Chemical and isotopic equilibrium between CO2 and CH4 in fumarolic gas discharges: Generation of CH4 in arc magmatic-hydrothermal systems

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH₄) within two subduction-related magmatic-hydrothermal environments.Apparent temperatures derived from carbon isotope partitioning between CH₄ and CO₂ of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H₂O-H₂-CO₂-CO-CH₄ geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH₄, CO₂ and H₂O implying that carbon isotope partitioning between CO₂ and CH₄ in both systems is controlled by aquifer temperature.N₂/³He and CH₄/³He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH₄ may have been primarily generated through the reduction of CO₂ by H₂ in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH₄ and subsequent re-equilibration with co-existing CO₂ cannot be ruled out entirely. CO₂/³He ratios and δ¹³C_CO2 values imply that the evolved CO₂ either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH₄ during thermometamorphism.     

Incremental vacuum dehydration-decarbonation experiments on a natural gibbsite (α-Al(OH3)): CO2 abundance and δC values

Incremental vacuum dehydration-decarbonation experiments were performed at 190°C on chemically “cleaned” aliquots of a gibbsite-dominated, Eocene-age bauxite sample with evolution of CO₂ and H₂O. “Plateau” F (CO₂/H₂O ratios) and δ¹³C values of the CO₂ derived from gibbsite were attained over the dehydration interval, X_v(H₂) = 0.16 to 0.67 (i.e., 16 to 67% breakdown of gibbsite). The plateau value of F for gibbsite was 0.0043 ± 0.0003, while the corresponding δ¹³C value of evolved CO₂ was −16.0‰±0.4‰. Additional experiments on chemically cleaned aliquots included (1) treatment with a solution of 0.3M Na-Citrate + 0.1M Na-Dithionite and (2) an exchange experiment with 0.1 bar of ¹³C-depleted CO₂ (−46‰) at 105°C for 64.5 h. Neither of these additional treatments resulted in a measurable perturbation of plateau values of F or δ¹³C for CO₂ evolved from gibbsite during dehydroxylation. These results support published work on Holocene samples which suggested that CO₂ occluded in gibbsite may preserve information on δ¹³C values of CO₂ in ancient terrestrial systems. The plateau values of F observed in the Eocene gibbsite indicate that it may be possible to experimentally calibrate a relationship between the concentration of CO₂ occluded in gibbsite and CO₂ in the environment at the time of crystallization. Such a calibration would significantly enhance the value of gibbsite as a source of information on ancient oxidized carbon systems.     

Formation of methane concentration and electromagnetic-field anomalies in southwestern Peter the Great Gulf (Sea of Japan)

We report methane concentrations in the bottom water layer and the upper layer of bottom sediments and the results of acoustic explorations of methane seeps on the shelf bordering the continental slope of the Sea of Japan region, in which electromagnetic Schumann’s resonance oscillations were earlier recorded at continental-slope water depths of 500, 1000, and 2000 m. The occurrence of Schumann’s resonances at such great depths is explained by an increase (a factor of more than 25) in the electrical resistivity of a ~ 2000 m thick sediment layer with the pore space largely filled with free methane. A new method is proposed for determining the depth of the sources of anomalous concentrations of methane in bottom sediments or in the bottom water layer on a deep shelf. The method is based on recording Schumann’s resonances during measurements of the natural electric field at a series of increasing depths in areas bordering the continental slope.     

Extreme methane deuterium,nitrogen and helium enrichment in natural gas from the Homorod seep (Romania)

