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1.
Organic sulfur compounds are ubiquitous in natural oil and gas fields and moderate-low temperature sulfide ore deposits. Previous studies have shown that organic sulfur compounds are important in enhancing the rates of thermochemical sulfate reduction (TSR) reactions, but the details of these reaction mechanisms remain unclear. In order to assess the extent of sulfate reduction in the presence of labile sulfur species at temperature conditions near to those where TSR occurs in nature, we conducted a series of experiments using the fused silica capillary capsule (FCSS) method. The tested systems containing labile sulfur species are MgSO4 + 1-pentanethiol (C5H11SH) + 1-octene (C8H16), MgSO4 + 1-octene (C8H16), MgSO4 + 1-pentanethiol (C5H11SH), 1-pentanethiol (C5H11SH)+H2O, and MgSO4 + 1-pentanethiol (C5H11SH) + ZnBr2 systems. Our results show that: (1) intermediate oxidized carbon species (ethanol and acetic acid) are formed during TSR simulation experiments when 1-pentanethiol is present; (2) in the presence of ZnBr2, 1-pentanethiol can be oxidized by sulfate to CO2 at 200 °C, which is within the temperature range observed in natural TSR; and (3) the precipitation of sulfide minerals may significantly promote the rate of TSR, indicating that the rates of in situ TSR reactions in ore deposits could be much faster than previously thought. This may be important for understanding the possibility of in situ TSR as a mechanism for the precipitation of metal sulfides in some ore deposits. These findings provide important experimental evidence for understanding the role of organic sulfur compounds in TSR reactions and the pathway of TSR reactions initiated by organic sulfur compounds under natural conditions.  相似文献   

2.
The origin of the combustible gases in groundwater from glacial-outwash and fractured-bedrock aquifers was investigated in northern Tioga County, Pennsylvania. Thermogenic methane (CH4) and ethane (C2H6) and microbial CH4 were found. Microbial CH4 is from natural in situ processes in the shale bedrock and occurs chiefly in the bedrock aquifer. The δ13C values of CH4 and C2H6 for the majority of thermogenic gases from water wells either matched or were between values for the samples of non-native storage-field gas from injection wells and the samples of gas from storage-field observation wells. Traces of C2H6 with microbial CH4 and a range of C and H isotopic compositions of CH4 indicate gases of different origins are mixing in sub-surface pathways; gas mixtures are present in groundwater. Pathways for gas migration and a specific source of the gases were not identified. Processes responsible for the presence of microbial gases in groundwater could be elucidated with further geochemical study.  相似文献   

3.
The origin of the combustible gases in groundwater from glacial-outwash and fractured-bedrock aquifers was investigated in northern Tioga County, Pennsylvania. Thermogenic methane (CH4) and ethane (C2H6) and microbial CH4 were found. Microbial CH4 is from natural in situ processes in the shale bedrock and occurs chiefly in the bedrock aquifer. The δ13C values of CH4 and C2H6 for the majority of thermogenic gases from water wells either matched or were between values for the samples of non-native storage-field gas from injection wells and the samples of gas from storage-field observation wells. Traces of C2H6 with microbial CH4 and a range of C and H isotopic compositions of CH4 indicate gases of different origins are mixing in sub-surface pathways; gas mixtures are present in groundwater. Pathways for gas migration and a specific source of the gases were not identified. Processes responsible for the presence of microbial gases in groundwater could be elucidated with further geochemical study.  相似文献   

