Characterization of the CO2 fluid adsorption in coal as a function of pressure using neutron scattering techniques (SANS and USANS)

Small angle neutron scattering techniques have been applied to investigate the phase behavior of CO₂ injected into coal and possible changes in the coal pore structure that may result from this injection. Three coals were selected for this study: the Seelyville coal from the Illinois Basin (R_o = 0.53%), Baralaba coal from the Bowen Basin (R_o = 0.67%), and Bulli 4 coal from the Sydney Basin (R_o = 1.42%). The coals were selected from different depths to represent the range of the underground CO₂ conditions (from subcritical to supercritical) which may be realized in the deep subsurface environment. The experiments were conducted in a high pressure cell and CO₂ was injected under a range of pressure conditions, including those corresponding to in-situ hydrostatic subsurface conditions for each coal. Our experiments indicate that the porous matrix of all coals remains essentially unchanged after exposure to CO₂ at pressures up to 200 bar (1 bar = 10⁵ Pa). Each coal responds differently to the CO₂ exposure and this response appears to be different in pores of various sizes within the same coal. For the Seelyville coal at reservoir conditions (16 °C, 50 bar), CO₂ condenses from a gas into liquid, which leads to increased average fluid density in the pores (ρ_pore) with sizes (r) 1 × 10⁵ ≥ r ≥ 1 × 10⁴ Å (ρ_pore ≈ 0.489 g/cm³) as well as in small pores with size between 30 and 300 Å (ρ_pore ≈ 0.671 g/cm³). These values are by a factor of three to four higher than the density of bulk CO₂ (ρ_CO2) under similar thermodynamic conditions (ρ_CO2 ≈ 0.15 g/cm³). At the same time, in the intermediate size pores with r ≈ 1000 Å the average fluid density is similar to the density of bulk fluid, which indicates that adsorption does not occur in these pores. At in situ conditions for the Baralaba coal (35 ^OC, 100 bar), the average fluid density of CO₂ in all pores is lower than that of the bulk fluid (ρ_pore / ρ_CO2 ≈ 0.6). Neutron scattering from the Bulli 4 coal did not show any significant variation with pressure, a phenomenon which we assign to the extremely small amount of porosity of this coal in the pore size range between 35 and 100,000 Å.     

Methane and carbon dioxide sorption on a set of coals from India

Complete sorption isotherm characteristics of methane and CO₂ were studied on fourteen sub-bituminous to high-volatile bituminous Indian Gondwana coals. The mean vitrinite reflectance values of the coal samples are within the range of 0.64% to 1.30% with varying maceral composition. All isotherms were conducted at 30 °C on dry, powdered coal samples up to a maximum experimental pressure of ~ 7.8 MPa and 5.8 MPa for methane and CO₂, respectively.The nature of the isotherms varied widely within the experimental pressure range with some of the samples remained under-saturated while the others attained saturation. The CO₂ to methane adsorption ratios decreased with the increase in experimental pressure and the overall variation was between 4:1 and 1.5:1 for most of the coals. For both methane and CO₂, the lower-ranked coal samples generally exhibited higher sorption affinity compared to the higher-ranked coals. However, sorption capacity indicates a U-shaped trend with rank. Significant hysteresis was observed between the ad/desorption isotherms for CO₂. However, with methane, hysteresis was either absent or insignificant. It was also observed that the coal maceral compositions had a significant impact on the sorption capacities for both methane and CO₂. Coals with higher vitrinite contents showed higher capacities while internite content indicated a negative impact on the sorption capacity.     