Methane (CH₄) in terrestrial environments, whether microbial, thermogenic, or abiogenic, exhibits a large variance in C and H stable isotope ratios due to primary processes of formation. Isotopic variability can be broadened through secondary, post-genetic processes, such as mixing and isotopic fractionation by oxidation. The highest and lowest ¹³C and ²H (or D, deuterium) concentrations in CH₄ found in various geologic environments to date, are defined as “natural” terrestrial extremes. We have discovered a new extreme in a natural gas seep with values of deuterium concentrations, δD_CH4, up to + 124‰ that far exceed those reported for any terrestrial gas. The gas, seeping from the small Homorod mud volcano in Transylvania (Romania), also has extremely high concentrations of nitrogen (> 92 vol.%) and helium (up to 1.4 vol.%). Carbon isotopes in CH₄, C₂H₆ and CO₂, and nitrogen isotopes in N₂ indicate a primary organic sedimentary origin for the gas (a minor mantle component is suggested by the ³He/⁴He ratio, R/Ra ~ 0.39). Both thermogenic gas formation modeling and Rayleigh fractionation modeling suggest that the extreme deuterium enrichment could be explained by an oxidation process characterised by a δD_CH4 and δ¹³C_CH4 enrichment ratio (ΔH/ΔC) of about 20, and may be accounted for by abiogenic oxidation mediated by metal oxides. All favourable conditions for such a process exist in the Homorod area, where increased heat flow during Pliocene–Quaternary volcanism may have played a key role. Finally we observed rapid variations (within 1 h) in C and H isotope ratios of CH₄, and in the H₂S concentrations which are likely caused by mixing of the deep oxidized CH₄–N₂–H₂S–He rich gas with a microbial methane generated in the mud pool of one of the seeps.We hypothesize that the unusual features of Homorod gas can be the result of a rare combination of factors induced by the proximity of sedimentary organic matter, mafic, metal-rich volcanic rocks and salt diapirs, leading to the following processes: a) primary thermogenic generation of gas at temperatures between 130 and 175 °C; b) secondary alteration through abiogenic oxidation, likely triggered by the Neogene–Quaternary volcanism of the eastern Transylvanian margin; and c) mixing at the surface with microbial methane that formed through fermentation in the mud volcano water pool. The Homorod gas seep is a rare example that demonstrates how post-genetic processes can produce extreme gas isotope signatures (thus far only theorized), and that extremely positive δD_CH4 values cannot be used to unambiguously distinguish between biotic and abiotic origin.     

X-ray absorption studies of CH3Hg-binding sites in humic substances

Methylmercury cation (CH₃Hg⁺) is known to have a strong affinity for organic matter in soil, sedimentary, and aquatic environments. The objective of this study is to determine the dominant ligands binding CH₃Hg⁺ in humic acids by evaluating several CH₃Hg⁺-ligand complexation models, using mercury L_III-edge extended X-ray absorption fine structure (EXAFS). The model CH₃Hg⁺ binding ligands examined in this study include thiol (-SH), hydrogen polysulfide (-SSH or -SSSH), sulfide (-S-), disulfide (-SS-), carboxyl (-COOH), and amine (-NH₂). Based on the atomic geometry around mercury in each model structure, we distinguished CH₃Hg⁺-binding ligands in two different humic acids (soil and aquatic). We observed CH₃Hg⁺ preferentially binds to thiol ligands. After saturating reactive thiol ligands, the majority of CH₃Hg⁺ binds to carboxyl ligands rather than to amine or other reduced sulfur ligands than thiol. We found no evidence of significant CH₃Hg⁺-sulfide/disulfide or CH₃Hg⁺-hydrogen polysulfide complexes in any samples. When CH₃Hg⁺ binds to a humic ligand, the C-Hg bond in CH₃Hg⁺ remains intact. Some heavy atoms are proximately coordinated around the mercury atom in the sample containing the highest CH₃Hg⁺ levels used in this study.     

A unified equation for calculating methane vapor pressures in the CH4-H2O system with measured Raman shifts

A unified equation has been derived by using all available data for calculating methane vapor pressures with measured Raman shifts of C-H symmetric stretching band (υ₁) in the vapor phase of sample fluids near room temperature. This equation eliminates discrepancies among the existing data sets and can be applied at any Raman laboratory. Raman shifts of C-H symmetric stretching band of methane in the vapor phase of CH₄-H₂O mixtures prepared in a high-pressure optical cell were also measured at temperatures between room temperature and 200 °C, and pressures up to 37 MPa. The results show that the CH₄υ₁ band position shifts to higher wavenumber as temperature increases. We also demonstrated that this Raman band shift is a simple function of methane vapor density, and, therefore, when combined with equation of state of methane, methane vapor pressures in the sample fluids at elevated temperatures can be calculated from measured Raman peak positions. This method can be applied to determine the pressure of CH₄-bearing systems, such as methane-rich fluid inclusions from sedimentary basins or experimental fluids in hydrothermal diamond-anvil cell or other types of optical cell.     

