首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Lein  A. Yu.  Rusanov  I. I.  Zakharova  E. E.  Flint  M. V.  Ivanov  M. V. 《Doklady Earth Sciences》2010,432(1):687-689
Within the mass of recent (unit-I) and ancient Black Sea (unit-II) sediments on the outer shelf of the Russian sector of the Black Sea, the rates of anoxic processes participating in diagenetic transformations of carbon and sulfur compounds were first measured using 35S and 14C radioactive tracers. The main energy source for biogeochemical processes in (unit-I) sediments is the organic matter (OM) supplied to the bottom from the water mass. In (unit-II) sediments, this is methane in a migratory form proved by the excess of its oxidation rate over that of its generation. In recent silt, the primary microbial process is sulfate reduction; in unit-II, this is methane anoxic oxidation by the consortium of archeides and sulfate reductants. The organic matter produced in methane oxidation, in turn, acts as an energy source for the community of anaerobic heterotrophic microorganisms in the bottom sediments, which are remote from the water-sediment interface.  相似文献   

2.
The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO42−-CH4 transition where H2S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H2S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe2+ diffusing up from below. The H2S-Fe2+ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO42− and 10 yr for H2S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO42−-CH4 and H2S-Fe2+ cause the trapping of isotopically heavy iron sulfide with δ34S = +15 to +33‰ at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO42− diffusing downward into the SO42−-CH4 transition has an isotopic composition of +19‰, close to the +23‰ of H2S diffusing upward. These isotopic compositions are, however, very different from the porewater SO42− (+43‰) and H2S (−15‰) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H2S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth’s history.  相似文献   

3.
Permian Khuff reservoirs along the east coast of Saudi Arabia and in the Arabian Gulf produce dry sour gas with highly variable nitrogen concentrations. Rough correlations between N2/CH4, CO2/CH4 and H2S/CH4 suggest that non-hydrocarbon gas abundances are controlled by thermochemical sulfate reduction (TSR). In Khuff gases judged to be unaltered by TSR, methane δ13C generally falls between −40‰ and −35‰ VPDB and carbon dioxide δ13C between −3‰ and 0‰ VPDB. As H2S/CH4 increases, methane δ13C increases to as much as −3‰ and carbon dioxide δ13C decreases to as little as −28‰. These changes are interpreted to reflect the oxidation of methane to carbon dioxide.Khuff reservoir temperatures, which locally exceed 150 °C, appear high enough to drive the reduction of sulfate by methane. Anhydrite is abundant in the Khuff and fine grained nodules are commonly rimmed with secondary calcite cement. Some cores contain abundant pyrite, sphalerite and galena. Assuming that nitrogen is inert, loss of methane by TSR should increase N2/CH4 of the residual gas and leave δ15N unaltered. δ15N of Paleozoic gases in Saudi Arabia varies from −7‰ to 1‰ vs. air and supports the TSR hypothesis. N2/CH4 in gases from stacked Khuff reservoirs varies by a factor of 19 yet the variation in δ15N (0.3–0.5‰) is trivial.Because the relative abundance of hydrogen sulfide is not a fully reliable extent of reaction parameter, we have attempted to assess the extent of TSR using plots of methane δ13C versus log(N2/CH4). Observed variations in these parameters can be fitted using simple Rayleigh models with kinetic carbon isotope fractionation factors between 0.98 and 0.99. We calculate that TSR may have destroyed more than 90% of the original methane charge in the most extreme instance. The possibility that methane may be completely destroyed by TSR has important implications for deep gas exploration and the origin of gases rich in nitrogen as well as hydrogen sulfide.  相似文献   

