Determination of in-situ stress direction from cleat orientation mapping for coal bed methane exploration in south-eastern part of Jharia coalfield, India

Accurate prediction of in-situ stress directions plays a key role in any Coal Bed Methane (CBM) exploration and exploitation project in order to estimate the production potential of the CBM reservoirs. Permeability is one of the most important factors for determination of CBM productivity. The coal seams in Jharia coalfield generally show low permeability in the range of 0.5 md to 3 md. To estimate the in-situ stress direction in the study area, an attempt has been made to undertake the cleat orientation mapping of four regional coal seams of two underground coal mines located at south-eastern part of Jharia coalfield, India. Cleat orientation mapping is critical to determine the maximum principal compressive horizontal stress (S_H) direction for CBM exploration and exploitation, which in turn controls the direction of maximum gas or water flow though coal beds. From the field study it is found that the average face and butt cleat azimuths are towards N15°W and N75°E respectively. Average permeability of the four above-mentioned major coal seams has been calculated from well logs of nine CBM wells distributing over an area of 7.5 km², adjacent to the underground mines. The cleat orientations are congruous with the regional lineament pattern and fits well with the average permeability contour map of the study area to infer the orientation of in-situ maximum horizontal stress. Goodness of fit for the exponential regressions between vertical stress and permeability for individual coal seams varies between 0.6 and 0.84. The cleat orientation is further validated from the previous fracture analysis using FMI well log in Parbatpur area located southern part of the Jharia coalfield. The major coal seams under the study area exhibit directional permeability, with the maximum permeability, oriented parallel to the direction of face cleat orientation.     

Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field,Taupo Volcanic Zone,New Zealand

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW_e). Soil CO₂ degassing was quantified with 2663 CO₂ flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m⁻²) using published soil temperature heat flow functions. Both CO₂ flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO₂ gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO₂ emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO₂ emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they contributed little (<1%) to pre-production CO₂ emissions due to the loss of >99% of the original CO₂ content due to depressurisation and boiling as the fluids ascended to the surface. Consequently, the soil has persisted as the major (99%) pathway of CO₂ release to the atmosphere from the high temperature reservoir at Ohaaki. The CO₂ flux and heat flow surveys indicate that despite 20 a of production the variability in location, spatial extent and magnitude of CO₂ flux remains consistent with established geochemical and geophysical models of the Ohaaki Field. At both OHW and OHE carbon isotopic analyses of soil gas indicate a two-stage fractionation process for moderate-flux (>60 g m⁻² d⁻¹) sites; boiling during fluid ascent within the underlying reservoir and isotopic enrichment as CO₂ diffuses through porous media of the soil zone. For high-flux sites (>300 g m⁻² d⁻¹), the δ¹³CO₂ signature (−7.4 ± 0.3‰ OHW and −6.5 ± 0.6‰ OHE) is unaffected by near-surface (soil zone) fractionation processes and reflects the composition of the boiled magmatic CO₂ source for each respective upflow. Flux thresholds of <30 g m⁻² d⁻¹ for purely diffusive gas transport, between 30 and 300 g m⁻² d⁻¹ for combined diffusive–advective transport, and ?300 g m⁻² d⁻¹ for purely advective gas transport at Ohaaki were assigned. δ¹³CO₂ values and cumulative probability plots of CO₂ flux data both identified a threshold of ∼15 g m⁻² d⁻¹ by which background (atmospheric and soil respired) CO₂ may be differentiated from hydrothermal CO₂.     

Mineral control of arsenic content in thermal waters from volcano-hosted hydrothermal systems: Insights from island of Ischia and Phlegrean Fields (Campanian Volcanic Province, Italy)