4.
《Applied Geochemistry》2001,16(7-8):895-910
Coalbed gases in the Lower Silesian Coal Basin (LSCB) of Poland are highly variable in both their molecular and stable isotope compositions. Geochemical indices and stable isotope ratios vary within the following ranges: hydrocarbon (CHC) index CHC=CH4/(C2H6+ C3H8) from 1.1 to 5825, wet gas (C2+) index C2+=(C2H6+ C3H8+ C4H10+ C5H12) / (CH4+ C2H6+ C3H8+ C4H10+ C5H12) 100 (%) from 0.0 to 48.3%, CO2–CH4 (CDMI) index CDMI=CO2/(CO2+ CH4) 100 (%) from 0.1 to 99.9%, δ13C(CH4) from −66.1 to −24.6‰, δD(CH4) from −266 to −117‰, δ13C(C2H6) from −27.8 to −22.8‰, and δ13C(CO2) from −26.6 to 16.8‰. Isotopic studies reveal the presence of 3 genetic types of natural gases: thermogenic (CH4, higher gaseous hydrocarbons, and CO2), endogenic CO2, and microbial CH4 and CO2. Thermogenic gases resulted from coalification processes, which were probably completed by Late Carboniferous and Early Permian time. Endogenic CO2 migrated along the deep-seated faults from upper mantle and/or magma chambers. Minor volumes of microbial CH4 and CO2 occur at shallow depths close to the abandoned mine workings. “Late-stage” microbial processes have commenced in the Upper Cretaceous and are probably active at present. However, depth-related isotopic fractionation which has resulted from physical and physicochemical (e.g. diffusion and adsorption/desorption) processes during gas migration cannot be neglected. The strongest rock and gas outbursts occur only in those parts of coal deposits of the LSCB which are dominated by large amounts of endogenic CO2.  相似文献   

5.
Luna 16 and Luna 20 samples were analyzed for volatilizable species using vacuum pyrolysis to 1400°C. The major gaseous products evolved (ranging from 10–650 μg/g) were H2O, CO, CO2, N2 and CH4. Minor components (all < 10 μg/g) included NH3, HCN, NO, SO2, H2S, C2H2, C2H4, C2H6, C3H6 and higher hydrocarbons, benzene, toluene, and the polymeric contaminants Teflon® and silicone oil. The total carbon and nitrogen contents (μg/g) for these sieved samples (< 125 μm) were: Luna 16—C 418, N 134 and Luna 20—C 380, N 80.  相似文献   

6.
The single-crystal of humboldtine [Fe2+(C2O4) · 2H2O] was first synthesized and the crystal structure has been refined. Single-crystal X-ray diffraction data were collected using an imaging-plate diffractometer system and graphite-monochromatized MoKα radiation. The crystal structure of humboldtine was refined to an agreement index (R1) of 3.22% calculated for 595 unique observed reflections. The mineral crystallizes in the monoclinic system, space group C2/c, with unit cell dimensions of a = 12.011 (11), b = 5.557 (5), c = 9.920 (9) Å, β = 128.53 (3)?, V = 518.0 (8) Å3, and Z = 4. In this crystal structure, the alternation of oxalate anions [(C2O4)2?] and Fe2+ ions forms one-dimensional chain structure parallel to [010]; water molecules (H2O)0 create hydrogen bonds to link the chains, where (H2O)0 is essentially part of the crystal structure. The water molecules with the two lone electron pairs (LEPs) on their oxygen atom are tied obliquely to the chains, because the one lone electron pair is considered to participate in the chemical bonds with Fe2+ ions. Humboldtine including hydrogen bonds is isotypic with lindbergite [Mn2+(C2O4) · 2H2O]. The donor–acceptor separations of the hydrogen bonds in humboldtine are slightly shorter than those in lindbergite, which suggests that the hydrogen bonds in the former are stronger than those in the latter. The infrared and Raman spectra of single-crystals of humboldtine and lindbergite confirmed the differences in hydrogen-bond geometry. In addition, Fe2+–O stretching band of humboldtine was split and broadened in the observed Raman spectrum, owing to the Jahn–Teller effect of Fe2+ ion. These interpretations were also discussed in terms of bond-valence theory.  相似文献   