A review of the geochemistry of methane in natural gas hydrate

The largest accumulations on Earth of natural gas are in the form of gas hydrate, found mainly offshore in outer continental margin sediment and, to a lesser extent, in polar regions commonly associated with permafrost. Measurements of hydrocarbon gas compositions and of carbon-isotopic compositions of methane from natural gas hydrate samples, collected in subaquatic settings from around the world, suggest that methane guest molecules in the water clathrate structures are mainly derived by the microbial reduction of CO₂ from sedimentary organic matter. Typically, these hydrocarbon gases are composed of > 99% methane, with carbon-isotopic compositions (δ¹³C_PDB) ranging from − 57 to − 73‰. In only two regions, the Gulf of Mexico and the Caspian Sea, has mainly thermogenic methane been found in gas hydrate. There, hydrocarbon gases have methane contents ranging from 21 to 97%, with δ¹³C values ranging from − 29 to − 57‰. At a few locations, where the gas hydrate contains a mixture of microbial and thermal methane, microbial methane is always dominant. Continental gas hydrate, identified in Alaska and Russia, also has hydrocarbon gases composed of > 99% methane, with carbon-isotopic compositions ranging from − 41 to − 49‰. These gas hydrate deposits also contain a mixture of microbial and thermal methane, with thermal methane likely to be dominant. Published by Elsevier Science Ltd     

Kinetic nitrogen isotope fractionation associated with thermal decomposition of NH3: Experimental results and potential applications to trace the origin of N2 in natural gas and hydrothermal systems

Ammonia (NH₃) is the major intermediate phase in the pathway of nitrogen (N) transfer from the fixed N phases (e.g., in crustal material) to free N₂ (e.g., in natural gas reservoirs and volcanic gases). Yet the N isotopic behavior during these N-cycling processes remains poorly known. In an attempt to contribute to the understanding of N cycling using N isotopes, we carried out laboratory experiments to investigate the N isotopic effect associated with thermal decomposition of ammonia (2NH₃ → N₂ + 3H₂). Pure NH₃ (with initial δ¹⁵N_NH3 of ∼ −2‰, relative to air standard) was sealed into quartz tubes and thermally decomposed at 600, 700 or 800 °C from 2 hours to 500 days. With the progress of the reaction, the δ¹⁵N of the remaining NH₃ and the accumulated N₂ increased from −2 to +35‰ and from −20 to −2‰, respectively. The differences of the N-isotope fractionations at the three temperatures are not significant. Modeling using the Rayleigh distillation model yielded similar kinetic N-isotope fractionation factors (α_N2-NH3) of 0.983 ± 0.002 for 600, 700 and 800 °C. Applied to geological settings, this significant isotope discrimination (∼17‰) associated with partial decomposition of NH₃/NH₄⁺ from crustal sources (δ¹⁵N_average ∼ +6.3‰) can produce mantle-like (i.e. ∼ −5‰) or even lower δ¹⁵N values of N₂. This may explain the large variation of δ¹⁵N (−20 to +30‰) of N₂ in natural gas reservoirs. It can also possibly explain the extreme ¹⁵N-depletion of N₂ in some volcanic gases. This possibility has to be carefully considered when using N isotopes to trace geological N cycling across subduction zones by analysis of volcanic N₂.     

Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ¹³C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane.     

Solubility of pyromorphite Pb5(PO4)3Cl-mimetite Pb5(AsO4)3Cl solid solution series

Pyromorphite Pb₅(PO₄)₃Cl and mimetite Pb₅(AsO₄)₃Cl are isostructural minerals with apatite. Due to their high environmental stability, they have gained considerable attention as metals sequestration agents in water treatment and contaminated soil remediation. Pyromorphite and mimetite can form a continuous solid solution series in near-Earth surface environments. Precipitation of the end members and intermediate members of the series is likely to occur in the areas where the cost-effective in situ immobilization reclamation method, based on phosphate amendments, is applied. In contrast to the widely studied thermodynamic parameters of pyromorphite and mimetite, knowledge of the thermodynamics of their solid solutions is sparse. To supplement the data, a number of compounds from the pyromorphite-mimetite series were synthesized at room temperature using a method to simulate the conditions in the near-Earth surface environments. Afterwards, batch dissolution and dissolution-recrystallization experiments of seven synthesized precipitates were conducted at 25 °C, pH = 2 and in a 0.05 M KNO₃ background electrolyte. The experiments were carried out for a period of 6 (dissolution) and 14 (dissolution-recrystallization) months. A plateau in the [Pb] evolution patterns was used to determine equilibrium. All seven dissolutions were congruent, and the ionic activity products (IAP) of the minerals from the pyromorphite-mimetite solid solution series were calculated based on the dissolution reaction: . The IAPs for pyromorphite and mimetite exhibit a significant difference in values over three orders of magnitude between approximately 10⁻⁷⁹ for pyromorphite and approximately 10⁻⁷⁶ for mimetite. The series appeared to be ideal, and Lippmann and Roozboom diagrams were used for better understanding of its thermodynamics. The results indicated a strong tendency of pyromorphite to partition into the solid phase in the series, which explains some of the naturally observed phenomena. The improvement of the lattice stability of the mimetite due to isostructural phosphate substitutions in anionic sites was observed. The thermodynamic data reported in this study supplement existing databases used in geochemical modeling.     

