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1.
The carbon and hydrogen isotopic composition of biogenic gas is of great importance for the study of its generation pathway and reservoiring characteristics. In this paper, the formation pathways and reservoiring characteristics of biogenic gas reservoirs in China are described in terms of the carbon and hydrogen isotopic compositions of 31 gas samples from 10 biogenic gas reservoirs. The study shows that the hydrogen isotopic compositions of these biogenic gas reservoirs can be divided into three intervals: δ>−200‰, −250‰<δ<-−200‰ and δ<−250‰. The forerunners believed that the main generation pathway of biogenic gas under the condition of continental fresh water is acetic fermentation. Our research results showed that the generation pathway of biogenic gas under the condition of marine facies is typical CO2- reduction, the biogenic gas has heavy hydrogen isotopic composition: its δ values are higher than −200‰; that the biogenic gas under the condition of continental facies also was generated by the same way, but its hydrogen isotopic composition is lighter than that of biogenetic gas generated under typical marine facies condition: −250‰<δ<−200‰, the δ values may be related to the salinity of the water medium in ancient lakes. From the relevant data of the Qaidam Basin, it can be seen that the hydrogen isotopic composition of biogenic methane has the same variation trend with increasing salinity of water medium. There are biogenic gas reservoirs formed in transitional regions under the condition of continental facies. These gas reservoirs resulted from both CO2-reduction and acetic fermentation, the formation of which may be related to the non-variant salinity of ancient water medium and the relatively high geothermal gradient, as is the case encountered in the Baoshan Basin. The biogenic gas generating in these regions has light hydrogen isotopic composition: δ<−250‰, and relatively heavy carbon isotopic composition. There is a fairly strong negative correlation between the carbon isotopic composition and the hydrogen isotopic composition. The generation mechanism and pathway of carbon, and the hydrogen isotopic composition of biogenic gas may be used to ascertain whether biogenic gas samples from the natural world are of industrial utilization value. In general, the biogenic gas formed by way of acetic fermentation is not propitious to the formation of gas reservoirs.  相似文献   

2.
The Rushan gold deposit, explored in recent years in the Jiaodong area, Shandong Province, is a quartz vein-type gold deposit hosted in granite. The temperature of its major mineralization episode is between 220°C and 280°C. The salinity of the ore-forming fluid is 5 % to 9% NaCl equivalent, with H2O and CO2 as the dominant gas constituents. The fluid is rich in Na+, Ca2+ and Cl, but relatively impoverished in K+ and F, characterized by either Ca2+ > Na+ > K+ (in three samples) or Na+ > Ca2+ > K+ (in six samples). Hydrogen and oxygen isotopes in the ore-forming fluid are highly variable with δ18 ranging between − 7.70‰ and 5. 97‰ and between − 128‰ and − 71‰. The possibility of lamprophyre serving as the source of gold can be excluded in view of its low gold content on the order of 2.5 × 10−9. Rb-Sr isochron ages of the deposit and the host Kunyushan granite are ( 104.8 ± 1.5) Ma and 134.6 Ma respectively with the respective initial Sr ratios of 0. 71307 and 0.7096. It is considered that the emplacement of the lamprophyre under a tensile environment had provided sufficient heat energy to facilitate deep circulation of meteoric water by which ore metals were extracted from the Kunyushan granite through long-term water-rock reaction. This project was financially supported by the National Natural Science Foundation of China.  相似文献   

3.
Most altered clay minerals in uranium ore deposits in granites in the selected provinces of South China haveδ 18O m values ranging from 6.22 to 7.24,δDm from −60 to −70,δ 18O from +3.05 to −3.07, and from −20.2 to −37.5‰. Relative enrichment of32S in the uranium ore deposits and greater variations in Pb isotopic composition of galenas from them show that uranium ores in the granites were formed in such a way that uranium in shallow-source granites had been mobilized by heated meteoric waters and then migrated to local favourable locations along great faults to form uranium ore deposits. Zhang Shaoli, Yang Wenjin, Tang Chunjing and Xu Wenxin did part of this work.  相似文献   

4.
Natural gas pools with the high contents of CO2 were discovered during exploring the middle fault zone of the Hailar-Tamtsag Basin. So far this kind of gas reservoir with CO2 with characteristics of carbon isotope is spe-cial. The stable carbon isotope of CO2 in the study area is relatively light with δ13 CCO2 values ranging from -13.1‰ to -8.2‰. The 40Ar/36Ar values of associated argon gas range from 916 to 996, with R/Ra of 1.20-1.26. Based on comprehensive analysis, it is believed that the CO2 gas in this study area is of crust mantle source.  相似文献   