4.
Previous geochemical and microbiological studies in the Cariaco Basin indicate intense elemental cycling and a dynamic microbial loop near the oxic-anoxic interface. We obtained detailed distributions of sulfur isotopes of total dissolved sulfide and sulfate as part of the on-going CARIACO time series project to explore the critical pathways at the level of individual sulfur species. Isotopic patterns of sulfate (δ34SSO4) and sulfide (δ34SH2S) were similar to trends observed in the Black Sea water column: δ34SH2S and δ34SSO4 were constant in the deep anoxic water (varying within 0.6‰ for sulfide and 0.3‰ for sulfate), with sulfide roughly 54‰ depleted in 34S relative to sulfate. Near the oxic-anoxic interface, however, the δ34SH2S value was ∼3‰ heavier than that in the deep water, which may reflect sulfide oxidation and/or a change in fractionation during in situ sulfide production through sulfate reduction (SR). δ34SH2S and Δ33SH2S data near the oxic-anoxic interface did not provide unequivocal evidence to support the important role of sulfur-intermediate disproportionation suggested by previous studies. Repeated observation of minimum δ34SSO4 values near the interface suggests ‘readdition’ of 34S-depleted sulfate during sulfide oxidation. A slight increase in δ34SSO4 values with depth extended over the water column may indicate a reservoir effect associated with removal of 34S-depleted sulfur during sulfide production through SR. Our δ34SH2S and Δ33SH2S data also do not show a clear role for sulfur-intermediate disproportionation in the deep anoxic water column. We interpret the large difference in δ34S between sulfate and sulfide as reflecting fractionations during SR in the Cariaco deep waters that are larger than those generally observed in culturing studies.  相似文献   

5.
Pyritization in late Pleistocene sediments of the Black Sea is driven by sulfide formed during anaerobic methane oxidation. A sulfidization front is formed by the opposing gradients of sulfide and dissolved iron. The sulfidization processes are controlled by the diffusion flux of sulfide from above and by the solid reactive iron content. Two processes of diffusion-limited pyrite formation were identified. The first process includes pyrite precipitation with the accumulation of iron sulfide precursors with the average chemical composition of FeSn (n = 1.10-1.29), including greigite. Elemental sulfur and polysulfides, formed from H2S by a reductive dissolution of Fe(III)-containing minerals, serve as intermediates to convert iron sulfides into pyrite. In the second process, a “direct” pyrite precipitation occurs through prolonged exposure of iron-containing minerals to dissolved sulfide. Methane-driven sulfate reduction at depth causes a progressive formation of pyrite with a δ34S of up to +15.0‰. The S-isotopic composition of FeS2 evolves due to contributions of different sulfur pools formed at different times. Steady-state model calculations for the advancement of the sulfidization front showed that the process started at the Pleistocene/Holocene transition between 6360 and 11 600 yr BP. Our study highlights the importance of anaerobic methane oxidation in generating and maintaining S-enriched layers in marine sediments and has paleoenvironmental implications.  相似文献   

6.
Carbon and hydrogen isotopic compositions of New Zealand geothermal gases   总被引:1,自引:0,他引:1  
Carbon and hydrogen isotopic compositions are reported for methane, hydrogen and carbon dioxide from four New Zealand geothermal areas: Ngawha, Wairakei, Broadlands and Tikitere. Carbon-13 contents are between ?24.4 and ?29.5%. (PDB) for methane, and between ?3.2 and ?9.1%. for carbon dioxide. Deuterium contents are between ?142 and ?197%. (SMOW) for methane and between ?310 and ?600%. for hydrogen. The different areas have different isotopic compositions with some general relationships to reservoir temperature.The isotopic exchange of hydrogen with water indicates acceptable reservoir temperatures of 180–260°C from most spring samples but often higher than measured temperatures in well samples. Indicated temperatures assuming 13C equilibria between CH4 and CO2 are 100–200°C higher than measured maxima. This difference may be due to partial isotopic equilibration or may reflect the origin of the methane. Present evidence cannot identify whether the methane is primordial, or from decomposing sediments or from reduction of magmatic CO2. The isotopic equilibria between CH4, CO2, H2 and H2O are reviewed and a new semi-empirical temperature scale proposed for deuterium exchange between methane and water.  相似文献   

7.
A detailed model is presented of methane photochemistry in the primitive terrestrial atmosphere along with speculation about its interpretation. Steady-state CH4 mixing ratios of 10−6–10−4 could have been maintained by a methane source of about 1011 cm−2 s−1, which is comparable to the modern biogenic methane production rate. In the absence of a source, methane would have disappeared in <104 years, being either oxidized, or polymerized into more complex hydrocarbons. The source strength needed to maintain a steady CH4 mixing ratio and the degree to which methane could have polymerized to form higher hydrocarbons depend upon the amount of CO2 present in the early atmosphere. The dependence on H2 is much weaker. Infrared absorption by methane, and especially by other hydrocarbon species, may have supplemented the greenhouse warming due to carbon dioxide. A radiative model is needed to establish this effect quantitatively. The destruction of the methane greenhouse early in the Proterozoic may have triggered the Huronian glaciation.These calculations also suggest that atmospheres rich in both CO2 and CH4 may be photochemically unstable with respect to conversion to CO.  相似文献   