The structural evolution of organic matter during maturation of coals and its impact on petroleum potential and feedstock for the deep biosphere

The structural evolution of coals during coalification from peat to the end of the high volatile bituminous coal rank (VR_r = 0.22–0.81%) has been studied using a natural maturity series from New Zealand. Samples were studied using a range of standard coal analyses, Rock–Eval analysis, infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and pyrolysis gas chromatography (Py-GC). The structural evolution of coal during diagenesis and moderate catagenesis is dominated by defunctionalisation reactions leading to the release of significant amounts of oxygen and thereby to an enrichment of aromatic as well as aliphatic structures within the residual organic matter. Based on the evolution of pyrolysis yields and elemental compositions with maturity it can be demonstrated that oxygen loss is the major cause for increasing Hydrogen Index values or hydrocarbon generating potentials of coals at such maturity levels. For the first time, the loss of oxygen in form of CO₂ has been quantified. During maturation from peat to high volatile bituminous coal ranks ∼10–105 mg CO₂/g TOC has been released. This is equivalent to 2.50E−4 to 1.25E−3 mg CO₂ generated from every litre of sediment per year falling into the range of deep biosphere utilisation rates. Immature coals, here New Zealand coals, therefore manifest the potential to feed deep terrestrial microbial life, in contrast to more mature coals (VR_r > ∼0.81%) for which defunctionalisation processes become less important.     

Adsorption kinetics of CO2, CH4, and their equimolar mixture on coal from the Black Warrior Basin,West-Central Alabama

Laboratory experiments were conducted to investigate the adsorption kinetic behavior of pure and mixed gases (CO_2, CH₄, approximately equimolar CO₂ + CH₄ mixtures, and He) on a coal sample obtained from the Black Warrior Basin at the Littleton Mine (Twin Pine Coal Company), Jefferson County, west-central Alabama. The sample was from the Mary Lee coal zone of the Pottsville Formation (Lower Pennsylvanian). Experiments with three size fractions (45–150 µm, 1–2 mm, and 5–10 mm) of crushed coal were performed at 40 °C and 35 °C over a pressure range of 1.4–6.9 MPa to simulate coalbed methane reservoir conditions in the Black Warrior Basin and provide data relevant for enhanced coalbed methane recovery operations. The following key observations were made: (1) CO₂ adsorption on both dry and water-saturated coal is much more rapid than CH₄ adsorption; (2) water saturation decreases the rates of CO₂ and CH₄ adsorption on coal surfaces, but it appears to have minimal effects on the final magnitude of CO₂ or CH₄ adsorption if the coal is not previously exposed to CO₂; (3) retention of adsorbed CO₂ on coal surfaces is significant even with extreme pressure cycling; and (4) adsorption is significantly faster for the 45–150 μm size fraction compared to the two coarser fractions.     

Three-dimensional carbon dioxide-induced strain distribution within a confined bituminous coal

Sequestration of carbon dioxide in unmineable coal seams is an option to reduce carbon dioxide emissions. It is well known that the interaction of carbon dioxide with unconfined coal induces swelling. This paper contributes three-dimensional strain distribution in confined coal at microstructural level using high-resolution X-ray computerized tomography data and image analysis. Swelling and compression/compaction of regions in the coal matrix occurs with CO₂ uptake. Normal strain varies between ? 1.15% and 0.93%, ? 3.11% and 0.94%, ? 0.43% and 0.30% along x, y and z axes respectively. Volumetric strain varies between ? 4.25% and 1.25%. The positive strains reported are consistent with typical range for unconstrained swelling. However, the average volumetric strains value (? 0.34%) reflect overall volume reduction. Overall swelling is apparently influenced by the confining stresses. The magnitudes of normal strains are heterogeneous and anisotropic. The swelling vs. compression/compaction observed after CO₂ uptake is localized and likely lithotype dependant.     

Assessing the potential for CO2 adsorption in a subbituminous coal,Huntly Coalfield,New Zealand,using small angle scattering techniques