Thermochemistry of yavapaiite KFe(SO4)2: Formation and decomposition

Yavapaiite, KFe(SO₄)₂, is a rare mineral in nature, but its structure is considered as a reference for many synthetic compounds in the alum supergroup. Several authors mention the formation of yavapaiite by heating potassium jarosite above ca. 400°C. To understand the thermal decomposition of jarosite, thermodynamic data for phases in the K-Fe-S-O-(H) system, including yavapaiite, are needed. A synthetic sample of yavapaiite was characterized in this work by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermal analysis. Based on X-ray diffraction pattern refinement, the unit cell dimensions for this sample were found to be a = 8.152 ± 0.001 Å, b = 5.151 ± 0.001 Å, c = 7.875 ± 0.001 Å, and β = 94.80°. Thermal decomposition indicates that the final breakdown of the yavapaiite structure takes place at 700°C (first major endothermic peak), but the decomposition starts earlier, around 500°C. The enthalpy of formation from the elements of yavapaiite, KFe(SO₄)₂, ΔH°_f = −2042.8 ± 6.2 kJ/mol, was determined by high-temperature oxide melt solution calorimetry. Using literature data for hematite, corundum, and Fe/Al sulfates, the standard entropy and Gibbs free energy of formation of yavapaiite at 25°C (298 K) were calculated as S°(yavapaiite) = 224.7 ± 2.0 J.mol⁻¹.K⁻¹ and ΔG°_f = −1818.8 ± 6.4 kJ/mol. The equilibrium decomposition curve for the reaction jarosite = yavapaiite + Fe₂O₃ + H₂O has been calculated, at pH₂O = 1 atm, the phase boundary lies at 219 ± 2°C.     

Free energy of formation for green rust sodium sulphate (NaFe6Fe3(OH)18(SO4)2(s))

In a recent study, sulphate-bearing green rust (GR_SO4) was shown to incorporate Na⁺ in its structure (NaFe^II₆Fe^III₃(OH)₁₈(SO₄)_2(s); GR_Na,SO4). The compound was synthesised by aerial oxidation of Fe(OH)_2(s) in the presence of NaOH. This paper reports on its free energy of formation .Freshly synthesised GR_Na,SO4 was titrated with 0.5 M H₂SO₄ in an inert atmosphere at 25 °C, producing dissolved Fe²⁺ and magnetite or goethite. Solution concentrations, PHREEQC and the MINTEQ database were used to calculate reaction constants for the reactions:

     

Comparative studies on compounds occluded inside asphaltenes hierarchically released by increasing amounts of H2O2/CH3COOH

Being the heaviest fraction of crude oils, asphaltenes are liable to aggregate, and other molecules in the oils can be steadily adsorbed onto, and even occluded inside the macromolecular structures of the asphaltenes. These occluded compounds inside the asphaltenes can survive over geological time in oil reservoirs owing to effective protection by the macromolecular structures of the asphaltenes. The asphaltenes of a crude oil (ZG31) from the central Tarim Basin, NW China, were hierarchically degraded by increasing the amount of H₂O₂/CH₃COOH to release the occluded compounds. Besides the common components, series of even numbered n-alk-1-enes and 3-ethylalkanes were detected among the occluded compounds. Comparison of the biomarker distributions and the compound-specific C isotopic results between the compounds from the maltenes and those from the occluded fraction, the ZG31 reservoir was suggested to have been charged multiple times, with different charges being derived from different strata of source rocks.     

