A model of early evolution of karst conduits affected by subterranean CO2 sources

 In investigating early karstification of one-dimensional conduits by computer models, so far one has assumed that the CO₂ content of the calcite aggressive water stems entirely from the surface. Subterranean sources of CO₂, however, can rejuvenate the solutional power of water already close to equilibrium with respect to calcite, and boost dissolution rates. In a first scenario we have investigated the influence of a punctual source of CO₂ as the most simple case of release of CO₂ into a karstifiable fracture at some position KL from its entrance of the widening joint with length L, (K<1). The results show that only a small increase of the p _CO2 in the solution to about 0.01 atm is sufficient to reduce the breakthrough times to about 0.3 with respect to the case, where no CO₂ is delivered. Other sources of CO₂ are due to the metabolic activity of microorganisms. The existence of such diverse subterraneous microbial life in karst systems is demonstrated. Whether situated on the fissure surfaces or free floating in the karst water, one basic product of their metabolism is CO₂. This contributes over the whole flow path to the p _CO2 of the karst water. Therefore in a second scenario we assumed a constant rate of CO₂-input along parts of the fracture, as could be delivered by the activity of aerobic bacteria dwelling at its walls. Such a scenario also applies to an extended diffuse CO₂ migration from volcanic activity deep underground. In this case drastic reductions of the breakthrough time by about one order of magnitude are observed. These reductions are enhanced when the fracture aperture width of the initial fracture decreases. The physicochemical mechanisms of enhancement of karstification are discussed in detail by considering the evolution of the fracture aperture width and of the dissolution rates in space and time. Received: 17 December 1998 · Accepted 23 April 1999     

Diurnal Variations of Hydrochemistry in a Travertine-depositing Stream at Baishuitai, Yunnan, SW China

Diurnal variations of hydrochemistry were monitored at a spring and two pools in a travertine-depositing stream at Baishuitai, Yunnan, SW China. Water temperature, pH and specific conductivity were measured in intervals of 5 and 30 min for periods of 1 to 2 days. From these data the concentrations of Ca²⁺, HCO₃⁻, calcite saturation index, and CO₂ partial pressure were derived. The measurements in the spring of the stream did not show any diurnal variations in the chemical composition of the water. Diurnal variations, however, were observed in the water of the two travertine pools downstream. In one of them, a rise in temperature (thus more CO₂ degassing) during day time and consumption of CO₂ due to photosynthesis of submerged aquatic plants accelerated deposition of calcite, whereas in the other pool, where aquatic plants flourished and grew out of the water (so photosynthesis was taking place in the atmosphere), the authors suggest that temperature-dependent root respiration underwater took place, which dominated until noon. Consequently, due to the release of CO₂ by the root respiration into water, which dominated CO₂ production by degassing induced by temperature increase, the increased dissolution of calcite was observed. This is the first time anywhere at least in China that the effect of root respiration on diurnal hydrochemical variations has been observed. The finding has implications for sampling strategy within travertine-depositing streams and other similar environments with stagnant water bodies such as estuaries, lakes, reservoirs, pools and wetlands, where aquatic plants may flourish and grow out of water.     

Effect of injected CO2 on geochemical alteration of the Altmark gas reservoir in Germany