5.
Based on the oxygen isotopic compositions of 133 wolframite samples and 110 quartz samples collected from 30 tungsten ore deposits in south China, in conjunction withδD values and other data, these deposits can be divided into four types.
(1)  Reequilibrated magmatic water-hydrothermal tungsten ore deposits. Theδ 18O values of wolframite and quartz samples from this type of tungsten ore deposits are about +5–+12‰, respectively. The calculatedδ 18O values of ore fluids in equilibrium with quartz are about +6.5‰, and theδ values of fluid inclusions in quartz range from −40 to −70‰
(2)  Meteoric water-hydrothermal tungsten ore deposits. Theδ 18O values of wolframite in this type of tungsten deposits are around −1‰
(3)  Stratiform tungsten ore deposits. In these deposits, theδ 18O values of quartz and wolframite are about +17 and +3‰, respectively. It is considered that these stratiform tungsten ore deposits are genetically related to submarine hot-spring activities.
(4)  Complex mixed-hydrothermal tungsten ore deposits. These tungsten ore deposits are characterized by multi-staged mineralization. Theδ 18O values of early wolframite are around +5‰, but of later wolframite are lower than +4‰, indicating that the early wolframite was precipitated from reequilibrated magmatic water-hydrothermal solutions and the late one from the mixture of hydrothermal solutions with meteoric waters or mainly from meteoric waters.
Based on theδ 18O values of the coexisting quartz and wolframite and temperature data, two calibration equilibrium curves have been constructed, and the corresponding equations have been obtained:
  相似文献   

6.
The Serrinha gold deposit of the Gurupi Belt, northern Brazil, belongs to the class of orogenic gold deposits. The deposit is hosted in highly strained graphitic schist belonging to a Paleoproterozoic (∼2,160 Ma) metavolcano-sedimentary sequence. The ore-zones are up to 11 m thick, parallel to the regional NW–SE schistosity, and characterized by quartz-carbonate-sulfide veinlets and minor disseminations. Textural and structural data indicate that mineralization was syn- to late-tectonic and postmetamorphic. Fluid inclusion studies identified early CO2 (CH4-N2) and CO2 (CH4-N2)-H2O-NaCl inclusions that show highly variable phase ratios, CO2 homogenization, and total homogenization temperatures both to liquid and vapor, interpreted as the product of fluid immiscibility under fluctuating pressure conditions, more or less associated with postentrapment modifications. The ore-bearing fluid typically has 18–33mol% of CO2, up to 4mol% of N2, and less than 2mol% of CH4 and displays moderate to high densities with salinity around 4.5wt% NaCl equiv. Mineralization occurred around 310 to 335°C and 1.3 to 3.0 kbar, based on fluid inclusion homogenization temperatures and oxygen isotope thermometry with estimated oxygen fugacity indicating relatively reduced conditions. Stable isotope data on quartz, carbonate, and fluid inclusions suggest that veins formed from fluids with δ18OH2O and δDH2O (310–335°C) values of +6.2 to +8.4‰ and −19 to −80‰, respectively, which might be metamorphic and/or magmatic and/or mantle-derived. The carbon isotope composition (δ13C) varies from −14.2 to −15.7‰ in carbonates; it is −17.6‰ in fluid inclusion CO2 and −23.6‰ in graphite from the host rock. The δ34S values of pyrite are −2.6 to −7.9‰. The strongly to moderately negative carbon isotope composition of the carbonates and inclusion fluid CO2 reflects variable contribution of organic carbon to an originally heavier fluid (magmatic, metamorphic, or mantle-derived) at the site of deposition and sulfur isotopes indicate some oxidation of the originally reduced fluid. The deposition of gold is interpreted to have occurred mainly in response to phase separation and fluid-rock interactions such as CO2 removal and desulfidation reactions that provoked variations in the fluid pH and redox conditions.  相似文献   