7.
Reconnaissance surface geochemical survey for adsorbed soil gas analysis conducted in Proterozoic Bhima and Kaladgi Basins, have revealed occurrence of anomalous concentrations of light gaseous hydrocarbons i.e. C1 to C4 (CH4, C2H6, C3H8, i-C4H10 and n-C4H10) in the near surface soils. The concentrations of C1 and ΣC2+(C2H6+C3H8+ i-C4H10+ n-C4H10) in Bhima and Kaladgi Basins are in the range of 1–2594 ppb and 1 to 57 ppb and 1–1142 ppb and 1–490 ppb, respectively. The carbon isotopic data of adsorbed soil gas methane in few selected samples are in the range of −29.9 to −39‰ (PDB). The evaluation of adsorbed soil gas data indicates that all the gas components are cogenetic and hydrocarbon ratios of C1/(C2+C3) < 10 and C3/C1*1000 between 60–500 and 20–60 suggest that the adsorbed gases are derived from oil and gas-condensate zones. The carbon isotopic values of methane further support thermogenic origin of these migrated gases. The concentration distribution of C1 and ΣC2+ in the study areas illustrate C1 and ΣC2+ anomalies near Katamadevarhalli, Andola and Talikota in Bhima Basin and near Kaladgi, Lokapur and north of Mudhol in Kaladgi Basin. The hydrocarbon anomalies near the surface coincide with the favourable subsurface structural features and correlate with existing geochemical and geophysical data in these basins suggesting seepage related anomalies.  相似文献   

8.
The chemical composition of the gases emitted from a hornito close to the active lava lake of Erta'Ale, Ethiopia, as derived from chemical analyses on 18 samples collected on 23 January 1974, was found to be (in mol-%): H2O: 79.4, CO2: 10.4, total S: 7.36, HCl: 0.42, H2: 1.49, N2: 0.18, Ar: 0.001, CO: 0.46, and COS: 0.009. Thermodynamic considerations, based on the equilibria CO2 + H2 ? CO + H2O and CO2 + 3H2 + SO2 ? COS + 3H2O show that the analytical values represent the equilibrium composition of a gas mixture at the measured temperature of around 1130°C under close to the surface pressure conditions. Comparison of the Erta'Ale gas emissions with those from other volcanoes suggests a close similarity in their chemical composition. This similarity is considered to be due to common processes governing the release of gaseous species from a magma.  相似文献   

9.
Based on the synthesis of hydrogeochemical materials on Sb occurrence in carbonate and thermal waters and thermodynamic simulations, genetic analysis was conducted of the transformations of probable Sb migration species (particularly oxygen-bearing and sulfide ones), and their transformations were calculated depending on the main parameters of hydrogeochemical systems (\(P_{CO_2 } \), T, R/W, Eh, and pH). The oxygen 2HSbO 2 0 + 3H2S = Sb2S3 + 4H2O (2SbO 2 ? + 3HS? + 5H+ = Sb2S3 + 4H2O) and sulfide HSb2S 4 ? + H+ = Sb2S3 cr + H2S (Sb2S 4 2? + 2H+ = Sb2S3cr + H2S) models for the genesis of hydrogenic Sb2S3(cr) were simulated. Information on occurrences of carbonate and thermal waters in various regions worldwide was generalized, and the reasons were identified for the geochemical separation of As and Sb in carbonate and thermal waters. The causes and conditions of an increase in Sb concentrations in thermal waters were revealed, and Sb migration species in carbonate and thermal waters were identified for various parameters of hydrogeochemical systems. Variations in Sb speciation were demonstrated for hydrogeochemical systems depending on their boundary conditions (\(P_{CO_2 } \), T, and R/W). Models were outlined responsible for the precipitation of Sb2S3(cr) from carbonate and thermal waters.  相似文献   

10.
Concentrations and isotopic compositions were determined for H2, N2 and C extracted by stepwise pyrolysis from powdered meteorites, from residues of meteorites partially dissolved with aqueous HF, and from residues of meteorites reacted with HF-HCl solutions. The meteorites treated were the carbonaceous chondrites, Orgueil, Murray, Murchison, Renazzo and Cold Bokkeveld. Data determined for whole rock samples are in approximate agreement with previously published data. Acidification of the meteorites removed the inorganic sources of H2, so that H2 in the HF-HCl acid residues came primarily from insoluble organic matter, which makes up 70–80% fraction of the total carbon in carbonaceous meteorites. The δD in the organic matter differs markedly from previously determined values in organic matter in meteorites. The δD values of organic matter from acid residues of C1 and C2 carbonaceous chondrites range from +650 to + 1150%. The acid residues of the Renazzo meteorite, whose total H2 has a δD of +930‰, gave a δD value of +2500‰. Oxidation of the HF-HCl residue with H2O2 solution removes the high δD and the low δ15N components. The δ13C values range between ?10 and ?21 and δ15N values range between +40 and ?11. The δ15N of Renazzo is unusual; its values range between +150 and ?190.There is good correlation between δD and the concentration of H2 in the acid residues, but no correlation exists between δD, δ13C and δ15N in them. A simple model is proposed to explain the high δD values, and the relationships between δD values and the concentration of H2. This model depends on the irradiation of gaseous molecules facilitating reaction between ionic molecules, and indicates that an increase in the rate of polymerization and accumulation of organic matter on grains would produce an increase in the deuterium concentration in organic matter.  相似文献   