Capturing CO₂ from point sources and storing it in geologic formations is a potential option for allaying the CO₂ level in the atmosphere. In order to evaluate the effect of geological storage of CO₂ on rock-water interaction, batch experiments were performed on sandstone samples taken from the Altmark reservoir, Germany, under in situ conditions of 125 °C and 50 bar CO₂ partial pressure. Two sets of experiments were performed on pulverized sample material placed inside a closed batch reactor in (a) CO₂ saturated and (b) CO₂ free environment for 5, 9 and 14 days. A 3M NaCl brine was used in both cases to mimic the reservoir formation water. For the “CO₂ free” environment, Ar was used as a pressure medium. The sandstone was mainly composed of quartz, feldspars, anhydrite, calcite, illite and chlorite minerals. Chemical analyses of the liquid phase suggested dissolution of both calcite and anhydrite in both cases. However, dissolution of calcite was more pronounced in the presence of CO₂. In addition, the presence of CO₂ enhanced dissolution of feldspar minerals. Solid phase analysis by X-ray diffraction and Mössbauer spectroscopy did not show any secondary mineral precipitation. Moreover, Mössbauer analysis did not show any evidence of significant changes in redox conditions. Calculations of total dissolved solids’ concentrations indicated that the extent of mineral dissolution was enhanced by a factor of approximately 1.5 during the injection of CO₂, which might improve the injectivity and storage capacity of the targeted reservoir. The experimental data provide a basis for numerical simulations to evaluate the effect of injected CO₂ on long-term geochemical alteration at reservoir scale.     

Étude expérimentale de la réactivité du CO2 supercritique vis-à-vis de phases minérales pures. Implications pour la séquestration géologique de CO2

Carbon dioxide sequestration in deep aquifers and depleted oilfields is a potential technical solution for reducing green-house gas release to the atmosphere: the gas containment relies on several trapping mechanisms (supercritical CO₂, CO_2(sc), dissolution together with slow water flows, mineral trapping) and on a low permeability cap-rock to prevent CO_2(sc), which is less dense than the formation water, from leaking upwards. A leakproof cap-rock is thus essential to ensure the sequestration efficiency. It is also crucial for safety assessment to identify and assess potential alteration processes that may damage the cap-rock properties: chemical alteration, fracture reactivation, degradation of injection borehole seals, etc. The reactivity of the host-rock minerals with the supercritical CO₂ fluid is one of the potential mechanisms, but it is altogether unknown. Reactivity tests have been carried out under such conditions, consisting of batch reactions between pure minerals and anhydrous supercritical CO₂, or a two-phase CO₂/H₂O fluid at 200?°C and 105/160 bar. After 45 to 60 days, evidence of appreciable mineral-fluid reactivity was identified, including in the water-free experiments. For the mixed H₂O/CO₂ experiments, portlandite was totally transformed into calcite; anorthite displayed many dissolution patterns associated with calcite, aragonite, tridymite and smectite precipitations. For the anhydrous CO₂ experiments, portlandite was totally carbonated to form calcite and aragonite; anorthite also displayed surface alteration patterns with secondary precipitation of fibrous calcite. To cite this article: O. Regnault et al., C. R. Geoscience 337 (2005).     

The geochemical effects of benzene,toluene, and xylene (BTX) biodegradation

The geochemical effects of microbially mediated degradation of aromatic hydrocarbons were observed as changes in solution composition of an artificial groundwater in packed-sand laboratory columns. Benzene, toluene, and xylene, both individually and in a combined fashion, were used as substrates in biodegradation experiments conducted under oxygenated and anoxic conditions in columns filled with quartz, calcite, or Fe³⁺-coated quartz sand. Typically, column effluent had increased concentrations of dissolved inorganic C, decreased pH, and decreased concentrations of NO₃ and dissolved O₂ relative to column influent. Efficiency of CO₂ generation was similar for the three different substrates, ranging from 22.5 to 26.6% organic C converted to CO₂. When all three substrates were combined, the percentage of CO₂ produced fell within the range observed in the single substrate experiments. Nitrate disappearance was more varied as a function of substrate identity, with greatest amounts lost when toluene was the substrate. Calcite dissolved as a result of CO₂ generated during the biodegradation reactions, and empirically calculated dissolution rates varied between 1.9 and 4.0 x 10⁻⁹ mmol cm⁻² s⁻¹. The calcite dissolution rate was slower than the biodegradation rate, as evidenced by excess generation of CO₂ relative to Ca²⁺ production. The decrease in pH was less in experiments with calcite present than in those with quartz sand present due to buffering by calcite dissolution. Dissolution of Fe oxyhydroxides was not observed under any experimental conditions.     