Small angle scattering techniques (SAXS and SANS) have been used to investigate the microstructural properties of the subbituminous coals (R_max 0.42–0.45%) from the Huntly Coalfield, New Zealand. Samples were collected from the two thick (> 5 m) coal seams in the coalfield and have been analysed for methane and carbon dioxide sorption capacity, petrography, pore size distribution, specific surface area and porosity.Specific surface area (SSA) available for carbon dioxide adsorption, extrapolated to a probe size of 4 Å, ranged from 1.25 × 10⁶ cm^? 1 to 4.26 × 10⁶ cm^? 1 with total porosity varying from 16% to 25%. Porosity was found to be predominantly composed of microporosity, which contributed the majority of the available SSA. Although considerable variation was seen between samples, the results fit well with published rank trends.Gas holding capacity at the reservoir pressure (approximately 4 MPa) ranged from 2.63 to 4.18 m³/t for methane on a dry, ash-free basis (daf) and from 22.00 to 23.72 m³/t daf for carbon dioxide. The resulting ratio of CO₂:CH₄ ranged from 5.7 to 8.6, with an average of 6.7:1.Holding capacities for both methane and carbon dioxide on a dry ash free basis (daf) were found to be correlated with sample microporosity. However, holding capacities for the two gases on an as analysed (aa) basis (that is including mineral matter and moisture), showed no such correlation. Carbon dioxide (aa) does show a negative correlation with both specific surface area and microporosity. As the coals have low inorganic matter content, the reversal is thought to be related to moisture which is likely concentrated in the pore size range 12.5–125 Å. Methane holding capacity, both daf and aa, correlates with macroporosity, thus suggesting that the holding capacity of micropores is diminished by the presence of moisture in the pores.     

Modeling of coal bed methane (CBM) production and CO2 sequestration in coal seams

A mathematical model was developed to predict the coal bed methane (CBM) production and carbon dioxide (CO₂) sequestration in a coal seam accounting for the coal seam properties. The model predictions showed that, for a CBM production and dewatering process, the pressure could be reduced from 15.17 MPa to 1.56 MPa and the gas saturation increased up to 50% in 30 years for a 5.4 × 10⁵ m² of coal formation. For the CO₂ sequestration process, the model prediction showed that the CO₂ injection rate was first reduced and then slightly recovered over 3 to 13 years of injection, which was also evidenced by the actual in seam data. The model predictions indicated that the sweeping of the water in front of the CO₂ flood in the cleat porosity could be important on the loss of injectivity. Further model predictions suggested that the injection rate of CO₂ could be about 11 × 10³ m³ per day; the injected CO₂ would reach the production well, which was separated from the injection well by 826 m, in about 30 years. During this period, about 160 × 10⁶ m³ of CO₂ could be stored within a 21.4 × 10⁵ m² of coal seam with a thickness of 3 m.     

Long-term pCO2 dynamics in rivers in the Chesapeake Bay watershed

Streams and rivers are major exporters of C and other dissolved materials from watersheds to coastal waters. In streams and rivers, substantial amounts of terrigenous organic C is metabolized and degassed as CO₂ to the atmosphere. A long-term evaluation of CO₂ dynamics in streams is essential for understanding factors controlling CO₂ dynamics in streams in response to changes in climate and land-use. Long-term changes in the partial pressure of CO₂ (pCO₂) were computed in the Anacostia River and the lower Potomac River in the Chesapeake Bay watershed. Long-term estimates were made using routine monitoring data of pH, total alkalinity, and dissolved nutrients from 1985 to 2006 at 14 stations. Longitudinal variability in pCO₂ dynamics was also investigated along these rivers downstream of the urban Washington D.C. metropolitan area. Both rivers were supersaturated with CO₂ with respect to atmospheric CO₂ levels (392 μatm) and the highly urbanized Anacostia waters (202–9694 μatm) were more supersaturated than the Potomac waters (557–3800 μatm). Long-term variability in pCO₂ values may be due to changes in river metabolism and organic matter and nutrient loadings. Both rivers exchange significant amounts of CO₂ with the atmosphere (i.e., Anacostia at 0.2–72 mmol m⁻² d⁻¹ and Potomac at 0.12–24 mmol m⁻² d⁻¹), implying that waterways receiving organic matter and nutrient subsidies from urbanized landscapes have the potential to increase river metabolism and atmospheric CO₂ fluxes along the freshwater–estuarine continuum.     