7.
The Hongshan copper deposit is a typical cryptoexplosive breccia-type deposit, which occurs in a metamorphic rock series of the Mesoproterozoic Taoxiyuan Formation. Orebodies are distributed inside and outside porphyry-cryptoexplosive breccia pipes. The isotope geochemistry of the deposit is consistent with the origin of porphyry breccia: the δ18OH2O values ranging from 1.2‰ to 6.1‰ and the δ34S values varying from 0 to 2.5‰. 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios of pyrite, which coexists with ore minerals, indicate it was derived from the orogenic belt. Thermodynamic analysis indicates that the main metals were deposited largely as a result of the decreasing of proton concentrations associated with H2S and CO2 exsolution during explosion and temperature dropping. Based on K-Ar dating of quartz coexisting with ore minerals, the age of mineralization was estimated to be 97.1–98.8 Ma, which suggests that mineralization occurred between the Early and Late Cretaceous. According to the relevant information obtained, a diagenetic and metallogenic pattern in the area has been presented in this paper.  相似文献   

8.
The Qixia gold deposit is one of the important quartz vein-type deposits hosted in metamorphic rocks in the east of Shandong, China. Compositionally the wolframite which is associated with gold mineralization in the deposit is rich in iron, but poor in manganese, showing that this mineral crystallized from hydrothermal solution at low temperature. The temperatures at the main metallogenic stage of the Qixia gold deposit are within the range of 160–270°C. The gaseous phases in fluid inclusions are dominated by H2O and CO2, while Na+, Ca2+ and Cl are the major species in the fluid phase with K+ and F present in relatively small amounts. The salinities of fluids are 4.2 wt% –8.0 wt% NaCl equiv. Meanwhile, the fluid is characterized by either Ca2+ < Na+ < K+ (in five samples) or Na+ < Ca2+ < K+ (in two samples), quite similar to the composition of ore-forming fluid derived from meteoric water. Primary data on the hydrogen and oxygen isotopic compositions of the ore-forming fluid fall within a wide range: = − 56‱ − 95‱. and = − 3. 6‱ − 4. 5‱ relative to SMOW. These isotopic values fully reflect the distribution features of meteoric water which has exchanged with the metamorphic rocks of the Jiaodong Group at different temperatures and W/ R ratios, and the metallogenic process is characterized by low W/R ratios. The Rb-Sr isochron age of the Qixia gold deposit is 125.8 ± 1.7 Ma, with (87Sr/86Sr)i being 0.7168, and the time interval between the gold deposit and its country rocks (granite or metamoprhic rocks) is very large. The formation of the Qiaxia gold deposit is directly related to the evolution of geological history in eastern Shandong, and a genetic model in which the deep convective circulating meteoric water reacts with the country rocks can be used to explain the metallogenic mechanism of the deposit. This project was financially supported by the National Natural Science Foundation of China (No. 49000020).  相似文献   

9.
Two kinds of mylonite series rocks, felsic and mafic, have been recognized in the NW-striking shear zone of the Jiapigou gold belt. During ductile deformation, a large amount of fluid interacted intensively with the mylonite series rocks: plagioclases were sericitized and theAn values declined rapidly, finally all of them were transformed to albites; dark minerals were gradually replaced by chlorites (mostly ripidolite). Meanwhile, large-scale and extensive carbonation also took place, and the carbonatization minerals varied from calcite to dolomite and ankerite with the development of deformation. The δ13C values of the carbonates are −3.0‰ – −5.6‰ suggesting a deep source of carbon. The ductile deformation is nearly an iso-volume one (f v≈1). With the enhancement of shear deformation, SiO2 in the two mylonite series rocks was depleted, while volatile components suchs as CO2 and H2O, and some ore-forming elements such as Au and S were obviously enriched. But it is noted that the enrichment of Au in both the mylonite series rocks did not reach the paygrade of gold. The released SiO2 from water-rock interactions occurred in the form of colloids and absorbed gold in the fluid. When brittle structures were formed locally in the ductile shear zone, the ore-forming fluids migrated to the structures along microfractures, and preciptated auriferous quartz because of reduction of pressure and temperature. Fluid inclusion study shows that the temperature and pressure of the ore-forming fluids are 245–292°C and 95.4–131.7 MPa respectively; the salinity is 12.88–16.33wt% NaCl; the fluid-phase is rich in Ca2+, K+, Na+, Mg2+, F and Cl, while the gaseous phases are rich in CO2 and CH4. The δD and δ18O, values of the ore-forming fluid are −84.48‰ – −91.73‰ and −0.247‰ – +2.715‰ respectively, suggesting that the fluid is composed predominantly of meteoric water. This project is financially supported by the National Natural Science Foundation of China (No. 9488010).  相似文献   

