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1.
The concentrations of black carbon (BC) and δ13CBC were determined in sediments of three dated cores from the Pearl River estuary (core PR-3) and adjacent northern South China Sea (cores SS-30, E2). For comparison, the total organic C (TOC) contents and δ13CTOC in the sediments were also measured. Relatively higher concentrations and fluxes of BC were found in sedimentary core PR-3, taken in the Pearl River estuary. The BC concentration profiles or fluxes correlated well with fossil-fuel usage in the Pearl River Delta. Maximum BC fluxes occurred in the late 1970s to early 1980s as recorded in core PR-3, and in the 1950s (core SS-30), reflecting the maximum BC emission in the Pearl River Delta and Hong Kong region, respectively. After the 1980s, a rapid decrease of BC fluxes and a light δ13CBC excursion were presumably due to improvements in combustion and pollution-control technologies and a shift of energy structure from biomass and coal to a mixture of coal, gas, oil and biomass. The fossil BC that contributed to total BC in core PR-3 increased from 20–30% to 70–80% during the last five decades. The study also shows that BC correlates well with terrestrial organic matter and that the ratio of BC to TOC is a good pollution indicator in relation to anthropogenic activities.  相似文献   

2.
Carbon isotope and molecular compositions of Mississippian to Upper Cretaceous mud gases have been examined from four depth profiles across the Western Canada Sedimentary Basin (WCSB). The profiles range from the shallow oil sands in the east (R0 = 0.25) to the very mature sediments in the overthrust zone to the west (R0 = 2.5). In the undisturbed WCSB, δ13C1δ13C2 and δ13C2δ13C3 cross-plots show three maturity and alteration trends: (1) pre-Cretaceous gas sourced from type II kerogen; (2) Cretaceous Colorado Group gas; and (3) Lower Cretaceous Mannville Group biodegraded gas. A fourth set of distinctly different maturity trends is recognized for Lower Cretaceous gas sourced from type III kerogen in the disturbed belt of the WCSB. Displacement of these latter maturity trends to high δ13C2 values suggests that the sampled gas was trapped after earlier formed gas escaped, probably as a result of overthrusting. Unusually 13C-enriched gas (δ13C1 = −34‰, δ13C2 = −13‰, and δ13C3 = 0‰), from the Gething Formation in the disturbed belt, is the result of late stage gas cracking in a closed system. In general, gas maturity is consistent with the maturity of the host sediments in the WCSB, suggesting that migration and mixing of gases was not pervasive on a broad regional and stratigraphic scale. The ‘Deep Basin’ portion of the WCSB is an exception. Here extensive cross-formational homogenization of gases has occurred, in addition to updip migration along the most permeable stratigraphic units.  相似文献   

3.
Ultrahelvetic units of the Eastern Alps were deposited on the distal European continental margin of the (Alpine) Tethys. The Rehkogelgraben section (“Buntmergelserie”, Ultrahelvetic unit, Upper Austria) comprises a 5 m thick succession of upper Cenomanian marl-limestone cycles overlain by a black shale interval composed of three black shale layers and carbonate-free claystones, followed by lower Turonian white to light grey marly limestones with thin marl layers. The main biostratigraphic events in the section are the last occurrence of Rotalipora and the first occurrences of Helvetoglobotruncana helvetica and Quadrum gartneri. The thickest black shale horizon has a TOC content of about 5%, with predominantly marine organic matter of kerogen type II. Vitrinite reflectance and Rock-Eval parameter Tmax (<424 °C) indicate low maturity. HI values range from 261 to 362 mg HC/g TOC. δ13C values of bulk rock carbonates display the well documented positive shift around the black shale interval, allowing correlation of the Rehkogelgraben section with other sections such as the Global Boundary Stratotype Section and Point (GSSP) succession at Pueblo, USA, and reference sections at Eastbourne, UK, and Gubbio, Italy. Sediment accumulation rates at Rehkogelgraben (average 2.5 mm/ka) are significantly lower than those at Pueblo and Eastbourne.  相似文献   