This paper documents arsenic concentrations in 157 groundwater samples from the island of Ischia and the Phlegrean Fields, two of the most active volcano-hosted hydrothermal systems from the Campanian Volcanic Province (Southern Italy), in an attempt to identify the environmental conditions and mineral-solution reactions governing arsenic aqueous cycling. On Ischia and in the Phlegrean Fields, groundwaters range in composition from NaCl brines, which we interpret as the surface discharge of deep reservoir fluids, to shallow-depth circulating fluids, the latter ranging from acid-sulphate steam-heated to hypothermal, cold, bicarbonate groundwaters. Arsenic concentrations range from 1.6 to 6900 μg·l^− 1 and from 2.6 to 3800 μg·l^− 1 in the Phlegrean Fields and on Ischia, respectively. They increase with increasing water temperature and chlorine contents, and in the sequence bicarbonate groundwaters < steam-heated groundwaters < NaCl brines. According to thermochemical modeling, we propose that high As concentrations in NaCl brines form after prolonged water-rock interactions at reservoir T, fO₂ and fH₂S conditions, and under the buffering action of an arsenopyrite + pyrite + pyrrhotite rock assemblage. On their ascent toward the surface, NaCl brines become diluted by As-depleted meteoric-derived bicarbonate groundwaters, giving rise to hybrid water types with intermediate to low As contents. Steam-heated groundwaters give their intermediate to high As concentrations to extensive rock leaching promoted by interaction with As-bearing hydrothermal steam.     

The solubility of molybdenum dioxide and trioxide in HCl-bearing water vapour at 350 °C and pressures up to 160 bars

The solubility and speciation of the assemblage MoO₂-MoO₃ in water vapour were investigated in experiments conducted at 350 °C, P_total from 59 to 160 bar and fHCl from 0 to 3.4 bar (0-2.0 mol%). Measured solubility at these conditions ranges from 22 to 2500 ppm (∑fMo from 4.4 × 10⁻⁴ to 6.5 × 10⁻² bar). The concentration of Mo in the vapour at fHCl below 0.1 bar is similar to that in pure water vapour, but increases by two orders of magnitude at fHCl above 0.1 bar. The fugacity of gaseous Mo species is independent of chloride concentration at fHCl below 0.1 bar, but increases with increasing fHCl above this pressure. The dominant Mo species at fHCl below 0.1 bar is interpreted to be the same as it is in pure water vapour, and to form as a result of the reaction

(A1)     

Internally consistent thermodynamic data for magnesium sulfate hydrates

Experimental studies on the stability of several Mg-sulfate hydrates including epsomite (MgSO₄·7H₂O), hexahydrite (MgSO₄·6H₂O), starkeyite (MgSO₄·4H₂O), and kieserite (MgSO₄·H₂O) as a function of temperature and relative humidity are in poor agreement with calculations based on thermodynamic properties of these substances taken from the literature. Therefore, we synthesized four different MgSO₄ hydrates and measured their enthalpies of formation by solution calorimetry at T = 298.15 K. The resulting enthalpies of formation from the elements are:

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Δ_fH⁰₂₉₈ (epsomite) = −3387.7 ± 1.3 kJmol⁻¹

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Δ_fH⁰₂₉₈ (hexahydrite) = −3088.1 ± 1.1 kJmol⁻¹

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Δ_fH⁰₂₉₈ (sanderite, MgSO₄·2H₂O) = −1894.9 ± 1.3 kJmol⁻¹

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Δ_fH⁰₂₉₈ (kieserite) = −1612.4 ± 1.3 kJmol⁻¹

Using mathematical programming (MAP) techniques, standard thermodynamic values consistent both with our calorimetric data and previously published humidity brackets could be derived:

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Epsomite: Δ_fH⁰₂₉₈ = −3388.7 kJmol⁻¹, S⁰₂₉₈ = 371.3 Jmol⁻¹ K⁻¹, Δ_fG⁰₂₉₈ = −2871.0 kJmol⁻¹

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Hexahydrite: Δ_fH⁰₂₉₈ = −3087.3 kJmol⁻¹, S⁰₂₉₈ = 348.5 Jmol⁻¹ K⁻¹, Δ_fG⁰₂₉₈ = −2632.3 kJmol⁻¹

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Starkeyite: Δ_fH⁰₂₉₈ = −2496.1 kJmol⁻¹, S⁰₂₉₈ = 259.9 Jmol⁻¹ K⁻¹, Δ_fG⁰₂₉₈ = −2153.8 kJmol⁻¹