Neocomian paleogeography,gas hydrate cementation of sediments,and abnormal sequences of the Bazhenov Formation (West Siberia)

Abnormal zones of the Bazhenov Formation originated in the Neocomian as a result of protobazhenite reworking by submarine slide and slump waste wedgings, which eroded and deformed slope toe protobazhenite. But gas hydrate (GH) cementation might restrict the rock ability for plastic deformation. The conditions for GH thermodynamic stability in protobazhenites are inferred from reconstructions of paleogeographic and paleo-oceanic evironments. Joint analysis of Neocomian marine paleodepths and deep water paleotemperatures provides an explanation of the Bazhenov abnormal-zone extension.     

新矿物中华铈矿Ba2Ce(CO3)3F

新近发现一种含钡和稀土的氟碳酸盐矿物,经电子探针、矿物化学、X-射线粉品、X-射线能谱、电子衍射、扫瞄电予显微镜和透射电子显微镜等分析,偏光显微镜和反光显微镜光性鉴定,差热分析以及显微硬度、比重和其他物理性质测定,确定是一种新矿物。     

Iron isotope fractionation between pyrite (FeS2), hematite (Fe2O3) and siderite (FeCO3): A first-principles density functional theory study

In addition to equilibrium isotopic fractionation factors experimentally derived, theoretical predictions are needed for interpreting isotopic compositions measured on natural samples because they allow exploring more easily a broader range of temperature and composition. For iron isotopes, only aqueous species were studied by first-principles methods and the combination of these data with those obtained by different methods for minerals leads to discrepancies between theoretical and experimental isotopic fractionation factors. In this paper, equilibrium iron isotope fractionation factors for the common minerals pyrite, hematite, and siderite were determined as a function of temperature, using first-principles methods based on the density functional theory (DFT). In these minerals belonging to the sulfide, oxide and carbonate class, iron is present under two different oxidation states and is involved in contrasted types of interatomic bonds. Equilibrium fractionation factors calculated between hematite and siderite compare well with the one estimated from experimental data (ln α⁵⁷Fe/⁵⁴Fe = 4.59 ± 0.30‰ and 5.46 ± 0.63‰ at 20 °C for theoretical and experimental data, respectively) while those for Fe(III)_aq-hematite and Fe(II)_aq-siderite are significantly higher that experimental values. This suggests that the absolute values of the reduced partition functions (β-factors) of aqueous species are not accurate enough to be combined with those calculated for minerals. When compared to previous predictions derived from Mössbauer or INRXS data [Polyakov V. B., Clayton R. N., Horita J. and Mineev S. D. (2007) Equilibrium iron isotope fractionation factors of minerals: reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mössbauer spectroscopy. Geochim. Cosmochim. Acta71, 3833-3846], our iron β-factors are in good agreement for siderite and hematite while a discrepancy is observed for pyrite. However, the detailed investigation of the structural, electronic and vibrational properties of pyrite as well as the study of sulfur isotope fractionation between pyrite and two other sulfides (sphalerite and galena) indicate that DFT-derived β-factors of pyrite are as accurate as for hematite and siderite. We thus suggest that experimental vibrational density of states of pyrite should be re-examined.     

CTR diffraction and grazing-incidence EXAFS study of U(VI) adsorption onto α-Al2O3 and α-Fe2O3 (11?02) surfaces

Evaluation of the long-term health risks of uranium contamination in soils, sediments, and groundwater requires a fundamental understanding of the various processes affecting subsurface transport of uranium, including adsorption processes at mineral/water interfaces. In this study, the sites of binding and surface complexation of U(VI) adsorbed on the (11?02) surfaces of α-Al₂O₃ and α-Fe₂O₃ have been determined using crystal truncation rod (CTR) diffraction and grazing incidence extended X-ray absorption fine structure (GI-EXAFS) spectroscopy. The available binding sites on the (11?02) surfaces were constrained through bond valence and steric analyses. On both surfaces, U(VI) forms uranyl-carbonato ternary complexes to surface oxygens that are singly coordinated to aluminum or iron. On the α-Al₂O₃ (11?02) surface, a monodentate complex results, whereas on the α-Fe₂O₃ (11?02) surface, the binding is bidentate to adjacent singly coordinated oxygen sites (i.e., binuclear). Differences in protonation of the singly coordinated oxygen atoms, surface charging, U(VI) aqueous speciation, substrate structure, or the electronic structure of surface functional groups may be the cause of these differences in adsorption geometry. Both XPS and CTR diffraction reveal higher U(VI) surface coverages on the α-Fe₂O₃ (11?02) surface than on the α-Al₂O₃ (11?02) surface. This difference cannot be the result of differences in defect concentration alone as CTR diffraction is not sensitive to U(VI) sorbed to defect sites, implying that the α-Fe₂O₃ (11?02) surface has an intrinsically higher affinity for U(VI). The surface complexes observed in this study are different from the bidentate, mononuclear complexes typically derived for U(VI) on powdered aluminum- and iron-(oxyhydr)oxides and clay minerals using U L_III-edge EXAFS spectroscopy. However, the presence of monodentate, mononuclear and bidentate, binuclear complexes may have been overlooked in past EXAFS studies on such substrates, as these complexes have U-Al or U-Fe interatomic distances that are too large to be easily detected by EXAFS spectroscopy.     