Small angle X-ray scattering mapping and kinetics study of sub-critical CO2 sorption by two Australian coals

Time- and position-resolved synchrotron small angle X-ray scattering data were acquired from samples of two Australian coal seams: Bulli seam (Bulli 4, R_o = 1.42%, Sydney Basin), which naturally contains CO₂ and Baralaba seam (R_o = 0.67%, Bowen Basin), a potential candidate for sequestering CO₂. This experimental approach has provided unique, pore-size-specific insights into the kinetics of CO₂ sorption in the micro- and small mesopores (diameter 5 to 175 Å) and the density of the sorbed CO₂ at reservoir-like conditions of temperature and hydrostatic pressure.For both samples, at pressures above 5 bar, the density of CO₂ confined in pores was found to be uniform, with no densification in near-wall regions. In the Bulli 4 sample, CO₂ first flooded the slit pores between polyaromatic sheets. In the pore-size range analysed, the confined CO₂ density was close to that of the free CO₂. The kinetics data are too noisy for reliable quantitative analysis, but qualitatively indicate faster kinetics in mineral-matter-rich regions.In the Baralaba sample, CO₂ preferentially invaded the smallest micropores and the confined CO₂ density was up to five times that of the free CO₂. Faster CO₂ sorption kinetics was found to be correlated with higher mineral matter content but, the mineral-matter-rich regions had lower-density CO₂ confined in their pores. Remarkably, the kinetics was pore-size dependent, being faster for smaller pores.These results suggest that injection into the permeable section of an interbedded coal-clastic sequence could provide a viable combination of reasonable injectivity and high sorption capacity.     

Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems

A series of methane (CH₄) adsorption experiments on bulk organic rich shales and their isolated kerogens were conducted at 35 °C, 50 °C and 65 °C and CH₄ pressure of up to 15 MPa under dry conditions. Samples from the Eocene Green River Formation, Devonian–Mississippian Woodford Shale and Upper Cretaceous Cameo coal were studied to examine how differences in organic matter type affect natural gas adsorption. Vitrinite reflectance values of these samples ranged from 0.56–0.58 %R_o. In addition, thermal maturity effects were determined on three Mississippian Barnett Shale samples with measured vitrinite reflectance values of 0.58, 0.81 and 2.01 %R_o.For all bulk and isolated kerogen samples, the total amount of methane adsorbed was directly proportional to the total organic carbon (TOC) content of the sample and the average maximum amount of gas sorption was 1.36 mmol of methane per gram of TOC. These results indicate that sorption on organic matter plays a critical role in shale-gas storage. Under the experimental conditions, differences in thermal maturity showed no significant effect on the total amount of gas sorbed. Experimental sorption isotherms could be fitted with good accuracy by the Langmuir function by adjusting the Langmuir pressure (P_L) and maximum sorption capacity (Γ_max). The lowest maturity sample (%R_o = 0.56) displayed a Langmuir pressure (P_L) of 5.15 MPa, significantly larger than the 2.33 MPa observed for the highest maturity (%R_o > 2.01) sample at 50 °C.The value of the Langmuir pressure (P_L) changes with kerogen type in the following sequence: type I > type II > type III. The thermodynamic parameters of CH₄ adsorption on organic rich shales were determined based on the experimental CH₄ isotherms. For the adsorption of CH₄ on organic rich shales and their isolated kerogen, the heat of adsorption (q) and the standard entropy (Δs⁰) range from 7.3–28.0 kJ/mol and from −36.2 to −92.2 J/mol/K, respectively.     

Dissolution kinetics of Devonian carbonates at circum-neutral pH, 50 bar pCO2, 105 °C,and 0.4 M: The importance of complex brine chemistry on reaction rates

The dissolution kinetics of carbonate rocks sampled from the Keg River Formation in Northeast British Columbia were measured at 50 bar pCO₂ and 105 °C, in both natural and synthetic brines of 0.4 M ionic strength. Natural brines yielded reaction rates of −12.16 ± 0.11 mol cm⁻² s⁻¹ for Log R_Ca, and −12.64 ± 0.05 for Log R_Mg. Synthetic brine yielded faster rates of reaction than natural brines. Experiments performed on synthetic brines, spiked with 10 mmol of either Sr or Zn, suggest that enhanced reaction rates observed in synthetic brines are due to a lack of trace ion interaction with mineral surfaces. Results were interpreted within the surface complexation model framework, allowing for the discrimination of reactive surface sites, most importantly the hydration of the >MgOH surface site. Dissolution rates extrapolated from experiments predict that CO₂ injected into the Keg River Formation will dissolve a very minor portion of rock in contact with affected formation waters.     

