils from the Uinta Basin, Utah. Normally, oil source beds are not rich in terrestrial plant matter and the five-ring naphthene content of the source bed hydrocarbons, as well as that of the produced oils, is low.The n-paraffins generated by oil source beds rich in terrestrial plant matter are characterized by abnormally low (C21 + C22)/(C28 + C29) ratios of 0.6–1.2. In oils of dominantly marine origin, this ratio is in the range 1.5–5.0. The ratio of marine to terrestrial organic matter in source beds appears to influence both the naphthene composition and the n-paraffin composition of the generated oils.Evidence is presented that petroleum n-parainns originate from slow thermal cracking of fatty acids contained in fats and waxes. Reaction equations are discussed which explain the major geochemical observations, including the difference in carbon-number distribution of the assumed parental fatty acids and of their descendant n-paraffins. In normal oils, which originate mostly from fat rich marine organic matter, the n-paraffin concentration tapers off above C20. The molecular weight range of the fatty acids of plant waxes is considerably higher than that of fats. If plant waxes contribute strongly to the oil source material, the molecular weight distribution of the petroleum n-paraffins formed is abnormal and high carbon numbers in the C24-C32 range dominate.  相似文献   

15.
Geochemical, mineralogical and biological indicators preserved in sediments are widely used to reconstruct past climate change, but proxies differ in the degree to which their utility as climate indicators has been validated via laboratory experiments, modern spatial calibrations, or down‐core comparisons with instrumental climate data. Multi‐proxy studies provide another means of evaluating interpretations of proxies. This paper presents a multi‐proxy assessment comparing 19 sub‐centennially resolved late Holocene proxy records, covering the period 300–1900 AD, from seven Icelandic marine and lacustrine core sites. We employ simple statistical comparisons between proxy reconstructions to evaluate their correlations over time and, ultimately, their utility as proxies for regional climate. Proxies examined include oxygen isotopic composition of benthic and planktonic foraminifera, abundance of the sea‐ice biomarker IP25, allochthonous quartz in marine sediments (a proxy for drift ice around Iceland), marine carbonate abundance, total organic carbon concentration, chironomid assemblages, lacustrine biogenic silica and carbon/nitrogen ratios in lake sediments. Most of the examined proxy records, including temperature and sea‐ice proxies, correlate strongly with each other over multi‐centennial timescales, and thus do appear to record changes in regional climate. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

16.
Young kerogens isolated from seven freshwater lakes, six river mouths and four marine surface sediments were subjected to pyrolysis in vacuo. Their pyrolysates were trapped and separated subsequently for determination of hydrocarbons, fatty acids and alcohols. The abundances, carbon number distributions of long (C12) polymethylene chain lipid compounds and relative abundances of pristenes are proposed as possible indices applicable to discrimination between young kerogens from freshwater lacustrine and marine sediments. Some oil-shale kerogens of Eocene and Permian age were pyrolyzed in the same way, where the chain-length distributions of the pyrolysis products showed similar trends as those observed for the pyrolysis of young kerogens.  相似文献   

17.
An isobathic transect of marine surface sediments from 1°N to 28°S off southwest Africa was used to further evaluate the potential of the chain length distribution and carbon stable isotope composition of higher plant n-alkanes as proxies for continental vegetation and climate conditions. We found a strong increase in the n-C29–33 weighted mean average δ13C values from −33‰ near the equator to around −26‰ further south. Additionally, C25–35 n-alkanes reveal a southward trend of increasing average chain length from 30.0 to 30.5. The data reflect the changing contribution of plants employing different photosynthetic pathways (C3 and C4) and/or being differently influenced by the environmental conditions of their habitat. The C4 plant proportions calculated from the data (ca. 20% for rivers draining the rainforest, to ca. 70% at higher latitude) correspond to the C4 plant abundance in continental catchment areas postulated by considering prevailing wind systems and river outflows. Furthermore, the C4 plant contribution to the sediments correlates with the mean annual precipitation and aridity at selected continental locations in the postulated catchment areas, suggesting that the C4 plant fraction in marine sediments can be used to assess these environmental parameters.  相似文献   

18.
Three methods are presented on how to purify acetylated sterols, acetylated triterpenols and individual alkenones for hydrogen isotope analysis from marine and lacustrine sediments using reverse-phase high performance liquid chromatography (RP-HPLC). The main advantages over previous HPLC methods are reduced operator time, increased automation and the ability to simultaneously purify multiple target compounds from a sample. These gains are achieved primarily by acetylating compounds prior to purification rather than after, and also by using a fraction collector with semi-preparatory rather than analytic configuration. The effectiveness of the method is demonstrated for (i) dinosterol and taraxerol in sediment from the brackish pond Poza del Diablo, Galápagos, (ii) for di- and tri-unsaturated C37 and C38 alkenones in cultured Emiliania huxleyi, (iii) for brassicasterol, and di-, tri- and tetra-unsaturated C37 alkenones in sediment from Manito Lake, Saskatchewan, Canada, and (iv) for brassicasterol, dinosterol and di-, tri- and tetra-unsaturated C37 alkenones in sediment from the Great Salt Lake, Utah. The purification process yields 80–90% recoveries and results in no measurable hydrogen isotope alteration.  相似文献   

19.
In order to understand the distribution characteristics of biomarkers in source rocks,which may be related to organic input,Quaternary sediments from the Caohai Basin and the Chaiwobu Lake were analyzed for sterols,As a result,various sterols,have been found in the sediments.The composition of sterols in the sediments revealed that cholesterols and cholestadienols are more abundant than their C29 counterparts in the Chaiwobu Lake sediments and that C29 sterols are more abundant in the peats from the Caohai Basin,It is also found that stanol/sterol ratios in clays are higher than in peats.Studies show that organic input to the Chaiwobu Lake is mainly plankton and zooplankton and to the Caohai Basin is mainly terrestrial high plant.The authors have proposed that the relative abundance of C27 or C29 sterane in source rocks may reflect input characteristics to some extent and the stanol/sterol ratios may reflect the redox conditions of the depositional environments.  相似文献   

20.
Terrestrial faulted lacustrine basin is considered as a favorable place for the development of source rocks,especially the fault basins in eastern China.Based on molecular composition study of saturated and aromatic hydrocarbons in the extracts of source rocks of the Yingcheng and Shahezi formations in the Lishu Fault Depression,it is revealed that the extracts of source rocks are provided with low ratio of Pr/Ph,low content of C24 tetracyclic terpanes,high content of tricyclic terpanes and gammacerane,relatively high content of C27 steranes in the sag belt and its periphery;relatively high ratio of Pr/Ph,relatively high content of tetracyclic terpanes and gammacerane,low content of C27 steranes and obvious advantages of C29 steranes in its gentle slope belt;with high ratio of Pr/Ph,high content of C19,C20 tricyclic and C24 tetracyclic terpanes,very low content of gammacerane and C27 steranes,and high content of C29 steranes in the edge of fault depression.According to the organic matter input and sedimentary environment,three types of source rocks have been established,which,respectively,are the mode of mixing organic matter input in deep and semi-deep lake,the advantage of terrigenous input in shallow lake and terrigenous input in shore-shallow lacustrine.The first mode is supposed to generate oil and gas,while the second one tends to generate oil.The distribution characteristics of oil and gas in the Lishu Fault Depression are very likely to be controlled by hydrocarbon generating characteristic of different source rock types.  相似文献   

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