11.
This study describes a new approach for characterizing high molecular weight compounds in Type I kerogen, involving both nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron mass spectrometry (FTICR-MS). Kerogen isolated from the Mahogany zone of the Green River Formation was examined directly using high resolution magic angle spinning (HRMAS) NMR to obtain liquid-like multidimensional spectra. It was then successively extracted with n-pentane, dichloromethane and pyridine. Pyridine extraction was also performed for comparison with the successive extractions. Using solid-state NMR, we show that the sum of the successive extracts and the single pyridine extract are quantitatively representative of the unextracted kerogen. This suggests that a non-invasive characterization of Green River kerogen can be obtained by examining the soluble extracts, all of which were subjected to ESI-FTICR-MS to identify a wide series of compounds. Series of polar CHO, CHOS and CHON compounds between C12 and C50+ were found. In all the extracts the two homologous series of acids (CnH2nO2 and CnH2n−2O4) dominated. Collision-induced dissociation was also employed to identify the different functional groups comprising the different series. The CHO series contained carboxylic acid and alkoxyl groups, whereas the CHOS and CHON series contained sulfoxide groups and nitrile-type compounds. The results also show that pyridine extraction can be used either for screening a large series of samples or for the specific study of CHO compounds. However for a detailed and complete study of the different homologous series we recommend using the successive extraction protocol.  相似文献   

12.
The barium deposits in Ankang and Xunyang counties,Shaanxi Province,China,occur in the northernmost part of the world-class barium metallogenic belt in south Qinling.The deposits are hosted by the Lower Silurian carbonaceous siliceous rocks,with a unique combination of barite and witherite.The homogenization temperatures of fluid inclusions in the barite are mainly concentrated between 135 and 155 ℃,whereas those from the witherite have two peaks of 165-175 ℃,and 215-225℃,respectively.Laser Raman analysis of fluid inclusions indicates that the vapor phase of fluid inclusions in barite is dominated by H_2O,although some contains N_2,H_2S,and CH_4.The compositions of the vapor and liquid phases of fluid inclusions in witherite can be divided into two end-members,one dominated by H_2O without other volatiles,and the other containing CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6 in addition to H_2O.CO_2,H_2S,and some CH_4 are interpreted as products of chemical reactions during mineralization.Organic gases(CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6) in the fluids were critical in the formation of barium sulfate versus carbonate.The δ~(34)S values of barite range from 38.26‰ to54.23‰(CDT),the δ~(34)S values of sulfides coexisting with barium minerals vary from 22.44‰ to25.11‰(CDT),and those in the wall rock from 11.60‰ to 19.06‰(CDT).We propose that the SO_4~(2-)generally experienced bacterial sulfate reduction in seawater before mineralization,and some SO_4~(2-)also experienced thermochemical sulfate reduction in hydrothermal system during mineralization.The δ~(13)C values of witherite range from-27.30‰ to-11.80‰(PDB),suggesting that carbon was sourced from organic substances(like CH_4,C_2H_4,and C_2H_6).The formation of witherite was possibly associated with thermochemical sulfate reduction,which caused the consumption of the organic gases and SO_4~(2-) in the hydrothermal solutions,consequently inhibiting barite formation.The important conditions for forming witherite include high fluid temperatures,high Ba~(2+) concentrations,CO_2 in the fluids,low HS~- concentrations,and the subsequent rapid diffusion of H_2S during thermochemical sulfate reduction of the fluids.  相似文献   