4.
Marine gas hydrates, one of the largest methane reservoirs on Earth, may greatly affect the deep sea sedimentary environment and biogeochemistry; however, the carbon geochemistry in gas hydrate-bearing sediments is poorly understood. In this study, we investigated the carbon variables in sediment core 973-3 from the southwestern Taiwan Basin in the South China Sea to understand the effect of environmental factors and archaeal communities on carbon geochemistry. The carbon profiles suggest the methanogenesis with the incerase of dissolved inorganic carbon(DIC) and high total organic carbon(TOC)(mean = 0.46%) originated from terrigenous organic matter(mean δ~(13)C_(TOC) value of-23.6‰) driven by the abundant methanogen ‘Methanosaeta and Methanomicrobiales'. The active anaerobic oxidation of methane is characterized by the increase of DIC and inorganic carbon(IC), and the depleted δ~(13)C_(IC), coupled with the increase of TOC and the decrease of δ~(13)C_(TOC) values owing to the methanotroph ‘Methanosarcinales/ANME' in 430–840 cm. Environmental factors and archaeal communities in core 973-3 are significantly correlated to carbon variables owing to methane production and oxidation. Our results indicate that the carbon geochemical characteristics are obviously responding to the formation and decomposition of gas hydrates. Furthermore, pH, Eh and grain size, and Methanosaeta greatly affect the carbon geochemistry in gas hydrate-associated sediments.  相似文献   

5.
A reversal of the conventional carbon isotope relationship, “terrestrial-lighter-than-marine” organic matter, has been documented for two Pennsylvanian (Desmoinesian) cyclothemic sequence cores from the Midcontinent craton of the central United States. “Deep” water organic-rich phosphatic black shales contain a significant proportion of algal-derived marine organic matter (as indicated by organic petrography, Rock-Eval hydrogen index and ratios) and display the lightest δ13C-values (max −27.80‰ for kerogen) while shallower water, more oxic facies (e.g. fossiliferous shales and limestones) contain dominantly terrestrial organic matter and have heavier δ13Ckerogen-values (to −22.87‰ for a stratigraphically adjacent coal). δ13C-values for extract fractions were relatively homogeneous for the organic-rich black shales with the lightest fraction (often the aromatics) being only 1‰, or less, more negative than the kerogen. Differences between extract fractions and kerogens were much greater for oxic facies and coals (e.g. saturates nearly 5‰ lighter than the kerogen).A proposed depositional model for the black shales calls upon a large influx of nutrients and humic detritus to the marine environment from the laterally adjacent, extremely widespread Pennsylvanian (peat) swamps which were rapidly submerged by transgression of the epicontinental seas. In this setting marine organisms drew upon a CO2-reservoir which was in a state of disequilibrium with the atmosphere, being affected by isotopically light “recycled-CO2” derived from the decomposition of peaty material in the water column and possibly from the anoxic diagenesis of organic matter in the sediments.  相似文献   

6.
Previous studies on the coal-bed methane potential of the Zonguldak basin have indicated that the gases are thermogenic and sourced by the coal-bearing Carboniferous units. In this earlier work, the origin of coal-bed gas was only defined according to the molecular composition of gases and to organic geochemical properties of the respective source rocks, since data on isotopic composition of gases were not available. Furthermore, in the western Black Sea region there also exist other source rocks, which may have contributed to the coal-bed gas accumulations. The aim of this study is to determine the origin of coal-bed gas and to try a gas-source rock correlation. For this purpose, the molecular and isotopic compositions of 13 headspace gases from coals and adjacent sediments of two wells in the Amasra region have been analyzed. Total organic carbon (TOC) measurements and Rock-Eval pyrolysis were performed in order to characterize the respective source rocks. Coals and sediments are bearing humic type organic matter, which have hydrogen indices (HI) of up to 300 mgHC/gTOC, indicating a certain content of liptinitic material. The stable carbon isotope ratios (δ13C) of the kerogen vary from −23.1 to −27.7‰. Air-free calculated gases contain hydrocarbons up to C5, carbon dioxide (<1%) and a considerable amount of nitrogen (up to 38%). The gaseous hydrocarbons are dominated by methane (>98%). The stable carbon isotope ratios of methane, ethane and propane are defined as δ13C1: −51.1 to −48.3‰, δ13C2: −37.9 to −25.3‰, δ13C3: −26.0 to −19.2 ‰, respectively. The δD1 values of methane range from −190 to −178‰. According to its isotopic composition, methane is a mixture, partly generated bacterially, partly thermogenic. Molecular and isotopic composition of the gases and organic geochemical properties of possible source rocks indicate that the thermogenic gas generation took place in coals and organic rich shales of the Westphalian-A Kozlu formation. The bacterial input can be related to a primary bacterial methane generation during Carboniferous and/or to a recent secondary bacterial methane generation. However, some peculiarities of respective isotope values of headspace gases can also be related to the desorption process, which took place by sampling.  相似文献   