10.
Quartz–carbonate–chlorite veins were studied in borehole samples of the RWTH-1 well in Aachen. Veins formed in Devonian rocks in the footwall of the Aachen thrust during Variscan deformation and associated fluid flow. Primary fluid inclusions indicate subsolvus unmixing of a homogenous H2O–CO2–CH4–(N2)–Na–(K)–Cl fluid into a H2O–Na–(K)–Cl solution and a vapour-rich CO2–(H2O, CH4, N2) fluid. The aqueous end-member composition resembles that of metamorphic fluids of the Variscan front zone with salinities ranging from 4 to 7% NaCl equiv. and maximum homogenisation temperatures of close to 400°C. Pressure estimates indicate a burial depth between 4,500 and 8,000 m at geothermal gradients between 50 and 75°C/26 MPa, but pressure decrease to sublithostatic conditions is also indicated, probably as a consequence of fracture opening during episodic seismic activity. A second fluid system, mainly preserved in pseudo-secondary and secondary fluid inclusions, is characterised by fluid temperatures between 200 and 250°C and salinities of <5% NaCl equiv. Bulk stable isotope analyses of fluids released from vein quartz, calcite, and dolomite by decrepitation yielded δDH2O values from −89 to −113 ‰, δ13CCH4 from −26.9 to −28.9‰ (VPDB) and δ13CCO2 from −12.8 to −23.3‰ (VPDB). The low δD and δ13C range of the fluids is considered to be due to interaction with cracked hydrocarbons. The second fluid influx caused partial isotope exchange and disequilibrium. It is envisaged that an initial short lived flux of hot metamorphic fluids expelled from the epizonal metamorphic domains of the Stavelot–Venn massif. The metamorphic fluid was focused along major thrust faults of the Variscan front zone such as the Aachen thrust. A second fluid influx was introduced from formation waters in the footwall of the Aachen thrust as a consequence of progressive deformation. Mixing of the cooler and lower salinity formation water with the hot metamorphic fluid during episodic fluid trapping resulted in an evolving range of physicochemical fluid inclusion characteristics.  相似文献   

11.
At Sams Creek, a gold-bearing, peralkaline granite porphyry dyke, which has a 7 km strike length and is up to 60 m in thickness, intrudes camptonite lamprophyre dykes and lower greenschist facies metapelites and quartzites of the Late Ordovician Wangapeka formation. The lamprophyre dykes occur as thin (< 3 m) slivers along the contacts of the granite dyke. δ18Omagma values (+5 to +8‰, VSMOW) of the A-type granite suggest derivation from a primitive source, with an insignificant mature crustal contribution. Hydrothermal gold–sulphide mineralisation is confined to the granite and adjacent lamprophyre; metapelite country rocks have only weak hydrothermal alteration. Three stages of hydrothermal alteration have been identified in the granite: Stage I alteration (high fO2) consisting of magnetite–siderite±biotite; Stage II consisting of thin quartz–pyrite veinlets; and Stage III (low fO2) consisting of sulphides, quartz and siderite veins, and pervasive silicification. The lamprophyre is altered to an ankerite–chlorite–sericite assemblage. Stage III sulphide veins are composed of arsenopyrite + pyrite ± galena ± sphalerite ± gold ± chalcopyrite ± pyrrhotite ± rutile ± graphite. Three phases of deformation have affected the area, and the mineralised veins and the granite and lamprophyre dykes have been deformed by two phases of folding, the youngest of which is Early Cretaceous. Locally preserved early-formed fluid inclusions are either carbonic, showing two- or three-phases at room temperature (liquid CO2-CH4 + liquid H2O ± CO2 vapour) or two-phase liquid-rich aqueous inclusions, some of which contain clathrates. Salinities of the aqueous inclusions are in the range of 1.4 to 7.6 wt% NaCl equiv. Final homogenisation temperatures (Th) of the carbonic inclusions indicate minimum trapping temperatures of 320 to 355°C, which are not too different from vein formation temperatures of 340–380°C estimated from quartz–albite stable isotope thermometry. δ18O values of Stage II and III vein quartz range from +12 and +17‰ and have a bimodal distribution (+14.5 and +16‰) with Stage II vein quartz accounting for the lower values. Siderite in Stage III veins have δ18O (+12 to +16‰) and δ13C values (−5‰, relative to VPDB), unlike those from Wangapeka Formation metasediments (δ13Cbulk carbon values of −24 to −19‰) and underlying Arthur Marble marine carbonates (δ18O = +25‰ and δ13C = 0‰). Calculated δ18Owater (+8 to +11‰, at 340°C) and (−5‰) values from vein quartz and siderite are consistent with a magmatic hydrothermal source, but a metamorphic hydrothermal origin cannot be excluded. δ34S values of sulphides range from +5 to +10‰ (relative to CDT) and also have a bimodal distribution (modes at +6 and +9‰, correlated with Stage II and Stage III mineralisation, respectively). The δ34S values of pyrite from the Arthur Marble marine carbonates (range from +3 to +13‰) and Wangapeka Formation (range from −4 to +9.5‰) indicate that they are potential sources of sulphur for sulphides in the Sams Creek veins. Another possible source of the sulphur is the lithospheric mantle which has positive values up to +14‰. Ages of the granite, lamprophyre, alteration/mineralisation, and deformation in the region are not well constrained, which makes it difficult to identify sources of mineralisation with respect to timing. Our mineralogical and stable isotope data does not exclude a metamorphic source, but we consider that the source of the mineralisation can best be explained by a magmatic hydrothermal source. Assuming that the hydrothermal fluids were sourced from crystallisation of the Sams Creek granite or an underlying magma chamber, then the Sams Creek gold deposit appears to be a hybrid between those described as reduced granite Au–Bi deposits and alkaline intrusive-hosted Au–Mo–Cu deposits.  相似文献   