8.
Methane release from soils of a Georgia salt marsh   总被引:1,自引:0,他引:1  
A seasonal study of methane release from marsh soils to the atmosphere indicates that ebullition is a significant process varying both seasonally and spatially. Release rates are higher during summer months than winter months and ebullition is greatest in the short Spartina alterniflora marshes and least in the tall S. alterniflora marshes. The annual amounts of methane released in the short and tall marshes are 53.1 and 0.4 gm?3 which represents a loss of 8.8 and 0.002% of the net carbon fixation in the two respective marsh types.In vitro experimentation shows that methane production is sensitive to changes in temperature and addition of H2 and CO2.  相似文献   

9.
天然气水合物成因探讨   总被引:18,自引:0,他引:18  
天然气水合物是未来的能源资源。其分布于极地地区、深海地区及深水湖泊中。在海洋里,天然气水合物主要分布于外大陆边缘和洋岛的周围,其分布与近代火山的分布范围具有一致性。同位素组成表明天然气水合物甲烷主要是由自养产甲烷菌还原CO2形成的。典型的大陆边缘沉积物有机碳含量低(<0.5%~1.0%),不足以产生天然气水合物带高含量的甲烷。赋存天然气水合物的沉积物时代主要为晚中新世-晚上新世,具有一定的时限性,并且天然气水合物与火山灰或火山砂共存,表明其形成与火山-热液体系有一定联系。火山与天然气水合物空间上的一致性表明,天然气水合物甲烷的底物可能主要是由洋底火山喷发带来的CO2。由前人研究结果推断 HCO3在脱去两个O原子的同时,可能发生了亲核重排,羟基 H原子迁移到 C原子上,形成了甲酰基(HCO),使甲烷的第一个 H原子来源于水。探讨了甲烷及其水合物的形成机制,提出了天然气水合物成因模型。  相似文献   

10.
The concentrations of CH4, SO42−, σCO2 and the carbon isotope compositions of ΣCO2 and CH4 in the pore-water of the GS sedimentary core collected from Guishan Island (Pearl River Estuary), South China Sea, were determined. The methane concentration in the pore-water shows dramatic changes and sulfate concentration gradients are linear at the base of the sulfate reduction zone for the station. The carbon isotope of methane becomes heavier at the sulfate-methane transition (SMT) likely because of the Raleigh distillation effect; 12CH4 was oxidized faster than 13CH4, and this caused the enrichment of residual methane δ 13C and δ 13C-ΣCO2 minimum. The geochemical profiles of the pore-water support the existence of anaerobic oxidation of methane (AOM), which is mainly controlled by the quality and quantity of the sedimentary organic matter. As inferred from the index of δ 13C-TOC value and TOC/TN ratio, the organic matter is a mix of mainly refractory terrestrial component plus some labile alga marine-derived in the study area. A large amount of labile organic matter (mainly labile alga marine-derived) is consumed via the process of sedimentary organic matter diagenesis, and this reduces the amount of labile organic matter incorporated into the base of the sulfate reduction zone. Due to the scarcity of labile organic matter, the sulfate will in turn be consumed by its reaction with methane and therefore AOM takes place. Based on a diffussion model, the portion of pore-water sulfate reduction via AOM is 58.6%, and the percentage of ΣCO2 in the pore-water derived from AOM is 41.4%. Thus, AOM plays an important role in the carbon and sulfur cycling in the marine sediments of Pearl River Estuary.  相似文献   