7.
We present an organic geochemical study of surface sediments of Lake Sarbsko, a shallow coastal lake on the middle Polish Baltic coast. The aim was to provide evidence concerning the origin of the organic matter (OM) and its compositional diversity in surface deposits of this very productive, highly dynamic water body. The content and composition of the OM in the bottom sediments were investigated at 11 sampling stations throughout the lake basin. OM sources were assigned on the basis of bulk indicators [total organic carbon (TOC), total nitrogen (TN), δ13CTOC and δ15N and extractable OM yield], biomarker composition of extractable OM and compound-specific C isotope signatures. The source characterization of autochthonous compounds was verified via phytoplankton analysis. The distribution of gaseous hydrocarbons in the sediments, as well as temporal changes in lake water pH, the concentration of DIC (dissolved inorganic carbon) and δ13CDIC were used to trace OM decomposition.The sedimentary OM is composed mainly of well preserved phytoplankton compounds and shows minor spatial variability in composition. However, the presence of CH4 and CO2 in the bottom deposits provides evidence for microbial degradation of sedimentary OM. The transformation of organic compounds in surface, bottom and pore waters via oxidative processes influences carbonate equilibrium in the lake and seasonally favours precipitation or dissolution of CaCO3.The data enhance our understanding of the relationships between the composition of sedimentary OM and environmental conditions within coastal ecosystems and shed light on the reliability of OM proxies for environmental reconstruction of coastal lakes.  相似文献   

8.
The stable carbon isotopic compositions of free and sulfur (S)-bound biomarkers derived from algae, (cyano)bacteria, archaea and higher plants and total organic carbon (TOC) during the first phase of the late Cenomanian/Turonian oceanic anoxic event (OAE) were measured in black shales deposited in the southern proto-Atlantic Ocean in the Cape Verde basin (DSDP Site 367) to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter. The average positive isotope excursions of TOC and biomarkers varied from 5.1‰ to 8.3‰. The δ13C values were cross correlated to infer potential common sources of biomarkers. This revealed common sources for C31 and C32 hopanes but no 1:1 relationship for pristane and phytane. The correlation of δ13CTOC with the δ13C value of sulfur (S)-bound phytane is the strongest. This is because S-bound phytane is derived from phytol that originates from all marine primary producers (algae and cyanobacteria) and thus represents a weighted average of their carbon isotopic compositions. The δ13C values of S-bound phytane and C35 hopane were also used to estimate pCO2 levels. Before the OAE burial event, pCO2 levels are estimated to be ca. 1300 ppmv using both biomarkers and the independent maximum Rubisco fractionation factors. At times of maximum organic carbon burial rates during the OAE, reconstructed pCO2 levels are estimated to be ca. 700 ppmv. However, compared to other C/T OAE sections the positive isotope excursion of S-bound phytane is also affected by an increased production during the OAE. When we compensate for this, we arrive at pCO2 levels around 1000 ppmv, a reduction of ca. 25%. This indicates that burial of organic matter can have a large effect on atmospheric CO2 levels.  相似文献   