Fluid types and their genetic meaning for the BIF-hosted iron ores,Krivoy Rog,Ukraine

This paper contributes to the understanding of the genesis of epigenetic, hypogene BIF-hosted iron deposits situated in the eastern part of Ukrainian Shield. It presents new data from the Krivoy Rog iron mining district (Skelevatske–Magnetitove deposit, Frunze underground mine and Balka Severnaya Krasnaya outcrop) and focuses on the investigation of ore genesis through application of fluid inclusion petrography, microthermometry, Raman spectroscopy and baro-acoustic decrepitation of fluid inclusions. The study investigates inclusions preserved in quartz and magnetite associated with the low-grade iron ores (31–37% Fe) and iron-rich quartzites (38–45% Fe) of the Saksaganskaya Suite, as well as magnetite from the locally named high-grade iron ores (52–56% Fe). These high-grade ores resulted from alteration of iron quartzites in the Saksaganskiy thrust footwall (Saksaganskiy tectonic block) and were a precursor to supergene martite, high-grade ores (60–70% Fe). Based on the new data two stages of iron ore formation (metamorphic and metasomatic) are proposed.The metamorphic stage, resulting in formation of quartz veins within the low-grade iron ore and iron-rich quartzites, involved fluids of four different compositions: CO₂-rich, H₂O, H₂O–CO₂(± N₂–CH₄)–NaCl(± NaHCO₃) and H₂O–CO₂(± N₂–CH₄)–NaCl. The salinities of these fluids were relatively low (up to 7 mass% NaCl equiv.) as these fluids were derived from dehydration and decarbonation of the BIF rocks, however the origin of the nahcolite (NaHCO₃) remains unresolved. The minimum P–T conditions for the formation of these veins, inferred from microthermometry are T_min = 219–246 °C and P_min = 130–158 MPa. The baro-acoustic decrepitation analyses of magnetite bands indicated that the low-grade iron ore from the Skelevatske–Magnetitove deposit was metamorphosed at T = ~ 530 °C.The metasomatic stage post-dated and partially overlapped the metamorphic stage and led to the upgrade of iron quartzites to the high-grade iron ores. The genesis of these ores, which are located in the Saksaganskiy tectonic block (Saksaganskiy ore field), and the factors controlling iron ore-forming processes are highly controversial. According to the study of quartz-hosted fluid inclusions from the thrust zone the metasomatic stage involved at least three different episodes of the fluid flow, simultaneous with thrusting and deformation. During the 1^st episode three types of fluids were introduced: CO₂–CH₄–N₂(± C), CO₂(± N₂–CH₄) and low salinity H₂O–N₂–CH₄–NaCl (6.38–7.1 mass% NaCl equiv.). The 2^nd episode included expulsion of the aqueous fluids H₂O–N₂–CH₄–NaCl(± CO₂, ± C) of moderate salinities (15.22–16.76 mass% NaCl equiv.), whereas the 3^rd event involved high salinity fluids H₂O–NaCl(± C) (20–35 mass% NaCl equiv.). The fluids most probably interacted with country rocks (e.g. schists) supplying them with CH₄ and N₂. The high salinity fluids were most likely either magmatic–hydrothermal fluids derived from the Saksaganskiy igneous body or heated basinal brines, and they may have caused pervasive leaching of Fe from metavolcanic and/or the BIF rocks. The baro-acoustic decrepitation analyses of magnetite comprising the high-grade iron ore showed formation T = ~ 430–500 °C. The fluid inclusion data suggest that the upgrade to high-grade Fe ores might be a result of the Krivoy Rog BIF alteration by multiple flows of structurally controlled, metamorphic and magmatic–hydrothermal fluids or heated basinal brines.     