11.
We collected sediment samples and pore water samples from the surface sediment on the Daini Atsumi Knoll, and analyzed the sediments for CH4, C2H6, and δ13CCH4, and the pore fluids for CH4, C2H6, δ13CCH4, Cl, SO42−, δ18OH2O, and δDH2O, respectively. A comparison of the measured concentration and isotopic composition of methane in pore water samples with those in sediment samples revealed that methane was present in the sediment samples at a higher concentration and was isotopically heavier than those in the pore water samples. It suggests that the effect of the release of a sorbed gas bound to organic particles when heated prior to analysis of hydrocarbons was larger than that of the degassing process. A large amount of a sorbed gas would be a significant source of natural gas. Two striking features are the chemical and isotopic composition of the pore water samples taken from the different sites around the Daini Atsumi Knoll. In the KL09, KL10, and KP07 samples, Cl concentrations in the pore water samples showed depletion to a minimum of 460 mmol/kg, correspond to  17% dilution of seawater, however the latter was not enriched in CH4. The isotopic compositions of pore water samples suggested the low-Cl fluids in the pore water were not derived from dissociation of methane hydrate, but were derived from input of meteoric water. In contrast, in the KP05 samples from the north flank of the Daini Atsumi Knoll, pore water were characterized by CH4 enrichment more than 370 μmol/kg, but not depleted in Cl concentrations. The observed methane concentration in the KP05 samples is not sufficient for methane hydrate to form in situ, indicating that the existence of methane hydrate in the surface sediment is negligible, as supported by Cl concentration. Based on the stable carbon isotope ratio of methane in the pore fluid from the KP05 site (δ13CCH4 < − 50‰PDB), methane is thought to be of microbial origin. The pore waters in the surface sediments in the north flank of the Daini Atsumi Knoll were not directly influenced by upward fluid bearing methane of thermogenic origin from a deeper part of the sedimentary layer. However, extremely high methane concentration in the north flank site as compared with the concentration of pore water taken from the normal seafloor suggests that the north flank site is not the normal seafloor. We hypothesize that upward migration of chemically-reduced fluids from a deeper zone of the sedimentary layer reduces chemically-oxidized solutes in the surface sediment. As a consequence methane production replaced sulfate reduction as the microbial metabolism in the reduced environment of the surface sediment.  相似文献   

12.
The relationship among H2S, total organic carbon (TOC), total sulfur (TS) and total nitrogen contents of surface sediments (0–1 cm) was examined to quantify the relationship between H2S concentrations and TOC content at the sediment water interface in a coastal brackish lake, Nakaumi, southwest Japan. In this lake, bottom water becomes anoxic during summer due to a strong halocline. Lake water has ample dissolved SO4 2? and the surface sediments are rich in planktic organic matter (C/N 7–9), which is highly reactive in terms of sulfate reduction. In this setting the amount of TOC should be a critical factor regulating the activity of sulfate reduction and H2S production. In portions of the lake where sediment TOC content is less than 3.5 %, H2S was very low or absent in both bottom and pore waters. However, in areas with TOC >3.5 %, H2S was correlated with TOC content (pore water H2S (ppm) = 13.9 × TOC (%) ? 52.1, correlation coefficient: 0.72). H2S was also present in areas with sediment TS above 1.2 % (present as iron sulfide), which suggests that iron sulfide formation is tied to the amount of TOC. Based on this relationship, H2S production has progressively increased after the initiation of land reclamation projects in Lake Nakaumi, as the area of sapropel sediments has significantly increased. This TOC–H2S relationship at sediment–water interface might be used to infer H2S production in brackish–lagoonal systems similar to Lake Nakaumi, with readily available SO4 2? and reactive organic matter.  相似文献   

13.
Carbon stable-isotope compositions of coexisting carbon dioxide and methane from geothermal springs across the Central Andes of northern Chile and Bolivia are reported. A total of 60 samples were analyzed for δ13CCO2 and, of these, 10 were selected for δ13CCH4 analyses. The Central Andes are characterized by an active volcanic arc and an unusually thick (up to 75 km) continental crust behind the arc, beneath the high plateau region of the Altiplano. Furthermore, helium-isotope evidence suggests active mantle degassing in a 350-km-wide zone beneath the thick continental crust in the Central Andes (Hoke et al., 1994).

The present results show a wide range of δ13CCO2 (-14.9 to -0.6‰) and a surprisingly heavy δ13CCH4 (?20.9 to ?12.3‰). The difference between δ13CCO2 and δ13CCH4 13CCO2-CH4 ) for individual samples varies between 1.5‰ and 13.5‰. The δ13CCO2 results show wide and overlapping ranges in the samples collected from the Precordillera, the Volcanic Arc (or Western Cordillera), the Altiplano, and the Eastern Cordillera. The widest ranges occur in the Eastern Cordillera (?15.0 to ?4.8‰) and the Altiplano (?20 to ?6‰). The δ13CCO2 results for geothermal samples from the Volcanic Arc range between ?8.0‰ (Surire) and ?0.6‰ (Abra de Nappa), whereas δ13CCO2 measured in gases collected from geothermal springs in the Precordillera range from ?10 to ?5‰.