9.
In this article, we describe the geological features of the Ediacaran (upper Sinian), lower Cambrian and lower Silurian shale intervals in the Upper Yangtze Platform, South China, and report on the gas potential of 53 samples from these major marine shale formations. Reflected light microscopy, total organic carbon (TOC) measurement, Rock-Eval, carbon isotope ratio analysis, thermovaporization gas chromatography (Tvap-GC), and open pyrolysis gas chromatography (open py-GC) were used to characterize the organic matter. Measured TOC in this research is normally >2% and averages 5%. TOC contents are roughly positively correlated with increasing geological age, i.e. lower Silurian shales exhibit generally lower TOC contents than lower Cambrian shales, which in turn commonly have lower TOC contents than Ediacaran shales. Kerogen has evolved to the metagenesis stage, which was demonstrated by the abundant pyrobitumen on microphotographs, the high calculated vitrinite reflectance (Ro = 3%) via bitumen reflectance (Rb), as well as δ13 C of gas (methane) inclusions. Pyrolysates from Tvap-GC and open py-GC are quantitatively low and only light hydrocarbons were detected. The lower Silurian shale generally exhibits higher generation of hydrocarbon than the lower Cambrian and Ediacaran shale. Cooles’ method and Claypool’s equations were used to reconstruct the original TOC and Rock-Eval parameters of these overmature samples. Excellent original hydrocarbon generation was revealed in that the original TOC (TOCo) is between 5% and 23%, and original S1+S2 (S1o+S2o) is ranging from 29 to 215 mg HC/g rock.  相似文献   

10.
Ordos Basin, the second largest sedimentary basin in China, contains enormous natural gas resources. Each of the four giant gas fields discovered so far in this basin (i.e., Sulige, Yulin, Wushenqi and Jingbian) has over 100 billion cubic meters (bcm) or 3.53 trillion cubic feet (tcf) of proven gas reserves. This study examines the stable carbon isotope data of 125 gas samples collected from the four giant gas fields in the Ordos Basin. Source rocks in the Upper Paleozoic coal measures are suggested by the generally high δ13C values of C1–C4 gaseous hydrocarbons in the gases from the Sulige, Yulin and Wushenqi gas fields. While the δ13CiC4 value is higher than that of the δ13CnC4, the dominant ranges for the δ13C1, δ13C2, and δ13C3 values in these Upper Paleozoic reservoired gases are −34 to −32‰, −27 to −23‰, and −25 to −24‰, respectively. The δ13C values of methane, benzene and toluene in gases from the Lower Paleozoic reservoirs of the Jingbian field indicate a significant contribution from humic source rocks, as they are similar to those in the Upper Paleozoic reservoirs of the Sulige, Yulin and Wushenqi gas fields. However, the wide variation and reversal in the δ13C1, δ13C2 and δ13C3 values in the Jinbian gases cannot be explained using a single source scenario, thus the gases were likely derived dominantly from the Carboniferous-Permian coal measures with some contribution from the carbonates in the Lower Permian Taiyuan Formation. The gas isotope data and extremely low total organic carbon contents (<0.2% TOC) suggest that the Ordovician Majiagou Formation carbonates are unlikely to be a significant gas source rock, thus almost all of the economic gas accumulations in the Ordos Basin were derived from Upper Paleozoic source rocks.  相似文献   

11.
A maturity indexing procedure based on the isotopic difference between the total accumulated methane produced by exhaustive pyrolysis and the kerogen (Δ13C) and the mole ratio of methane to kerogen carbon (CMR), has been tested by applying a standardized technique, i.e. exhaustive pyrolysis (600°C for 120 hr) of extracted-powdered samples and measurement of the amounts and isotopic composition of the methane and kerogen carbon, on a suite of 15 Bakken shale samples.A linear relation was found between the carbon mole ratio of pyrolysis-derived methane and total organic carbon and the δ13C difference between the pyrolysis-derived methane and total organic carbon (r = −0.79); and between the amount of CH4 generated from exhaustive pyrolysis and H/C atomic ratios (r = +0.91).  相似文献   