12.
The Tono sandstone-type uranium mine area, middle Honsyu, Japan is composed of Miocene lacustrine sedimentary rocks in the lower part (18–22 Ma) and marine facies in the upper part (15–16 Ma). Calcite and pyrite occur as dominant diagenetic alteration products in these Neogene sedimentary rocks. The characteristics of calcite and pyrite differ significantly between lacustrine and marine facies. Abundant pyrite, calcite, organic matter, and small amounts of marcasite or pyrrhotite occur in the lacustrine facies, whereas small amounts of calcite and framboidal pyrite, organic matter and no marcasite or pyrrhotite are found within the marine units. The δ13C values of calcite in the lacustrine deposits are low (−19 to −6‰ PDB) but those in marine formation are high (−11 to +3‰). This implies that the contribution of marine carbonate is larger in upper marine sedimentary rocks, and carbon in calcite in the lower lacustrine formation was derived both from oxidation of organic matter and from dissolved marine inorganic carbon. The δ34S values of framboidal pyrite in the upper marine formation are low (−14 to −8‰ CDT), indicating a small extent of bacterial seawater sulfate reduction, whereas those of euhedral-subhedral pyrite in the lower lignite-bearing arkose sandstone are high (+10 to +43‰), implying a large extent of closed-system bacterial seawater sulfate reduction. The δ34S and δ13C data which deviate from a negative correlation line toward higher δ13C values suggest methanogenic CO2 production. During diagenesis of the lacustrine unit, large amounts of euhedral-subhedral pyrite were formed, facilitated by extensive bacterial reduction of seawater sulfate with concomitant oxidation of organic matter, and by hydrolysis reactions of organic matter, producing CH4 and CO2. Uranium minerals (coffinite and uraninite) were also formed at this stage by the reduction of U6+ to U4+. The conditions of diagenetic alteration within the lacustrine deposits and uranium mineralization is characterized by low Eh in which nearly equal concentrations of CH4 and HCO3 existed and reduced sulfur species (H2S, HS) are predominant among aqueous sulfur species, whereas diagenetic alteration of the marine formations was characterized by a predominance of SO4 2− among dissolved sulfur species. Modern groundwater in the lacustrine formation has a low Eh value (−335 mV). Estimated and measured low Eh values of modern and ancient interstitial waters in lacustrine environments indicate that a reducing environment in which U4+ is stable has been maintained since precipitation of uranium minerals. Received: 9 February 1996 / Accepted: 11 April 1997  相似文献   