•

Kieserite: Δ_fH⁰₂₉₈ = −1611.5 kJmol⁻¹, S⁰₂₉₈ = 126.0 Jmol⁻¹ K⁻¹, Δ_fG⁰₂₉₈ = −1437.9 kJmol⁻¹

Additionally, heat capacity measurements and standard entropy determinations of several magnesium sulfate hydrate minerals from the literature are analyzed and judged against estimates obtained from a linear combination of the heat capacities of MgSO₄ and hexagonal ice. The results of the MAP analysis are compared to these estimates to conclude that heat capacity and entropy correlate well with the number of waters of hydration. However, even the good correlation is not good enough to capture the fine variations in these properties. Consequently, their experimental measurement is inevitable if reliable thermodynamic data are sought. Our MAP thermodynamic data show that epsomite, hexahydrite, and kieserite have stability fields in the T-%RH space. Starkeyite is metastable. Although no MAP data could have been derived for pentahydrite (MgSO₄·5H₂O) and sanderite, their transient existence suggest that both of them are metastable as well.     

The influence factors of gas-bearing and geological characteristics of Niutitang Formation shale in the southern margin of Xuefeng Mountain ancient uplift: A case of Well Huangdi 1

In order to evaluate the geological characteristics and gas-bearing factors of Niutitang Formation within the Lower Cambrian of northern Guizhou, the Huangping area located at the southern edge of the ancient uplift belt of Xuefeng Mountain was selected as the target area, and Well Huangdi 1 was drilled for the geological survey of shale gas. Through geological background analysis and well logging and laboratory analysis such as organic geochemical test, gas content analysis, isothermal adsorption, and specific surface area experiments on Well Huangdi 1, the results show that the Niutitang Formation is a deep-water shelf, trough-like folds and thrust fault. The thickness of black shale is 119.95 m, of which carbonaceous shale is 89.6 m. The average value of organic carbon content is 3.55%, kerogen vitrinite reflectance value is 2.37% and kerogen type is sapropel-type. The brittle mineral content is 51% (quartz 38%), clay mineral content is 38.3%. The value of porosity and permeability are 0.5% and 0.0014 mD, which the reservoir of the Niutitang Formation belongs to low permeability with characteristics of ultra-low porosity. The gas content is 0.09 −1.31 m³/t with a high-value area and a second high-value area. By comparing with the geological parameters of adjacent wells in the adjacent area, the accumulation model of “sediment control zone, R_o control zone, structure controlling reservoir” in the study area is proposed. Therefore, deep-water shelf-slope facies, R_o is between high maturity-early stage of overmaturity and well-preserved zones in the Niutitang Formation in this area are favorable direction for the next step of shale gas exploration.     

Thermodynamic properties of H4SiO4 in the ideal gas state as evaluated from experimental data

Solid phases of silicon dioxide react with water vapor with the formation of hydroxides and oxyhydroxides of silica. Recent transpiration and mass-spectrometric studies convincingly demonstrate that H₄SiO₄ is the predominant form of silica in vapor phase at water pressure in excess of 10⁻² MPa. Available literature transpiration and solubility data for the reactions of solid SiO₂ phases and low-density water, extending from 424 to 1661 K, are employed for the determination of Δ_fG⁰, Δ_fH⁰ and S⁰ of H₄SiO₄ in the ideal gas state at 298.15 K, 0.1 MPa. In total, there are 102 data points from seven literature sources. The resulting values of the thermodynamic functions of H₄SiO₄(g) are: Δ_fG⁰ = −1238.51 ± 3.0 kJ mol⁻¹, Δ_fH⁰ = −1340.68 ± 3.5 kJ mol⁻¹ and S⁰ = 347.78 ± 6.2 J K⁻¹ mol⁻¹. These values agree quantitatively with one set of ab initio calculations. The relatively large uncertainties are mainly due to conflicting data for H₄SiO₄(g) from various sources, and new determinations of would be helpful. The thermodynamic properties of this species, H₄SiO₄(g), are necessary for realistic modeling of silica transport in a low-density water phase. Applications of this analysis may include the processes of silicates condensation in the primordial solar nebula, the precipitation of silica in steam-rich geothermal systems and the corrosion of SiO₂-containing alloys and ceramics in moist environments.     