12.
Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian–Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, δ13Corg values lie mostly between −30‰ and −27‰, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C3 land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low δ13Corg values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian–Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.  相似文献   

13.
Inorganic gases are commonly seen in eastern China and occasionally in southern China from the shallow water columns above hot and cold springs. The gases contain 68% to nearly 100% CO2, with δ13CCO2 and δ13C1 values in the range of −1.18‰ to −6.00‰ and −19.48‰ to −24.94‰, respectively. All of the 34 large inorganic CO2 and one inorganic methane accumulations discovered in China are distributed in eastern parts of the country, from both onshore and continental shelf basins. No commercial inorganic gas accumulation has been found in central and western China. This is a review of the occurrence and geochemical characteristics of inorganic gas accumulations in Chinese sedimentary basins. A detailed study of gas samples collected from four representative inorganic CO2 pools and one possible inorganic methane pool indicates that inorganic alkane gases typically show δ13C1 values greater than −10‰ versus PDB (mostly −30‰), with a positive stable carbon isotope sequence of δ13C1 < δ 13C2 < δ13C3 < δ 13C4. In contrast, the δ13C1 values of biogenic alkane gases are lighter than −30‰, with a negative isotope sequence (i.e. δ13C1 > δ13C2 > δ 13C3 > δ13C4). Inorganic gases also tend to show less negative δ13CCO2 values (−10‰) than biogenic gases (<−10‰).  相似文献   

14.
Two sediment cores of up to 550 cm length from an intertidal flat of the German Wadden Sea near the island of Spiekeroog were investigated for the quantity and composition of fossil organic matter (OM). The lowermost parts of the cores are dominated by grey mud of a salt marsh facies containing mainly terrestrial OM estimated to account for 60–75% of the total OM, based on δ13C values and the ratio of short to long chain n-alkanols. The terrigenous origin of the dominant fraction is indicated, among others, by high proportions of C29 sterols and long chain n-alkanes typical of plant waxes. Coarse shell beds overlying the grey mud at 2–2.5 m depth represent a flooding and erosion event possibly related to heavy storm floods in the Middle Ages. Within the intertidal sand-dominated sediments in the upper parts of the cores total organic carbon (TOC) contents are generally low, ranging from 0.1% to 0.5%, and correlate well with the amount of mud fraction (r2 0.90). At the surface, marine OM has not undergone intense diagenetic alteration and so is the dominant fraction. Eroded peat particles are common throughout most of the sequence and values of the Phragmites peat indicator (PPI) > 5 indicate an origin from reed peat due to a high relative abundance of the n-C24 alkane. Changes in the composition of microbial communities over the depth interval investigated are documented by varying compositions of unsaturated fatty acids with 16 and 18 carbons. Eicosapentaenoic acid (EPA) was detected along the entire cores and indicates the presence of EPA-producing bacterial strains.  相似文献   

15.
We present the stable C isotope record of the changes within the past 20 yr in water level of two morphologically different lakes in central Poland. The aim was to explain the relationship between lake water level and the δ13C signature of bulk sedimentary organic matter (δ13CTOC) and to assess the potential of δ13CTOC as a paleolimnological proxy of lake level change. This was done by comparison of the fossil δ13CTOC record with instrumental data for lake level change in a shallow and small lake as well as in one large and deep basin. In both lakes the water table varied greatly between 1980 and 2000 AD. The δ13CTOC data were supplemented with δ15N and bulk geochemistry data, as well as paleoecological data. We show that δ13CTOC reacted to short term and low amplitude fluctuation in water level, but the response was highly dependent on the morphometry of the lake. In the shallow and small basin, δ13CTOC decreased along with lake level drop due to oxidation and greater input of organic matter from macrophytes colonizing the lake bottom. On the contrary, in the deep/large lake δ13CTOC decreased with increasing water level due to enhanced delivery of soil-derived OM to the lake during highstands. Our results have broad paleolimnological implications as they show that δ13CTOC cannot act as a universal paleohydrological proxy. Its interpretation for a particular lake can be ambiguous and must be supported with additional geochemical and paleocological information.  相似文献   