A preliminary study of mineralogy and geochemistry of four coal samples from northern Iran

This study is related to four Jurassic-age bituminous coal (0.69–1.02 Ro%) samples collected from coal mines from the west, central and east of central, Alborz in northern Iran. Geological settings played key roles in determining the geochemistry and mineralogy of coals from the central Alborz region of northern Iran. The mineralogy of coals from the eastern part of the region is dominated by kaolinite; halloysite; and carbonates such as calcite, dolomite/ankerite, and siderite. The coals were deposited in a lacustrine environment. In the western part of the region, where the depositional setting was also lacustrine with volcanic input and tonstein deposition (glass shards present), the coal primarily contains kaolinite (68%) and fluorapatite (26%). In contrast, coal from the central part of the region, which was deposited in a terrestrial environment and on eroded limestone and dolomite rocks, is dominated by dolomite (98%) with little input by kaolinite. These coals have low sulphur (0.35–0.70 wt.%), which is mostly in the organic form (0.34–0.69 wt.%). Pyritic sulphur is detected only in one coal and in small quantities. The boron contents of these coals range from 9 to 33 mg/kg, indicating that deposition occurred in a fresh water environment. Coal with higher concentrations of Ba, Sr, and P contain fluorapatite and goyazite–gorceixite series [BaAl₃ (PO₄)₂ (OH)₅, H₂O] minerals, which indicates volcanoclastic input. Compared to world coal averages, these coals exhibit low concentrations of elements of environmental concern, such as As (1.3–5.9 mg/kg), Cd (< 0.02–0.06 mg/kg), Hg (< 0.01–0.07 mg/kg) Mo (< 0.6–1.7 mg/kg), Pb (4.8–13 mg/kg), Th (0.5–21 mg/kg), Se (< 0.2–0.8 mg/kg) and U (0.2–4.6 mg/kg). Two of the northern Iranian coals have concentrations of Cl (2560 and 3010 mg/kg) that are higher than world coal average.     

Fe(III) mobilisation by carbonate in low temperature environments: Study of the solubility of ferrihydrite in carbonate media and the formation of Fe(III) carbonate complexes

The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO₂ concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO₂ varying between (0.982–98.154 kPa) at 25 °C.The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO₃ and Fe(CO₃)₃³⁻, with formation constants log^*β°_1,1,1 = 10.76 ± 0.38 and log β°_1,0,3 = 24.24 ± 0.42, respectively.The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO₂ and at T = (25 ± 1) °C, as log^*K_s,0 = 1.19 ± 0.41.The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO₂-rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers.     

Hydrothermal He and CO2 at Wudalianchi intra-plate volcano,NE China

Chemical and isotopic compositions have been measured for CO₂-rich bubbling gases discharging from cold springs in Wudalianchi intra-plate volcanic area, NE China. Observed ³He/⁴He ratios (2–3 R_A) and δ¹³C values of CO₂ (−5‰ to −3‰) indicate the occurrence of a mantle component released and transferred to the surface by the Cenozoic extension-related magmatic activities. The CO₂/³He ratios are in wide range of (0.4–97 × 10⁹). Based on the apparent mixing trend in a ³He/⁴He and δ¹³C of CO₂ diagram from all published data, the extracted magmatic end-member in the Wudalianchi Volcano has ³He/⁴He, δ¹³C and CO₂/³He value of ∼3.2 R_A, ∼−4.6‰ and ∼6 × 10¹⁰, respectively. These values suggest that the volatiles originate from the sub-continental lithospheric mantle (SCLM) in NE China and represent ancient fluids captured by prior metasomatic events, as revealed by geothermal He and CO₂ from the adjacent Changbaishan volcanic area.     