The relationships between 3He/4He, δ13CCO2 , and δ13CCH4 are used to distinguish between crustal and mantle origins. The wide (21‰) range in the is interpreted to reflect contributions from different CO2 sources that include organic and inorganic crustal and mantle carbon. Assuming isotopic equilibrium between coexisting methane and carbon dioxide, Δ13CCO2-CH4 suggests very high equilibrium temperatures, in excess of 530°C, for some geothermal systems that also are characterized by a high (up to 63%) mantle-derived helium component.

δ13CCH4 results suggest that methane has not formed by bacteriogenic processes or by thermal decomposition of organic matter, but rather abiogenically through the high-temperature reaction between H2 and CO2. The δ13CCH4 results for the samples from the Volcanic Arc and from two CO2-rich geothermal springs in the Altiplano (Coipasa-2 and Belen de Andamarca) are similar to those reported from hydrothermal fluids emitted from the East Pacific Rise (Welhan, 1988) and White Island, New Zealand (Hulston and McCabe, 1962), suggesting a mantle-derived carbon component in the methane.  相似文献   

14.
We report solid phase sulfur speciation of six cores from sediments underlying oxic, suboxic and anoxic-sulfidic waters of the Black Sea. Our dataset includes the five sulfur species [pyrite-sulfur, acid volatile sulfides (AVS), zerovalent sulfur (S(0)), organic polysulfides (RSx), humic sulfur] together with reactive iron and manganese, as quantified by dithionite extraction, and total organic carbon. Pyrite – sulfur was the major phase in all cores [200-400 µmol (g dry wt)- 1] except for the suboxic core. However, zerovalent sulfur and humic sulfur also reached very significant levels: up to about 109 and 80 µmol (g dry wt)- 1, respectively. Humic sulfur enrichment was observed in the surface fluff layers of the eastern central basin sediments where Unit-1 type depositional conditions prevail. Elemental sulfur accumulated as a result of porewater sulfide oxidation by reactive iron oxides in turbidities from the anoxic basin margin and western central basin sediments. The accumulation of elemental sulfur to a level close to that of pyrite-S in any part of central Black Sea sediments has never been reported before and our finding indicates deep basin turbidites prevent the build-up of dissolved sulfide in the sediment. This process also contributes to diagenetic pyrite formation whereas in the non-turbiditic parts of the deep basin water column formed (syngenetic) pyrite dominates the sulfur inventory. In slope sediments under suboxic waters, organic sulfur (humic sulfur + organic polysulfides) account for 33-42% of total solid phase S, indicating that the suboxic conditions favor organosulfur formation. Our study shows that the interactions between depositional patterns (Unit 1 vs. turbidite), redox state of overlying waters (oxic-suboxic-sulfidic) and organic matter content determine sulfur speciation and enable the accumulation of elemental sulfur and organic sulfur species close to a level of pyrite-S.  相似文献   

15.
The Dvurechenskii mud volcano (DMV) is located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea). The DMV was studied during the RV Meteor expedition M72/2 as an example of an active mud volcano system, to investigate the significance of submarine mud volcanism for the methane and sulfide budget of the anoxic Black Sea hydrosphere. Our studies included benthic fluxes of methane and sulfide, as well as the factors controlling transport, consumption and production of both compounds within the sediment. The pie-shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at its summit north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was repressed in this zone due to the upward flow of sulfate-depleted fluids through recently deposited subsurface muds, apparently limiting microbial methanotrophic activity. Consequently, the emission of dissolved methane into the water column was high, with an estimated rate of 0.46 mol m−2 d−1. On the wide plateau and edge of the mud volcano surrounding the summit, fluid flow and total methane flux were lower, allowing higher SR and AOM rates correlated with an increase in sulfate penetration into the sediment. Here, between 50% and 70% of the methane flux (0.07-0.1 mol m−2 d−1) was consumed within the upper 10 cm of the sediment. The overall amount of dissolved methane released from the entire mud volcano structure into the water column was significant with a discharge of 1.3 × 107 mol yr−1. The DMV maintains also high areal rates of methane-fueled sulfide production and emission of on average 0.05 mol m−2 d−1. This is a difference to mud volcanoes in oxic waters, which emit similar amounts of methane, but not sulfide. However, based on a comparison of this and other mud volcanoes of the Black Sea, we conclude that sulfide and methane emission into the hydrosphere from deep-water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.  相似文献   