16.
Three sediment cores were taken from the Pearl River estuary and adjacent northern South China Sea (SCS). These sediment cores span the time interval 1900–2000 AD. The stratigraphy of the concentration, the ratio of total organic carbon (TOC) to total nitrogen (TN) and stable isotope (δ13Corg) of organic carbon (OC) from three high-resolution sediment cores were analyzed. The stratigraphic profiles of OC concentration, TOC/TN ratios and δ13Corg for the near past 100 yrs indicate that terrestrial organic matter decreases from 68.3% to 27.4% of the TOC in the Pearl River estuary, while Dapeng Bay (offshore east of Hong Kong) apparently had throughout little terrestrial organic matter input. The highest deposited OC occurs at the Humen River mouth and the OC concentrations are higher in the outer estuary than in the inner shelf of the northern SCS. The deposited OC at the River mouth increased with time, which could be caused by the high precipitation of land-derived organic matter and the high input of terrestrial organic matter, which is likely related to the rapid urbanization and industrial development in the Pearl River Delta since the 1970s. The OC concentrations did not exhibit an obvious increase with time in most areas of the Pear River estuary and adjacent inner shelf of the SCS, but the algal-derived OC concentration inferred from the δ13Corg values increased with time especially from 1980 to 2000 in the outer Pearl River estuary and Dapeng Bay. This increase is presumably caused by enhanced primary marine productivity supported by higher anthropogenic nutrient inputs.  相似文献   

17.
Surface sediment samples were collected from the Squamish River Delta, British Columbia, in order to determine the role of sediment surface area in the preservation of organic matter (OM) in a paralic sedimentary environment. The Squamish Delta is an actively prograding delta, located at the head of Howe Sound.Bulk total organic carbon (TOC) values across the Squamish Delta are low, ranging from 0.1 to 1.0 wt.%. The carbon/total nitrogen ratio (Corg/N) ranges from 6 to 17, which is attributed to changes in OM type and facies variations. The <25-μm fraction has TOC concentrations up to 2.0 wt.%, and a Corg/N ratio that ranges from 14 to 16. The 53–106-μm fraction has higher TOC concentrations and Corg/N ratios relative to the 25–53-μm fraction. The Corg/N ratio ranges from 9 to 18 in the 53–106-μm fraction and 5.5–10.5 in the 25–53-μm fraction. Surface area values for bulk sediments are low (0.5–3.0 m2/g) due to the large proportion of silt size material. Good correlation between surface area and TOC in bulk samples suggests that OM is adsorbed to mineral surfaces. Similar relationships between surface area and TOC were observed in size-fractionated samples. Mineralogy and elemental composition did not correlate with TOC concentration.The relationships between surface area, TOC and total nitrogen (TN) can be linked to the hydrodynamic and sedimentological conditions of the Squamish Delta. As a result, the Squamish Delta is a useful modern analogue for the formation of petroleum source rocks in ancient deltaic environments, where TOC concentrations are often significantly lower than those in source rocks formed in other geological settings.  相似文献   