The oxidation state of sulfur in synthetic and natural glasses determined by X-ray absorption spectroscopy

Sulfur K-edge X-ray absorption near edge structure (XANES) spectra were recorded for experimental glasses of various compositions prepared at different oxygen fugacities (fO₂) in one-atmosphere gas-mixing experiments at 1400 °C. This sample preparation method only results in measurable S concentrations under either relatively reduced (log fO₂ < −9) or oxidised (log fO₂ > −2) conditions. The XANES spectra of the reduced samples are characterised by an absorption edge crest at 2476.4 eV, typical of S²⁻. In addition, spectra of Fe-bearing compositions exhibit a pronounced absorption edge shoulder. Spectra for all the Fe-free samples are essentially identical, as are the spectra for the Fe-bearing compositions, despite significant compositional variability within each group. The presence of a sulfide phase, such as might exsolve on cooling, can be inferred from a pre-edge feature at 2470.5 eV.The XANES spectra of the oxidised samples are characterised by an intense transition at 2482.1 eV, typical of the sulfate anion SO₄²⁻. Sulfite (SO₃²⁻) has negligible solubility in silicate melts at low pressures. The previous identification of sulfite species in natural glass samples is attributed to an artefact of the analysis (photoreduction of S⁶⁺). S⁴⁺ does, however, occur unambiguously with S⁶⁺ in Fe-free and Fe-poor compositions prepared in equilibrium with CaSO₄ at 4-16 kbar, and when buffered with Re/ReO₂ at 10 kbar. Solubility of S⁴⁺ thus requires partial pressures of SO₂ considerably in excess of 1 bar. A number of experiments were undertaken in an attempt to access intermediate fO₂s more applicable to terrestrial volcanism. Although these were largely unsuccessful, S²⁻ and S⁶⁺ were found to coexist in some samples that were not in equilibrium with the imposed fO₂.The XANES spectra of natural olivine-hosted melt inclusions and submarine glasses representative of basalts at, or close to, sulfide saturation show mainly dissolved S²⁻, but with minor sulfate, and additionally a peak at 2469.5 eV, which, although presumably due to immiscible sulfide, is 1 eV lower than that typical of FeS. These sulfate and sulfide-related peaks disappear with homogenisation of the inclusions by heating to 1200 °C followed by rapid quenching, suggesting that both these features are a result of cooling under natural conditions. The presence of small amounts of sulfate in otherwise reduced basaltic magmas may be explained by the electron exchange reaction: S²⁻ + 8Fe³⁺ = S⁶⁺ + 8Fe²⁺, which is expected to proceed strongly to the right with decreasing temperature. This reaction would explain why S²⁻ and S⁶⁺ are frequently found together despite the very limited fO₂ range over which they are thermodynamically predicted to coexist. The S XANES spectra of water-rich, highly oxidised, basaltic inclusions hosted in olivine from Etna and Stromboli confirm that nearly all S is dissolved as sulfate, explaining their relatively high S contents.     

Changes in optical properties, chemistry, and micropore and mesopore characteristics of bituminous coal at the contact with dikes in the Illinois Basin

Changes in high-volatile bituminous coal (Pennsylvanian) near contacts with two volcanic intrusions in Illinois were investigated with respect to optical properties, coal chemistry, and coal pore structure. Vitrinite reflectance (R_o) increases from 0.62% to 5.03% within a distance of 5.5 m from the larger dike, and from 0.63% to 3.71% within 3.3 m from the small dike. Elemental chemistry of the coal shows distinct reductions in hydrogen and nitrogen content close to the intrusions. No trend was observed for total sulfur content, but decreases in sulfate content towards the dikes indicate thermochemical sulfate reduction (TSR). Contact-metamorphism has a dramatic effect on coal porosity, and microporosity in particular. Around the large dike, the micropore volume, after a slight initial increase, progressively decreases from 0.0417 cm³/g in coal situated 4.7 m from the intrusive contact to 0.0126 cm³/g at the contact. Strongly decreasing mesopore and micropore volumes in the altered zone, together with frequent cleat and fracture filling by calcite, indicate deteriorating conditions for both coalbed gas sorption and gas transmissibility.     