Solubility of rhodochrosite (MnCO3) in water and seawater

The solubility product of rhodochrosite (MnCO₃) was measured in seawater, deionized water and dilute NaCl solutions. The solubility product extrapolated to infinite dilution at 25.0 C was (2.60 ± 0.07)× 10^?11. The stoichiometric solubility product measured in seawater of 34.27%. salinity was (3.24 ± 0.23) × 10^?9 at 25.0 C and (2.28 ± 0.24) × 10^?9 at 3.3 C. The stoichiometric solubility product is in good agreement with the value calculated from an ion association model. The enthalpy of the reaction is in fair agreement with the estimated value.     

The oxidative dissolution of arsenopyrite (FeAsS) and enargite (Cu3AsS4) by Leptospirillum ferrooxidans

Arsenopyrite (FeAsS) and enargite (Cu₃AsS₄) fractured in a nitrogen atmosphere were characterised after acidic (pH 1.8), oxidative dissolution in both the presence and absence of the acidophilic microorganism Leptospirillum ferrooxidans. Dissolution was monitored through analysis of the coexisting aqueous solution using inductively coupled plasma atomic emission spectroscopy and coupled ion chromatography-inductively coupled plasma mass spectrometry, and chemical changes at the mineral surface observed using X-ray photoelectron spectroscopy and environmental scanning electron microscopy (ESEM). Biologically mediated oxidation of arsenopyrite and enargite (2.5 g in 25 ml) was seen to proceed to a greater extent than abiotic oxidation, although arsenopyrite oxidation was significantly greater than enargite oxidation. These dissolution reactions were associated with the release of ∼917 and ∼180 ppm of arsenic into solution. The formation of Fe(III)-oxyhydroxides, ferric sulphate and arsenate was observed for arsenopyrite, thiosulphate and an unknown arsenic oxide for enargite. ESEM revealed an extensive coating of an extracellular polymeric substance associated with the L. ferrooxidans cells on the arsenopyrite surface and bacterial leach pits suggest a direct biological oxidation mechanism, although a combination of indirect and direct bioleaching cannot be ruled out. Although the relative oxidation rates of enargite were greater in the presence of L. ferrooxidans, cells were not in contact with the surface suggesting an indirect biological oxidation mechanism. Cells of L. ferrooxidans appear able to withstand several hundreds of ppm of As(III) and As(V).     

长岭凹陷深层天然气藏中CO_2及CH_4充注次序的流体包裹体证据

对长岭凹陷深层天然气藏储层——营城组火山岩中发育的流体包裹体进行了详细研究,结果表明在火山岩发育的石英、方解石细网脉中均存在较多的碳质流体包裹体,单个包裹体激光拉曼光谱分析结果表明其主要为CO2及CH4两种类型的碳质包裹体。其中方解石细网脉体中发育有原生及次生CH4包裹体,而含CO2包裹体多以原生包裹体产于石英细网脉中。很多含CO2包裹体的石英细脉中发现了含CH4包裹体的方解石脉体的角砾,这就表明石英细脉形成晚于方解石细脉。营城组火山岩储层中CO2及CH4包裹体的产状特征研究表明,松辽盆地深层天然气藏的形成系火山岩成岩后CO2及CH4等气体不同期次充注的结果,CH4气的充注时间早于CO2气,火山岩中发育的原生孔隙及次生裂隙为上述气体的充注和聚集提供了重要通道。