13.
The equilibrium composition was modeled for the water-carbonaceous chondrite matter system open to CO2 and CH4. It was shown that at 25°C, total pressure of 1 bar, and definite proportions between partial pressures of CO2 (10−5–10−8 bars) and CH4 (10−4–10−8 bar), the aqueous phase is characterized by a K/Na ratio of 4–12, which corresponds to the ratios of these elements in the cellular liquid of organisms. Aqueous phase has pH = 8−9, Eh = −450 ± 50 mV, and ammonia nitrogen, and K, Na, and Mg concentrations close to those in the cellular liquid.  相似文献   

14.
The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions aboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO2 were examined throughout the whole sea area at more than 200 sites. The δ13C varies from −22 and −24‰ where Atlantic waters enter the Kara Sea and in the North-eastern part of the water area to −27‰ in the Yenisei and Ob estuaries. The value of δ13C of the plankton is only weakly correlated with the δ13C of the organic matter from the sediments and is lower by as much as 3–4‰. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the riverwaters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the off-shore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from −29 to −35‰ in the riverine part, from −28 to −27‰ in the estuaries, and from −27.0 to −25% in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO2 concentrations, and long-distance CO2 supply to the sea with riverwaters. The data obtained on the isotopic composition of CO2 in the surface waters of the Kara Sea were used to map the distribution of δ13CCO 2. The complex of hydrocarbon gases extracted from the waters included methane, C2–C5, and unsaturated C2=–C4= hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3–5 μl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with δ13C from −105 to −90‰ first occurs in the sediments at depths of 40–200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the δ13C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (δ13C from −25 to −60‰) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea. Original Russian Text ? E.M. Galimov, L.A. Kodina, O.V. Stepanets, G.S. Korobeinik, 2006, published in Geokhimiya, 2006, No. 11, pp. 1139–1191.  相似文献   

15.
The effect of Co2 and CH4 degassing from the mantle on the carbon isotopic composition of diamond has been quantitatively modeled in terms of the principles of Rayleigh distillation.Assuming the δ^13 C value of -5‰ for the mantle,the outgassing of CO2 can result in the large negative δ^13 C values of diamond,whereas the outgassing of CH4 can drive the δ^13C values of diamond in the positive direction.The theoretical expectations can be used to explain the full range of δ^13 C values from-34.4‰5 to 5‰ observed for natural diamonds.It is possible that diamond formation was triggered by the degassing of Co2 and/or CH4 from the mantle and the associated fractional crystallization of carbonate-bearing melt.  相似文献   

16.
The Pering deposit is the prime example of Zn–Pb mineralisation hosted by stromatolitic dolostones of the Neoarchean to Paleoproterozoic Transvaal Supergroup. The hydrothermal deposit centers on subvertical breccia pipes that crosscut stromatolitic dolostones of the Reivilo Formation, the lowermost portion of the Campbellrand Subgroup. Four distinct stages of hydrothermal mineralisation are recognised. Early pyritic rock matrix brecciation is followed by collomorphous sphalerite mineralisation with replacive character, which, in turn, is succeeded by coarse grained open-space-infill of sphalerite, galena, sparry dolomite, and quartz. Together, the latter two stages account for ore-grade Zn–Pb mineralisation. The fourth and final paragenetic stage is characterised by open-space-infill by coarse sparry calcite. The present study documents the results of a detailed geochemical study of the Pering deposit, including fluid inclusion microthermometry, fluid chemistry and stable isotope geochemistry of sulphides (δ34S) and carbonate gangue (δ13C and δ18O). Microthermometric fluid inclusion studies carried out on a series of coarsely grained crystalline quartz and sphalerite samples of the latter, open-space-infill stage of the main mineralisation event reveal the presence of three major fluid types: (1) a halite–saturated aqueous fluid H2O–NaCl–CaCl2 (>33 wt% NaCl equivalent) brine, (2) low-salinity meteoric fluid (<7 wt% NaCl) and (3) a carbonic CH4–CO2–HS fluid that may be derived from organic material present within the host dolostone. Mixing of these fluids have given rise to variable mixtures (H2O–CaCl2–NaCl ±(CH4–CO2–HS), 2 to 25 wt% NaCl+CaCl2). Heterogeneous trapping of the aqueous and carbonic fluids occurred under conditions of immiscibility. Fluid temperature and pressure conditions during mineralisation are determined to be 200–210°C and 1.1–1.4 kbar, corresponding to a depth of mineralisation of 4.1–5.2 km. Chemical analyses of the brine inclusions show them to be dominated by Na and Cl with lesser amounts of Ca, K and SO4. Fluid ratios of Cl/Br indicate that they originated as halite saturated seawater brines that mixed with lower salinity fluids. Analyses of individual brine inclusions document high concentrations of Zn and Pb (∼1,500 and ∼200 ppm respectively) and identify the brine as responsible for the introduction of base metals. Stable isotope data were acquired for host rock and hydrothermal carbonates (dolomite, calcite) and sulphides (pyrite, sphalerite, galena and chalcopyrite). The ore-forming sulphides show a trend to 34S enrichment from pyrite nodules in the pyritic rock matrix breccia (δ34S = −9.9 to +3.7‰) to paragenetically late chalcopyrite of the main mineralisation event (δ34S = +30.0‰). The observed trend is attributed to Rayleigh fractionation during the complete reduction of sulphate in a restricted reservoir by thermochemical sulphate reduction, and incremental precipitation of the generated sulphide. The initial sulphate reservoir is expected to have had an isotopic signature around 0‰, and may well represent magmatic sulphur, oxidised and leached by the metal-bearing brine. The δ18O values of successive generations of dolomite, from host dolostone to paragenetically late saddle dolomite follow a consistent trend that yields convincing evidence for extensive water rock interaction at variable fluid–rock ratios. Values of δ13C remain virtually unchanged and similar to the host dolostone, thus suggesting insignificant influx of CO2 during the early and main stages of mineralisation. On the other hand, δ13C and δ18O of post-ore calcite define two distinct clusters that may be attributed to changes in the relative abundance in CH4 and CO2 during waning stages of hydrothermal fluid flow.  相似文献   