16.
The South Caspian sedimentary basin is a unique area with thick Mesozoic-Cenozoic sediments (up to 30–32 km) characterized by an extremely high fluid generation potential. The large amount of active mud volcanoes and the volumes of their gas emissions prove the vast scale of fluid generation. Onshore and offshore mud volcanoes annually erupt more than 109 cubic meters of gases consisting of CH4 (79–98%), and a small admixture of C2H6, C3H8, C4H10, C5H12, CO2, N, H2S, Ar, He. Mud volcanism is closely connected to the processes occurring in the South Caspian depression, its seismicity, fluctuations of the Caspian Sea level, solar activity and hydrocarbon generation.The large accumulations of gas hydrates are confined to the bottom sediments of the Caspian Sea, mud volcanoes crater fields (interval 0–0.4 m, sea depth 480 m) and to the volcanoes body at the depth of 480–800 from the sea bottom. Resources of HC gases in hydrates saturated sediments up to a depth of 100 m and are estimated at 0.2×1015–8×1015 m3. The amount of HC gases concentrated in them is 1011–1012 m3.The Caspian Sea, being an inland closed basin is very sensitive to climatic and tectonic events expressed in sea level fluctuations. During regressive stages as a result of sea level fall and the reducing of hydrostatic pressure the decomposition of gas hydrates and the releasing of a great volume of HC gases consisting mainly of methane are observed.From the data of deep drilling, seismoacoustics, and deep seismic mud volcanic activity in the South Caspian Basin started in the Lower Miocene. Activity reached its highest intensity at the boundary between the Miocene and Pliocene and was associated with dramatic Caspian Sea level fall in the Lower Pliocene of up to 600 m, which led to the isolation of the PaleoCaspian from the Eastern ParaTethys. Catastrophic reduction of PaleoCaspian size combined with the increasing scale of mud volcanic activity caused the oversaturation and intoxication of water by methane and led to the mass extinction of mollusks, fishes and other groups of sea inhabitants. In the Upper Pliocene and Quaternary mud volcanism occurred under the conditions of a semi-closed sea periodically connected with the Pontian and Mediterranean Basins. Those stages of Caspian Sea history are characterized by the revival of the Caspian organic world.Monitoring of mud volcanoes onshore of the South Caspian demonstrated that any eruption is predicted by seismic activation in the region (South-Eastern Caucasus) and intensive fluid dynamics on the volcanoes.  相似文献   

17.
Elemental composition was used to calculate the amounts of compounds produced during the diagenetic evolution of a coal series from the Mahakam delta (Kalimantan, Indonesia). These calculations were based on the following hypotheses: organic nitrogen does not take part in reactions and remains unchanged in the residual organic matter, the only compounds produced are water, carbon dioxide and hydrocarbons.This approach shows that carbon loss during diagenesis is mainly as CO2, and hydrogen loss is mainly as H2O. Hydrocarbon production is negligible, in accordance with absence of bacterial methane accumulations in the Mahakam delta.The δ13C of coals in the sequence becomes about 2 per mil more positive over the diagenetic depth range of coal evolution. Accounting for the coal δ13C change in terms of CO2 loss requires that the CO2 given off have δ13C of about ?40%.. Such negative CO2 has not been observed in natural systems, except when CH4 is undergoing oxidation. Several plausible causes for this effect are discussed.  相似文献   