Distribution rule of the in situ stress state and its influence on the permeability of a coal reservoir in the southern Qinshui Basin,China

The recent development of the coalbed methane (CBM) industry has a significant role in advancing hydraulic fracturing theory and technology. However, further development requires a better understanding of how fractures influence reservoir permeability. In situ stress data from 54 CBM wells in the southern Qinshui Basin, China, were obtained by the injection/falloff test method to analyse the effect of in situ stress on the permeability of the CBM reservoir. The types of in situ stress states were classified, and the coal reservoir permeability under different in situ stress states was analysed. The results indicate that the maximum horizontal principal stress (σ_H), minimum horizontal principal stress (σ_h) and vertical principal stress (σ_v) all have positive linear relationships with the coal seam burial depth. Three in situ stress states were observed from the shallow to deep regions of the CBM reservoir in the study area: σ_H?>?σ_h?>?σ_v, σ_H?>?σ_v?>?σ_h and σ_v?>?σ_H?>?σ_h, which account for 9, 76 and 15% of the test wells, respectively. Coal reservoir permeability decreases with increasing horizontal principal stress, whereas it first decreases with increasing σ_v, then increases and finally decreases. The variation in permeability with σ_v is due to the conversion of the in situ stress states. Coal reservoir permeability has obvious differences under different in situ stress states. The permeability is the largest when σ_v?>?σ_H?>?σ_h, followed by σ_H?>?σ_h?>?σ_v and smallest when σ_H?>?σ_v?>?σ_h. The permeability differences are caused by the fracture propagation shape of the rock strata under different in situ stress states.     

Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solutions

A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R_p) to the gross forward precipitation rate (R_f), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R_p has been experimentally measured under varying conditions, but the magnitude of R_f is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R_f can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R_b or k_b), since at equilibrium R_f = R_b, and R_p = 0. Hence it can be inferred that R_f ≈ R_p + R_b. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R_p (=R_f − R_b) ? R_b. For precipitation rates high enough that R_p ? R_b, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R_p ≈ R_b for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R_f for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R_p. Allowing R_b to vary as , consistent with available precipitation rate studies, produces a better fit to some trace element and isotopic data than a model where R_b is constant. This model can account for most of the experimental data in the literature on the dependence of ⁴⁴Ca/⁴⁰Ca and metal/Ca fractionation in calcite as a function of precipitation rate and temperature, and also accounts for ¹⁸O/¹⁶O variations with some assumptions. The apparent temperature dependence of Ca isotope fractionation in calcite may stem from the dependence of R_b on temperature; there should be analogous pH dependence at pH < 6. The proposed model may be valuable for predicting the behavior of isotopic and trace element fractionation for a range of elements of interest in low-temperature aqueous geochemistry. The theory presented is based on measureable thermo-kinetic parameters in contrast to models that require hyper-fast diffusivity in near-surface layers of the solid.     

Charging time of tight gas in the Upper Paleozoic of the Ordos Basin,central China

The Upper Paleozoic section contains a tight gas sandstone reservoir (of 2.75 × 10¹² m³) in the Ordos Basin, central China. The measured porosities (< 10%) and permeabilities (generally < 1 mD) are the result of significant mechanical and chemical compaction and precipitation of carbonate, quartz and authigenic clay cements. Fluid inclusion geochemistry and kinetic modeling (generation of gaseous components and δ¹³C₁) were integrated to constrain the timing of gas charge into the tight reservoir. The modeling results indicate that the natural gases in the present reservoir are similar to gases liberated from quartz inclusions in both composition and stable carbon isotope values and also similar to gas generated from Upper Paleozoic coal. The similar geochemistry suggests that an important phase of quartz cementation must have occurred after gas emplacement in the reservoirs during regional uplift at the end of the Cretaceous. The latest carbonate cement, postdating quartz cementation, consumed most of the late CO₂ generated from coal at high maturity (R_O > 1.7%) and reduced the reservoir quality dramatically. On the contrary, tight sandstones from non-producing areas have fluid inclusions that were trapped in quartz cements much earlier. These data indicate that natural gas migrated into the Upper Paleozoic reservoir when it still retained high porosity and permeability. The reservoir continued to experience porosity and permeability reduction from continued quartz and carbonate cementation after gas charging due to low gas saturation. Comparison of the relative timing of gas charging with that of sandstone cementation can help to predict areas of risk during tight gas exploration and development.     