17.
CO2 inclusions with density up to 1,197 kg m−3 occur in quartz–stibnite veins hosted in the low-grade Palaeozoic basement of the Gemericum tectonic unit in the Western Carpathians. Raman microanalysis corroborated CO2 as dominant gas species accompanied by small amounts of nitrogen (<7.3 mol%) and methane (<2.5 mol%). The superdense CO2 phase exsolved from an aqueous bulk fluid at temperatures of 183–237°C and pressures between 1.6 and 3.5 kbar, possibly up to 4.5 kbar. Low thermal gradients (∼12–13°C km−1) and the CO2–CH4–N2 fluid composition rule out a genetic link with the subjacent Permian granites and indicate an external, either metamorphogenic (oxidation of siderite, dedolomitization) or lower crustal/mantle, source of the ore-forming fluids.According to microprobe U–Pb–Th dating of monazite, the stibnite-bearing veins formed during early Cretaceous thrusting of the Gemeric basement over the adjacent Veporic unit. The 15- to 18-km depth of burial estimated from the fluid inclusion trapping PT parameters indicates a 8- to 11-km-thick Upper Palaeozoic–Jurassic accretionary complex overlying the Gemeric basement and its Permo-Triassic autochthonous cover.  相似文献   

18.
High pressure experimental studies of the melting of lherzolitic upper mantle in the absence of carbon and hydrogen have shown that the lherzolite solidus has a positive dP/dT and that the percentage melting increases quite rapidly above the solidus. In contrast, the presence of carbon and hydrogen in the mantle results in a region of ‘incipient’ melting at temperatures below the C,H-free solidus. In this region the presence or absence of melt and the composition of the melt are dependent on the amount and nature of volatiles, particularly the CO2, H2O, and CH4 contents of the potential C-H-O fluid. Under conditions of low (IW to IW + 1 log unit atP ∼ 20–35kb), fluids such as CH4+H2O and CH4+H2 inhibit melting, having a low solubility in silicate melts. Under these conditions, carbon and hydrogen are mobile elements in the upper mantle. At slightly higher oxygen fugacity (IW+2 log units,P∼20–35 kb) fluids in equilibrium with graphite or diamond in peridotite C-H-O are extremely water-rich. Carbon is thus not mobile in the mantle in this range and the melting and phase relations for the upper mantle lherzolite approximate closely to the peridotite-H2O system. Pargasitic amphibole is stable to solidus temperatures in fertile lherzolite compositions and causes a distinctive peridotite solidus, the ‘dehydration solidus’, with a marked change in slope (a ‘back bend’) at 29–30kb due to instability of pargasite at high pressure. Intersections of geothermal gradients with the peridotite-H2O solidi define the boundary between lithosphere (subsolidus) and asthenosphere (incipient melt region). This boundary is thus sensitive to changes in [affecting CH4:H2O:CO2 ratios] and to the amount of H2O and carbon (CO2, CH4) present. At higher conditions (IW + 3 log units), CO2-rich fluids occur at low pressures but there is a marked depression of the solidus at 20–21 kb due to intersection with the carbonation reaction, producing the low temperature solidus for dolomite amphibole lherzolite (T∼925°C, 21 to >31kb). Melting of dolomite (or magnesite) amphibole lherzolite yields primary sodic dolomitic carbonatite melt with low H2O content, in equilibrium with amphibole garnet lherzolite. The complexity of melting in peridotite-C-H-O provides possible explanations for a wide range of observations on lithosphere/asthenosphere relations, on mantle melt and fluid compositions, and on processes of mantle metasomatism and magma genesis in the upper mantle.  相似文献   