13.
Thermodynamic simulation of the system living matter (algae, zooplankton, or green plants) + mineral matter (25% carbonates + 75% clay minerals) + standard seawater at temperatures and pressure corresponding to diagenesis indicates that kerogen can be synthesized, together with hydrocarbons and carbon dioxide, in the reaction mix. The removal of CO2(g) and N2(g) from the system is favorable for the reaction Δ1C292H288O12 (s; H/C = 0.99, O/C = 0.041) → Δ2C128H68O7 (s; H/C = 0.53, O/C = 0.055) + xСH4(aq) + yCO2(aq) + zH2O, whose constant and stoichiometric coefficients were calculated based on the simulation results. It is demonstrated that a pressure increase is favorable, while a temperature increase is not, for the procedure of this reaction at P-T parameters of diagenesis: log K =–567 (20°C, 35 bar), 1170 (20°C, 200 bar),–1530 (20°C, 60 bar), and +1030 (20°C, 600 bar).  相似文献   

14.
Chlorine-35 magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra were collected at 14.1 and 18.8 Tesla fields to determine the atomic scale structural environments of the chloride ions in anhydrous and hydrous silicate and aluminosilicate glasses containing 0.2 to 0.7 wt% Cl. NMR peaks are broad and featureless, but are much narrower than the total chemical shift range for the nuclide in inorganic chlorides. Peak widths are primarily due to quadrupole interactions and to a lesser extent to chemical shift distributions. Peak positions are quite different for the Na- and Ca-containing glasses, suggesting that most Cl coordination environments contain network modifier cations. Comparison of peak positions and shapes for silicate and aluminosilicate glasses containing either Na or Ca suggests that there is no obvious contribution from Cl bonded to Al, and relative quantitation of peak areas indicates that there is no systematic undercounting of 35Cl spins in the aluminous vs. the Al-free samples. In Ca-Na silicate glasses with varying Ca/(Ca + Na), the mixed-cation glasses have intermediate chemical shifts between those of the end members, implying that there is not a strong preference of either Ca2+ or of Na+ around Cl. Hydrous Na-aluminosilicate glasses with H2O contents up to 5.9 wt% show a shift to higher frequency NMR signal with increasing H2O content, while the quadrupole coupling constant (CQ) remains constant at ∼3.3 MHz. However, the change in frequency is much smaller than that expected if H2O systematically replaced Na+ in the first-neighbor coordination shell around Cl. A series of hydrous Ca-aluminosilicate glasses with H2O contents up to 5.5 wt% show no shift in NMR signal with increasing H2O content. The CQ remains constant at ∼4.4 MHz, again suggesting no direct interaction between Cl and H2O in these samples.  相似文献   

15.
Hydrothermal experiments with H2O-CO2 fluids at Pfluid = 6 kbar yielded the following quilibrium conditions for reactions important in metamorphosed siliceous dolomites (T = °C; X = Xco2): (3) dolomite + 2 quartz = diopside + 2 CO2T = 620 ± 8X = 0.73 ± 0.03 (5) 5 dolomite + 8 quartz + H2O = tremolite + 3 calcite + 7 CO2T = 600 ± 5 550 ±5 540±5 500±5X = 0.66 ± 0.03 0.21 ± 0.03 0.21 ± 0.04 0.06 ± 0.02 (7) 3 dolomite + 4 quartz + H2O = talc + 3 calcite + 3 CO2T = 550±5 500±5 450 ±5X = 0.25 ± 0.05 0.07 ± 0.02 0.03 ± 0.02 (8) 2 dolomite + talc + 4 quartz = tremolite + 4 CO2T = 550 ± 5 540 ±5 500 ± 5X = 0.22 ± 0.03 0.21 ± 0.02 0.06 ± 0.02 A thermodynamically self-consistent 6 kbar T-XCO2, topology results by extrapolating equilibria from experimental brackets using a modified Redlich-Kwong equation for activities in H2O-CO2 mixtures. This topology restricts the assemblage talc + calcite to a narrow stability band in T-XCO2 space at XCO2 < 0.55 and T < 590°C. Accordingly, the occurrence of talc + calcite in pure siliceous dolomites metamorphosed at Pfluid = 6 kbar implies correspondingly water-rich fluids.  相似文献   