Impact of transition from local swelling to macro swelling on the evolution of coal permeability

Laboratory observations have shown that coal permeability under the influence of gas adsorption can change instantaneously from reduction to enhancement. It is commonly believed that this instantaneous switching of permeability is due to the fact that the matrix swelling ultimately ceases at higher pressures and the influence of effective stresses take over. In this study, our previously-developed poroelastic model is used to uncover the true reason why coal permeability switches from reduction to enhancement. This goal is achieved through explicit simulations of the dynamic interactions between coal matrix swelling/shrinking and fracture aperture alteration, and translations of these interactions to perrmeability evolution under unconstrained swellings. Our results of this study have revealed the transition of coal matrix swelling from local swelling to macro-swelling as a novel mechanism for this switching. Our specific findings include: (1) at the initial stage of CO₂ injection, matrix swelling is localized within the vicinity of the fracture compartment. As the injection continues, the swelling zone is extending further into the matrix and becomes macro-swelling. Matrix properties control the swelling transition from local swelling to macro swelling; (2) matrix swelling processes control the evolution of coal permeability. When the swelling is localized, coal permeability is controlled by the internal fracture boundary condition and behaves volumetrically; when the swelling becomes macro-swelling, coal permeability is controlled by the external boundary condition and behaves non-volumetrically; and (3) matrix properties control the switch from local swelling to macro swelling and the associated switch in permeability behavior from reduction to recovery. Based on these findings, a permeability switching model has been proposed to represent the evolution of coal permeability under variable stress conditions. This model is verified against our experimental data. It is found that the model predictions are consistent with typical laboratory and in-situ observations available in lietratures.     

Structure of H2O-saturated peralkaline aluminosilicate melt and coexisting aluminosilicate-saturated aqueous fluid determined in-situ to 800 °C and ∼800 MPa

The structure of H₂O-saturated silicate melts and of silicate-saturated aqueous solutions, as well as that of supercritical silicate-rich aqueous liquids, has been characterized in-situ while the sample was at high temperature (to 800 °C) and pressure (up to 796 MPa). Structural information was obtained with confocal microRaman and with FTIR spectroscopy. Two Al-bearing glasses compositionally along the join Na₂O•4SiO₂-Na₂O•4(NaAl)O₂-H₂O (5 and 10 mol% Al₂O₃, denoted NA5 and NA10) were used as starting materials. Fluids and melts were examined along pressure-temperature trajectories of isochores of H₂O at nominal densities (from PVT properties of pure H₂O) of 0.85 g/cm³ (NA10 experiments) and 0.86 g/cm³ (NA5 experiments) with the aluminosilicate + H₂O sample contained in an externally-heated, Ir-gasketed hydrothermal diamond anvil cell.Molecular H₂O (H₂O°) and OH groups that form bonds with cations exist in all three phases. The OH/H₂O° ratio is positively correlated with temperature and pressure (and, therefore, fugacity of H₂O, f_H2O) with (OH/H₂O°)^melt > (OH/H₂O°)^fluid at all pressures and temperatures. Structural units of Q³, Q², Q¹, and Q⁰ type occur together in fluids, in melts, and, when outside the two-phase melt + fluid boundary, in single-phase liquids. The abundance of Q⁰ and Q¹ increases and Q² and Q³ decrease with f_H2O. Therefore, the NBO/T (nonbridging oxygen per tetrahedrally coordination cations), of melt is a positive function of f_H2O. The NBO/T of silicate in coexisting aqueous fluid, although greater than in melt, is less sensitive to f_H2O.The melt structural data are used to describe relationships between activity of H₂O and melting phase relations of silicate systems at high pressure and temperature. The data were also combined with available partial molar configurational heat capacity of Qⁿ-species in melts to illustrate how these quantities can be employed to estimate relationships between heat capacity of melts and their H₂O content.     