19.
The effects of long-term exposure to elevated atmospheric CO2 (ambient + 340 ppmv) on carbon cycling were investigated for two plant communities in a Chesapeake Bay brackish marsh, one dominated by the C3 sedgeSchoenplectus americanus and the other by the C4 grassSpartina patens. Elevated CO2 resulted in a significant increase in porewater concentrations of DIC at 30 cm depth (p < 0.1). The CO2 treatment also yielded increases in DOC (15 to 27%) and dissolved CH4 (12–18%) in the C3 marsh (means for several depths over the period of June 1998 and June 1999), but not at a significant level. Elevated CO2 increased mean ecosystem emissions of CO2 (34–393 g C m−2 yr−1) and CH4 (0.21–0.40 g C m−2 yr−1) in the C3 community, but the effects were only significant on certain dates. For example, CO2 enrichment increased C export to the atmosphere in the C3 community during one of two winter seasons measured (p = 0.09). In the C4 community, gross photosynthesis responded relatively weakly to elevated CO2 (18% increase, p > 0.1), and the concomitant effects on dissolved carbon concentrations, respiration, and CH4 emissions were small or absent. We concluded that elevated CO2 has the potential to increase dissolved inorganic carbon export to estuaries.  相似文献   

20.
Scheelite mineralization accompanied by muscovite and albite, and traces of Mo-stolzite and stolzite occurs in epigenetic quartz vein systems hosted by two-mica gneissic schists, and locally amphibolites, of the Paleozoic or older Vertiskos Formation, in the Metaggitsi area, central Chalkidiki, N Greece. Three types of primary fluid inclusions coexist in quartz and scheelite: type 1, the most abundant, consists of mixed H2O-CO2 inclusions with highly variable (20–90 vol.%) CO2 contents and salinities between 0.2 and 8.3 equivalent weight % NaCl. Densities range from 0.79 to 0.99 g/cc; type 1 inclusions contain also traces (<2 mol%) of CH4. Type 2 inclusions are nearly 100 vol.% liquid CO2, with traces of CH4, and densities between 0.75 and 0.88 g/cc. Type 3 inclusions, the least abundant, contain an aqueous liquid of low salinity (0.5 to 8.5 equivalent weight% NaCl) with 10–30 vol.% H2O gas infrequently containing also small amounts of CO2 (<2 mol%); densities range from 0.72 to 0.99 g/cc. The wide range of coexisting fluid inclusion compositions is interpreted as a result of fluid immiscibility during entrapment. Immiscibility is documented by the partitioning of CH4 and CO2, into gas-rich (CO2-rich) type 1 inclusions, and the conformity of end-member compositions trapped in type 1 inclusions to chemical equilibrium fractionation at the minimum measured homogenization temperatures, and calculated homogenization pressures. Minimum measured homogenization temperatures of aqueous and gas-rich type 1 inclusions of 220°–250 °C, either to the H2O, or to the CO2 phase, is considered the best estimate of temperature of formation of the veins, and temperature of scheelite deposition. Corresponding fluid pressures were between 1.2 and 2.6 kbar. Oxygen fugacities during mineralization varied from 10−35 to 10−31 bar and were slightly above the synthetic Ni-NiO buffer values. The fluid inclusion data combined with δ18O water values of 3 to 6 per mil (SMOW) and δ13C CO2− fluid of −1.2 to +4.3 per mil (PDB), together with geologic data, indicate generation of mineralizing fluids primarily by late- to post-metamorphic devolatilization reactions. Received: 8 April 1997 / Accepted: 8 July 1997  相似文献   

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