18.
Anthropogenic activities often result in the emissions of methane (CH4) and carbon dioxide (CO2) which are the principal components of greenhouse gases. The mitigation of these gases to avert further occurrence of global warming has attracted a lot of research interest. In this study, the potential of greenhouse gases abatement via catalytic CO2 (dry) reforming of methane to syngas over samarium oxide-supported cobalt (20 wt% Co/80 wt% Sm2O3) catalyst was investigated. The 20 wt% Co/80 wt% Sm2O3 material was synthesized via wet impregnation method and characterized using different instrument techniques. The methane dry reforming reaction, as well as its kinetics over the catalyst, was studied in a stainless steel fixed-bed continuous flow reactor at feed (CH4:CO2) ratios range of 0.1–1.0, temperature range of 923–1023 K and gas hourly space velocity (GHSV) of 30,000 h?1. The 20 wt% Co/80 wt% Sm2O3 catalyst showed promising catalytic activity evident from the highest CH4 and CO2 conversion of ~71 and ~74% as well as the highest hydrogen (H2) and carbon monoxide (CO) yield of ~62 and ~73%, respectively. Moreover, the methane dry reforming over the 20 wt% Co/80 wt% Sm2O3 catalyst produces H2/CO ratio close to unity hence suitable for use as a chemical intermediate for synthesis of oxygenated fuels. The kinetic data obtained from the methane dry reforming were fitted to power law model. Apparent activation energies of 88.62, 80.12, 108.12 and 100.91 kJ mol?1 were obtained for CH4, CO2, H2 and CO, respectively. The characterization of the spent 20 wt% Co/80 wt% Sm2O3 catalyst after 4 h of time-on-stream has confirmed the presence of amorphous carbon which can easily be gasified.  相似文献   

19.
Abiotic methane in serpentinized peridotites (MSP) has implications for energy resource exploration, planetary geology, subsurface microbiology and astrobiology. Once considered a rare occurrence on Earth, reports of MSP are increasing for numerous localities worldwide in low temperature, land-based springs and seeps. We report the discovery of six methane-rich water springs and two ponds with active gas bubbling in the Ronda peridotite massif, in southern Spain. Water is hyperalkaline with typical hydrochemical features of active serpentinization (pH: 10.7 to 11.7, T: 17.1 to 21.5 °C, Ca–OH facies). Dissolved CH4 concentrations range from 0.1 to 3.2 mg/L. The methane stable C and H isotope ratios in the natural spring and bubbling sites (δ13CCH4: −12.3 to −37‰ VPDB; δ2HCH4: −280 to −333‰ VSMOW) indicate a predominant abiotic origin. In contrast, springs with manmade water systems, i.e., pipes or fountains, appear to have mixed biotic-abiotic origin (δ13CCH4: −44 to −69‰; δ2HCH4: −180 to −319‰). Radiocarbon (14C) analyses show that methane C in a natural spring is older than ca. 50,000 y BP, whereas dissolved inorganic carbon (DIC) analysed in all springs has an apparent 14C age ranging from modern to 2334 y BP. Therefore most, if not all, of the CH4 is allochthonous, i.e., not generated from the carbon in the hyperalkaline water. Methane is also released as bubbles in natural ponds and as diffuse seepages (∼101–102 mg CH4 m−2d−1) from the ground up to several tens of metres from the seeps and springs, albeit with no overt visual evidence. These data suggest that the gas follows independent migration pathways, potentially along faults or fracture systems, physically isolated from the hyperalkaline springs. Methane does not seem to be genetically related to the hyperalkaline water, which may only act as a carrier of the gas. Gas-bearing springs, vents and invisible microseepage in land-based peridotites are more common than previously thought. In addition to other geological sources, MSP is potentially a natural source of methane for the troposphere and requires more worldwide flux measurements.  相似文献   

20.
Sulfate reduction during seawater reaction with fayalite and with magnetite was rapid at 350°C, producing equilibrium assemblages of talc-pyrite-hematite-magnetite at low water/rock ratios and talc-pyrite-hematite-anhydrite at higher water/rock ratios. At 250°C, seawater reacting with fayalite produced detectable amounts of dissolved H2S, but extent of reaction of solid phases was minor after 150 days. At 200°C, dissolved H2S was not detected, even after 219 days, but mass balance calculations suggest a small amount of pyrite may have formed. Reaction stoichiometry indicates that sulfate reduction requires large amounts of H+, which, in subseafloor hydrothermal systems is provided by Mg metasomatism. Seawater contains sufficient Mg to supply all the H+ necessary for quantitative reduction of seawater sulfate.Systematics of sulfur isotopes in the 250 and 350°C experiments indicate that isotopic equilibrium is reached, and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H2S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号