16.
Distribution and isotopic composition (δ13C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20–35 m), reached uniform concentrations (55 μM/l) in the monimolimnion (35–64 m) and again increased with depth in monimolimnion bottom sediments (>400 μM/kg below 1 m sub-bottom depth). The μ13C[CH4] values in bottom sediment below 1 m sub-bottom depth (<?70 per mil) increased with vertical distance up the core (δ13C[CH4] = ?55 per mil at sediment surface). Monimolimnion δ13C[CH4] values (?55 to ?61 per mil) were greater than most δ13C[CH4] values found in the anoxic mixolimnion (92% of samples had δ13C[CH4] values between ?20 and ?48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50–60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of CH4[C2H6 + C3H8] were high (250–620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in δ13C[CH4] and CH4(C2H6 + C3H8) with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C2 to C4 alkane production by microorganisms.  相似文献   

17.
The effect of standard processing techniques on the δ13C value of plant tissue was tested using species representing the three photosynthetic pathways, including angiosperms and gymnosperms within the C3 taxonomic division. The species include Cowania mexicana (C3 angiosperm), Juniperus osteosperma (C3 gymnosperm), Opuntia spp. (crassulacean acid metabolism [CAM] angiosperm), and Atriplex canescens (C4 angiosperm). Each species is represented by 5 plants collected at two different sites, for a total of 10 samples. The samples were processed to whole plant tissue, holocellulose, α-cellulose, and nitrocellulose. An additional process was added with the discovery of residual Ca-oxalate crystals in holocellulose samples. Both C3 species show δ13C values becoming 13C enriched with increased processing. The CAM representative shows the opposite trend, with 13C depletion during the progression of treatments. The greatest range of values and most inconsistent trends occur in the C4 representative. Removal of the Ca-oxalate fraction resulted in different mean weight percentages and δ13C values among the species. Calculated δ13C values of the Ca-oxalate crystals show depletion from the tissue values in the two C3 species and enrichment in the C4 and CAM representatives. The C. mexicana samples show the greatest change between the tissue and Ca-oxalates (7.3‰) but the least mean weight percentage (11%), whereas A. canescens shows the greatest overall change, with a −2.8‰ isotopic shift and over 48% mean weight percentage. Variability within the samples undergoing each treatment remained relatively unchanged even with increased cellulose purity. This paper provides estimates of isotopic offsets necessary to correct from one treatment to another. Significant differences in δ13C among different treatments confirm the need to state the tissue fraction analyzed when reporting δ13C results.  相似文献   

18.
The solubility of gold in aqueous sulphide solutions has been determined from pH20°C ≈ 4 to pH20°C ≈ 9.5 in the presence of a pyrite-pyrrhotite redox buffer at temperatures from 160 to 300°C and 1000 bar pressure. Maximum solubilities were obtained in the neutral region of pH as, for example, with mNaHS = 0.15 m, pH20°C = 5.96, T = 309°C, P = 1000 bar where a gold solubility of 225 mg/kg was obtained. It was concluded that three thio gold complexes contributed to the solubility. The complex Au2(HS)2S2? predominated in alkaline solution, the Au(HS)2? complex occurred in the neutral pH region, and in the acid pH region, it was concluded with less certainty that the Au(HS)° complex was present. Formation constants calculated forAu2(HS)2S2? and Au (HS)2? emphasize their high stability. In the temperature range from 175 to 250°C, values of for Au2(HS)2S2? vary from ?53.0 to 47.9 (±1.6) and from ?23.1 to ?19.5 ( ± 1.5) for Au(HS)2?. Equilibrium constante for the dissolution reactions, Au° + H2S + HS? ? Au(HS)2? + 12H2 and 2Au° + H2S + 2H8? ? Au(HS)2? + H2 vary from pKm = +2.4 to +2.55 (±0.10) for Au2(HS)2S2? and from pKn = + 1.29 to + 1.19 (±0.10) for Au(HS)2? over the temperature range 175 to 250°C. Enthalpies of these dissolution reactions were calculated to be ΔHm° = ?5.2 ±2.0 kcal/mol and ΔHn° = +1.7 ±2.0 kcal/mol respectively. It was concluded that gold is probably transported in hydrothermal ore solutions as both thio and chloro complexes and may be deposited in response to changes in temperature, pressure, pH, oxidation potential of the system and total sulphur concentration.  相似文献   