Hydro-geochemical and isotopic fluid evolution of the Los Azufres geothermal field,Central Mexico

Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (T_mi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (T_h)  = 325 ± 5 °C. The boiling zone shows T_h = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO₂. Positive clathrate melting temperatures (fusion) with T_h = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO₂ (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ¹⁸O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ¹⁸O is due to the rock–water interaction at relatively high temperatures. δ¹³C stable isotope data show a magmatic source with a minor meteoric contribution for CO₂. The initial isotopic value δ³⁴S_RES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ³⁴S (FeS₂) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ¹⁸O.     

Ore petrography and chemistry of the tellurides from the Dongping gold deposit,Hebei Province,China

The Dongping gold deposit is a mesothermal lode gold deposit hosted in syenite. The ore petrography and chemistry of the tellurides from the alteration zone of the deposit have been studied in detail using optical microscopy, scanning electron microscopy, electron probe micro-beam and X-ray diffraction facilities. The tellurides, consisting mostly of calaverite, altaite, petzite tellurobismuthite and tetradymite, are hosted irregularly in pyrite fractures and voids. In the ore bodies, the species and quantity of tellurides decrease from the top downwards, accompanied with lowering of gold fineness, and the existence of tellurides exhibits a positive correlation with gold enrichment. Mineral paragenesis and chemical variations suggest that during evolution of the ore-forming fluids Te preferably incorporated with Pb to form altaite, followed in sequence by precipitation of petzite, and calaverite when Ag has been exhausted, and the residue fluids were enriched in Au, giving rise to formation of native gold. Calculation with reference of the fineness of native gold coexisting with the tellurides indicates that at 300 °C, log f (Te₂) varied between − 8.650 and − 7.625. Taking account of the Au–Ag–Te mineral paragenesis, it is inferred that log ƒ (Te₂) varies from − 9.12 to − 6.43, log ƒ (S₂) − 11.47 to − 8.86. In consideration of the physicochemical conditions for formation of tellurides, with comparison to some known telluride deposits, it is suggested that high log ƒ (Te₂) is a key factor for high fineness of native gold as well as precipitation of abundant tellurides.     

Interaction of U(VI) with Äspö diorite: A batch and in situ ATR FT-IR sorption study

Pristine diorite drill cores, obtained from the Äspö Hard Rock Laboratory (HRL, Sweden), were used to study the retention properties of fresh, anoxic crystalline rock material towards the redox-sensitive uranium. Batch sorption experiments and spectroscopic methods were applied for this study. The impact of various parameters, such as solid-to-liquid ratio (2–200 g/L), grain size (0.063–0.2 mm, 0.5–1 mm, 1–2 mm), temperature (room temperature and 10 °C), contact time (5–108 days), initial U(VI) concentration (3 × 10⁻⁹ to 6 × 10⁻⁵ M), and background electrolyte (synthetic Äspö groundwater and 0.1 M NaClO₄) on the U(VI) sorption onto anoxic diorite was studied under anoxic conditions (N₂). Comparatively, U(VI) sorption onto oxidized diorite material was studied under ambient atmosphere (pCO₂ = 10^−3.5 atm). Conventional distribution coefficients, K_d, and surface area normalized distribution coefficients, K_a, were determined. The K_d value for the U(VI) sorption onto anoxic diorite in synthetic Äspö groundwater under anoxic conditions by investigating the sorption isotherm amounts to 3.8 ± 0.6 L/kg which corresponds to K_a = 0.0030 ± 0.0005 cm (grain size 1–2 mm). This indicates a weak U sorption onto diorite which can be attributed to the occurrence of the neutral complex Ca₂UO₂(CO₃)₃(aq) in solution. This complex was verified as predominating U species in synthetic Äspö groundwater by time-resolved laser-induced fluorescence spectroscopy (TRLFS). Compared to U sorption at room temperature under anoxic conditions, U sorption is further reduced at decreased temperature (10 °C) and under ambient atmosphere. The U species in aqueous solution as well as sorbed on diorite were studied by in situ time-resolved attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy. A predominant sorbing species containing a UO₂(CO₃)₃⁴⁻ moiety was identified. The extent of U sorption onto diorite was found to depend more on the low sorption affinity of the Ca₂UO₂(CO₃)₃(aq) complex than on reduction processes of uranium.     