Sulfur K-edge XANES analysis of natural and synthetic basaltic glasses: Implications for S speciation and S content as function of oxygen fugacity

XANES analyses at the sulfur K-edge were used to determine the oxidation state of S species in natural and synthetic basaltic glasses and to constrain the fO₂ conditions for the transition from sulfide (S²⁻) to sulfate (S⁶⁺) in silicate melts. XANES spectra of basaltic samples from the Galapagos spreading center, the Juan de Fuca ridge and the Lau Basin showed a dominant broad peak at 2476.8 eV, similar to the spectra obtained from synthetic sulfide-saturated basalts and pyrrhotite. An additional sharp peak at 2469.8 eV, similar to that of crystalline sulfides, was present in synthetic glasses quenched from hydrous melts but absent in anhydrous glasses and may indicate differences in sulfide species with hydration or presence of minute sulfide inclusions exsolved during quenching. The XANES spectra of a basalt from the 1991 eruption of Mount Pinatubo, Philippines, and absarokitic basalts from the Cascades Range, Oregon, USA, showed a sharp peak at 2482.8 eV, characteristic of synthetic sulfate-saturated basaltic glasses and crystalline sulfate-bearing minerals such as hauyne. Basaltic samples from the Lamont Seamount, the early submarine phase of Kilauea volcano and the Loihi Seamount showed unequivocal evidence of the coexistence of S²⁻ and S⁶⁺ species, emphasizing the relevance of S⁶⁺ to these systems. XANES spectra of basaltic glasses synthesized in internally-heated pressure vessels and equilibrated at fO₂ ranging from FMQ − 1.4 to FMQ + 2.7 showed systematic changes in the features related to S²⁻ and S⁶⁺ with changes in fO₂. No significant features related to sulfite (S⁴⁺) species were observed. These results were used to construct a function that allows estimates of S⁶⁺/ΣS from XANES data. Comparison of S⁶⁺/ΣS data obtained by S Kα shifts measured with electron probe microanalysis (EPMA), S⁶⁺/ΣS obtained from XANES spectra, and theoretical considerations show that data obtained from EPMA measurements underestimate S⁶⁺/ΣS in samples that are sulfate-dominated (most likely because of photo-reduction effects during analysis) whereas S⁶⁺/ΣS from XANES provide a close match to the expected theoretical values. The XANES-derived relationship for S⁶⁺/ΣS as a function of fO₂ indicates that the transition from S²⁻ to S⁶⁻ with increasing fO₂ occurs over a narrower interval than what is predicted by the EPMA-derived relationship. The implications for natural systems is that small variation of fO₂ above FMQ + 1 will have a large effect on S behavior in basaltic systems, in particular regarding the amount of S that can be transported by basaltic melts before sulfide saturation can occur.     

沁水盆地南部TS地区煤层气储层测井评价方法

煤层气是一种自生自储于煤岩地层的非常规天然气资源,其储层测井评价内容及方法不同于常规天然气,在煤层气勘探开发过程中更关注于有关煤岩工业分析组分、基质孔隙度、裂缝渗透率及煤层含气量等一系列关键的储层参数。针对沁水盆地南部TS地区煤层气勘探目标层,分析了各种测井响应特征,采用回归分析法计算煤岩工业分析组分;针对煤层气含量影响因素众多且较为复杂的特点,结合相关地区煤岩样品实验分析结果,利用基于等温吸附实验的兰氏煤阶方程估算煤层含气量参数;通过煤岩孔隙结构的分析,采用变骨架密度的密度孔隙度计算公式求取煤岩总孔隙度,利用迭代逼近算法计算裂缝孔隙度;根据煤岩裂缝中面割理发育而端割理不甚发育的特点,以简化的单组系板状裂缝模型计算煤岩裂缝渗透率。通过对TS-A井进行实际计算,结果表明,煤岩工业分析组分和煤层含气量计算结果精度高,总孔隙度一般在5.5%左右,而裂缝孔隙度则大多小于0.5%,裂缝渗透率主要分布在0.001×10-3～10×10-3μm2之间,孔渗参数计算结果与相邻井区现有资料相符。采用测井方法可以快速、系统地对煤层气储层多种参数进行准确评价。     