18.
Groundwaters in the confined aquifers of the Chianan and Ilan coastal plains of Taiwan are rich in dissolved methane (CH4). Serious endemic “blackfoot disease”, which occurred in the Chianan plain, especially during AD1950-1970, has been demonstrated to have arisen from drinking highly reducing groundwater with abnormal arsenic and humic substance levels. In order to explore the origin of CH4 and its hydrological implications, stable carbon isotope ratios (δ13C) and radiocarbon (14C) ages of exsolved CH4, dissolved inorganic carbon (DIC), and sedimentary biogenic sediments from a total of 34 newly completed water wells at 16 sites were determined. The main results obtained are as follows: (1) The δ13CCH4 (−65‰ to −75‰) values indicate that, except for one thermogenic sample (δ13CCH4=38.2) from the Ilan plain, all CH4 samples analyzed were produced via microbially mediated CO2 reduction. Many δ13CDIC values are considerably greater than −10‰ and even up to 10‰ due to Rayleigh enrichment during CO2 reduction. (2) Almost all the 14C ages of CH4 samples from the shallow aquifer (I) (<60 m depth) are greater than the 14C ages of coexisting DIC and sediments, suggesting the presence of CH4 from underlying aquifers. (3) The 14C ages of coexisting CH4, DIC and sediments from aquifer (II) of the Chianan plain are essentially equal, reflecting in-situ generation of CH4 and DIC from decomposition of sedimentary organic matter and sluggishness of the groundwater flow. On the other hand, both CH4 and DIC from each individual well of the relatively deep aquifers (III) and (IV) in the Chianan plain are remarkably younger than the deposition of their coexisting sediments, indicating that current groundwaters entered these two aquifers much later than the deposition of aquifer sediments. (4) Each CH4 sample collected from the Ilan plain is older than coexisting DIC, which in turn is distinctly older than the deposition of respective aquifer sediments, demonstrating the presence of much older CO2 and CH4 from underlying strata.  相似文献   

19.
The presence of partially oxidized algal organic matter in oil-prone marine source rocks, is the rule rather than the exception. Partially oxidized, algal kerogen can still act as a significant source of liquid hydrocarbons. However, the corresponding peak of C12 + hydrocarbon generation is shifted to a considerably lower maturity level compared with that of the classical Type II kerogen. The extent of primary alteration-oxidation of marine algal kerogen is monitored by means of solid state microfluorescence spectroscopy. A new parameter, the Primary Alteration Factor (PAF) is established, and the relationships between PAF and H/C, O/C, HI, TOC and between PAF and %0δ13C are determined. The present data show large variations in the bulk chemistry of immature marine algal kerogens, and reveal evidence for gradational dehydrogenation/oxidation of the source organic matter. This contrasts with the recently proposed mechanism for kerogen formation. SEM analysis reveals a relationship between the physical breakdown of algal organic matter and the formation of liptodetrinite. FTIR analysis shows that the incorporation of primary oxygen in the kerogen macromolecules is not in the form of carbonyl or carboxyl functionalities. The presence of highly unreactive, stable oxygen, associated with aromatic structures in partially oxidized algal kerogen, is suggested by resistance of the kerogen to graphitization. The FTIR data also suggest the presence of aryl ether oxygen. The present findings raise fundamental questions regarding the mechanisms of kerogen cracking and kerogen formation, and have important implications for petroleum exploration.  相似文献   

20.
Variations in the carbon isotopic composition (δ13C) of pristane, phytane, n-heptadecane (n-C17), C29 ααα 20R sterane, and aryl isoprenoids provide evidence for a diverse community of algal and bacterial organisms in organic matter of the Upper Ordovician Maquoketa Group of the Illinois Basin. Carbon isotopic compositions of pristane and phytane from the Maquoketa are positively covariant (r = 0.964), suggesting that these compounds were derived from a common source inferred to be primary producers (algae) from the oxygenated photic zone. A variation of 3‰ in δ13C values (−31 to −34‰) for pristane and phytane indicates that primary producers utilized variable sources of inorganic carbon. Average isotopic compositions of n-C17 (−32‰) and C29 ααα 20R sterane (−31‰) are enriched in 13C relative to pristane and phytane (−33‰) suggesting that these compounds were derived from a subordinate group of primary producers, most likely eukaryotic algae. In addition, a substantial enrichment of 13C in aryl isoprenoids (−14 to −18‰) and the identification of tetramethylbenzene in pyrolytic products of Maquoketa kerogen indicate a contribution from photosynthetic green sulfur bacteria to the organic matter. The presence of anaerobic, photosynthetic green sulfur bacteria in organic matter of the Maquoketa indicates that anoxic conditions extended into the photic zone.The δ13C of n-alkanes and the identification of an unusual suite of straight-chain n-alkylarenes in the m/z 133 fragmentograms of Ordovician rocks rich in Gloeocapsomorpha prisca (G. prisca) indicate that G. prisca did not contribute to the organic matter of the Maquoketa Group.  相似文献   

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