19.
Purification protocols to extract pollen from lake sediments contain chemicals that alter the carbon and oxygen pollen-isotope values according to pollen characteristics and family affiliation. Modern (raw) pollen of broad-leaved (Alnus glutinosa, Betula pendula, Carpinus betulus, Corylus avellana, Fagus sylvatica and Quercus robur) and coniferous tree species (Picea abies and Pinus sylvestris) were treated with potassium hydroxide (KOH), hydrofluoric acid (HF), sodium hypochlorite (NaClO) and sulphuric acid (H2SO4) to test the impact on δ13Cpollen and δ18Opollen and assess the applicability in purification protocols. Pollen of broad-leaved and coniferous trees reacted differently to chemical exposure, but response patterns are generally alike. Alterations of δ13Cpollen values vary between + 1.0‰ (B. pendula, NaClO-treatment) and −5.0‰ (P. sylvestris, H2SO4-treatment). The δ13Cpollen values of raw and chemically treated samples seem to be related after treatments with KOH, NaClO and HF, whereas the application of H2SO4 led to inconsistent changes among species. The impact of chemicals on δ18Opollen are more diverse and offsets range between +1.1‰ (C. avellana, NaClO-treatment) and −17.9‰ (P. sylvestris, H2SO4-treatment). In general, the use of isotope-altering chemicals in purification protocols should be brought to a minimum, but the application of KOH and NaClO seems mostly unproblematic before δ13Cpollen and δ18Opollen analysis.  相似文献   

20.
The organic geochemical methods of hydrocarbon prospecting involve the characterization of sedimentary organic matter in terms of its abundance, source and thermal maturity, which are essential prerequisites for a hydrocarbon source rock. In the present study, evaluation of organic matter in the outcrop shale samples from the Semri and Kaimur Groups of Vindhyan basin was carried out using Rock Eval pyrolysis. Also, the adsorbed low molecular weight hydrocarbons, methane, ethane, propane and butane, were investigated in the near surface soils to infer the generation of hydrocarbons in the Vindhyan basin. The Total Organic Carbon (TOC) content in shales ranges between 0.04% and 1.43%. The S1 (thermally liberated free hydrocarbons) values range between 0.01–0.09 mgHC/gRock (milligram hydrocarbon per gram of rock sample), whereas the S2 (hydrocarbons from cracking of kerogen) show the values between 0.01 and 0.14 mgHC/gRock. Based on the Tmax (temperature at highest yield of S2) and the hydrogen index (HI) correlations, the organic matter is characterized by Type III kerogen. The adsorbed soil gas, CH4 (C1), C2H6 (C2), C3H8 (C3) and nC4H10, (nC4), concentrations measured in the soil samples from the eastern part of Vindhyan basin (Son Valley) vary from 0 to 186 ppb, 0 to 4 ppb, 0 to 5 ppb, and 0 to 1 ppb, respectively. The stable carbon isotope values for the desorbed methane (δ13C1) and ethane (δ13C2) range between −45.7‰ to −25.2‰ and −35.3‰ to −20.19‰ (VPDB), respectively suggesting a thermogenic source for these hydrocarbons. High concentrations of thermogenic hydrocarbons are characteristic of areas around Sagar, Narsinghpur, Katni and Satna in the Son Valley. The light hydrocarbon concentrations (C1–C4) in near surface soils of the western Vindhyan basin around Chambal Valley have been reported to vary between 1–2547 ppb, 1–558 ppb, 1–181 ppb, 1–37 ppb and 1–32 ppb, respectively with high concentrations around Baran-Jhalawar-Bhanpur-Garot regions (Kumar et al., 2006). The light gaseous hydrocarbon anomalies are coincident with the wrench faults (Kota – Dholpur, Ratlam – Shivpuri, Kannod – Damoh, Son Banspur – Rewa wrench) in the Vindhyan basin, which may provide conducive pathways for the migration of the hydrocarbons towards the near surface soils.  相似文献   

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