Old Smokey coal fire, Floyd County, Kentucky: Estimates of gaseous emission rates

Vent emissions of the Old Smokey coal fire, Floyd County, Kentucky, were studied in May and July, 2010. Vent emissions were generally lower in July, perhaps due to a shift in the fire front, change in vent structure, or another unidentified factor. Volatile organics in the vent gasses contain dangerous levels of toxic, carcinogenic, and other hazardous compounds. Benzene ranges to nearly 400 parts per billion (volume) at one vent. Toluene exceeds 104 parts per billion (volume) at the same vent.Flux rates for CO₂ and CO range to 85,000 mg/s/m² and 89 mg/s/m², respectively, for various vents for the two measuring times. Estimates of total CO₂ emissions, possibly less than 1000 t/year, are within the range of other eastern Kentucky coal fires.     

Use of biomarkers indices in a sediment core to evaluate potential pollution sources in a subtropical reservoir in Brazil

The presence of PAHs, n-alkanes, pristane, and phytanes in core sediment from the Vossoroca reservoir (Parana, southern Brazil) was investigated. The total concentration of the 16 PAHs varied from 15.5 to 1646 μg kg⁻¹. Naphthalene was present in all layers (3.34–74.0 μg kg⁻¹). The most abundant and dominant n-alkanes were n-C₁₅ and n-C₃₆, with average concentrations of 198.1 ± 46.8 and 522.9 ± 167.7 μg kg⁻¹, respectively. Lighter n-alkanes were distributed more evenly through the layers and showed less variation, specially n-C₉, n-C₁₂, and n-C₁₈, with average concentrations of 14.6 ± 3.0, 31.6 ± 1.9, and 95.0 ± 5.2 μg kg⁻¹, respectively; heavier n-alkanes were more unevenly distributed.     

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

Palaeo-hydrogeological control on groundwater As levels in Red River delta,Vietnam

To study the geological control on groundwater As concentrations in Red River delta, depth-specific groundwater sampling and geophysical logging in 11 monitoring wells was conducted along a 45 km transect across the southern and central part of the delta, and the literature on the Red River delta’s Quaternary geological development was reviewed. The water samples (n = 30) were analyzed for As, major ions, Fe²⁺, H₂S, NH₄, CH₄, δ¹⁸O and δD, and the geophysical log suite included natural gamma-ray, formation and fluid electrical conductivity. The SW part of the transect intersects deposits of grey estuarine clays and deltaic sands in a 15–20 km wide and 50–60 m deep Holocene incised valley. The NE part of the transect consists of 60–120 m of Pleistocene yellowish alluvial deposits underneath 10–30 m of estuarine clay overlain by a 10–20 m veneer of Holocene sediments. The distribution of δ¹⁸O-values (range −12.2‰ to −6.3‰) and hydraulic head in the sample wells indicate that the estuarine clay units divide the flow system into an upper Holocene aquifer and a lower Pleistocene aquifer. The groundwater samples were all anoxic, and contained Fe²⁺ (0.03–2.0 mM), Mn (0.7–320 μM), SO₄ (<2.1 μM–0.75 mM), H₂S (<0.1–7.0 μM), NH₄ (0.03–4.4 mM), and CH₄ (0.08–14.5 mM). Generally, higher concentrations of NH₄ and CH₄ and low concentrations of SO₄ were found in the SW part of the transect, dominated by Holocene deposits, while the opposite was the case for the NE part of the transect. The distribution of the groundwater As concentration (<0.013–11.7 μM; median 0.12 μM (9 μg/L)) is related to the distribution of NH₄, CH₄ and SO₄. Low concentrations of As (?0.32 μM) were found in the Pleistocene aquifer, while the highest As concentrations were found in the Holocene aquifer. PHREEQC-2 speciation calculations indicated that Fe²⁺ and H₂S concentrations are controlled by equilibrium for disordered mackinawite and precipitation of siderite. An elevated groundwater salinity (Cl range 0.19–65.1 mM) was observed in both aquifers, and dominated in the deep aquifer. A negative correlation between aqueous As and an estimate of reduced SO₄ was observed, indicating that Fe sulphide precipitation poses a secondary control on the groundwater As concentration.