Granulites,CO2 and graphite

Externally derived, pure CO₂ that mixes with a carbon-(under)saturated C-O-H fluid in lower crustal granulites may result in graphite precipitation if the host-rock oxygen fugacity (f_O2^rock) is below the upper f_O2 limit of graphite. The maximum relative amount of graphite that can precipitate varies between a few mol% up to more than 25 mol%, depending on pressure, temperature, and host-rock redox state. The maximum relative amount of graphite that can precipitate from an infiltrating CO₂ fluid into a dry granulite (CO fluid system) varies between zero and a few mol%. Thermodynamic evaluation of the graphite precipitation process shows that CO₂ infiltration into lower crustal rocks does not always result in a carbon (super)saturated fluid. In that case, graphite precipitation is only possible if carbon saturation can be reached as a result of the reaction CO₂ → CO + ½ O₂. Graphite that has been precipitated during granulite facies metamorphic conditions can subsequently be absorbed by a COH fluid during retrograde metamorphism. It is also possible, however, that significant amounts of graphite precipitate from a COH fluid during retrograde metamorphism. This study shows that interpreting the presence or absence of graphite in granulites with respect to CO₂ infiltration requires detailed information on the P–T–f_O2^rock conditions, the relative amount of CO₂ that infiltrates into the rock, and whether H₂O is present or not.     

Geology and fluid evolution of the Wangfeng orogenic-type gold deposit,Western Tian Shan,China

The Wangfeng gold deposit is located in Western Tian Shan and the central section of the Central Asian Orogenic Belt (CAOB). The deposit is mainly hosted in Precambrian metamorphic rocks and Caledonian granites and is structurally controlled by the Shenglidaban ductile shear zone. The gold orebodies consist of gold-bearing quartz veins and altered mylonite. The mineralization can be divided into three stages: quartz–pyrite veins in the early stage, sulfide–quartz veins in the middle stage, and quartz–carbonate veins or veinlets in the late stage. Ore minerals and native gold mainly formed in the middle stage. Four types of fluid inclusions were identified based on petrography and laser Raman spectroscopy: CO₂–H₂O inclusions (C-type), pure CO₂ inclusions (PC-type), NaCl–H₂O inclusions (W-type), and daughter mineral-bearing inclusions (S-type). The early-stage quartz contains only primary CO₂–H₂O fluid inclusions with salinities of 1.62 to 8.03 wt.% NaCl equivalent, bulk densities of 0.73 to 0.89 g/cm³, and homogenization temperatures of 256 °C–390 °C. Vapor bubbles are composed of CO₂. The middle-stage quartz contains all four types of fluid inclusions, of which the CO₂–H₂O and NaCl–H₂O types yield homogenization temperatures of 210 °C–340 °C and 230 °C–300 °C, respectively. The CO₂–H₂O fluid inclusions have salinities of 0.83 to 9.59 wt.% NaCl equivalent and bulk densities of 0.77 to 0.95 g/cm³, with vapor bubbles composed of CO₂, CH₄, and N₂. Fluid inclusions in the late-stage quartz are NaCl–H₂O solution with low salinities (0.35–3.87 wt.% NaCl equivalent) and low homogenization temperatures (122 °C–214 °C). The coexistence of inclusions of these four types in middle-stage quartz suggests that fluid boiling occurred in the middle-stage mineralization. Trapping pressures estimated from CO₂–H₂O inclusions are 110–300 MPa and 90–250 MPa for the early and middle stages, respectively, suggesting that gold mineralization mainly occurred at depths of about 10 km. In general, the Wangfeng gold deposit originated from a metamorphic fluid system characterized by low salinity, low density, and enrichment of CO₂. Depressurized fluid boiling caused gold precipitation. Given the regional geology, ore geology, fluid-inclusion features, and ore-forming age, the Wangfeng gold deposit can be classified as a hypozonal orogenic gold deposit.