Chemographic analysis of metabasite assemblages from c central Scottish Highlands

From the observed textures and mineral associations, chemographic relations have been derived in isobaric T-X_CO2 space for the minerals actinolite, ankerite, calcite, chlorine, epidote, and hornblende in Scottish Dalradian metabasites from Central Perthshire. Mineralogical variations in the carbonate-bearing metabasites within the distances of 0.5-1 km or so, are attributed to varying partial pressures of CO₂ operating during metamorphism.     

Low melting temperature for calcite at 1000 bars on the join CaCO3‐H2O – some geological implications

Melting experiments of calcite were performed on the join CaCO₃‐H₂O at a pressure of 1000 bars. The system evolves to the ternary CaO‐H₂O‐CO₂ system during melting experiments. Our experiments show that partial melting of calcite begins at a low temperature, below 650 °C. Such a low partial melting temperature for carbonates revives the debate about the presence of carbonate melts in the upper crust. More specifically, the conditions for carbonate partial melting are present in carbonate host rocks undergoing contact metamorphism at high temperatures in the presence of water‐rich fluid. The presence of carbonate melts influences physical parameters such as viscosity and permeability in contact aureoles, and, furthermore, decarbonation reactions release massive amounts of CO₂.     

Influences of air CO<Subscript>2</Subscript> on hydrochemistry of drip water and implications for paleoclimate study in a stream-developed cave,SW China

Cave air CO₂ is a vital part of the cave environment. Most studies about cave air CO₂ variations are performed in caves with no streams; there are few studies to date regarding the relationship of cave air CO₂ variations and drip water hydrochemistry in underground stream–developed caves. To study the relationship of underground stream, drip water, and cave air CO₂, monthly and daily monitoring of air CO₂ and of underground stream and drip water was performed in Xueyu Cave from 2012 to 2013. The results revealed that there was marked seasonal variation of air CO₂ and stream hydrochemistry in the cave. Daily variations of cave air CO₂, and of stream and drip water hydrochemistry, were notable during continuous monitoring. A dilution effect was observed by analyzing hydrochemical variations in underground stream and drip water after rainfall. High cave air CO₂ along with low pH and low δ¹³C_DIC in stream and drip water indicated that air CO₂ was one of the dominant factors controlling stream and drip water hydrochemistry on a daily scale. On a seasonal scale, stream flows may promote increased cave air CO₂ in summer; in turn, the higher cave air CO₂ could inhibit degassing of drip water and make calcite δ¹³C more negative. Variation of calcite δ¹³C (precipitated from drip water) was in reverse of monthly temperature, soil CO₂, and cave air CO₂. Therefore, calcite δ¹³C in Xueyu Cave could be used to determine monthly changes outside the cave. However, considering the different precipitation rate of sediment in different seasons, it was difficult to use stalagmites to reconstruct environmental change on a seasonal scale.     

Carbonate diagenesis and feldspar alteration in fracture-related bleaching zones (Buntsandstein,central Germany): possible link to CO<Subscript>2</Subscript>-influenced fluid–mineral reactions

Fracture-related bleaching of Lower Triassic Buntsandstein red beds of central Germany was related to significant carbonate diagenesis and feldspar alteration caused by CO₂-rich fluids. Using cathodoluminescence microscopy and spectroscopy combined with electron microprobe analysis and stable carbon isotope study, two major fluid–mineral interactions were detected: (1) zoned, joint-filling calcites and zoned pore-filling calcite cements, the latter replacing an earlier dolomite, were formed during bleaching. During the calcite formation and dolomite–calcite transformation, iron was incorporated into the calcite cement crystal cores due to Fe availability from the coeval bleaching. The dedolomitisation was ultimately associated with a volume increase. The related permeability decrease implies a certain degree of sealing and increasing retention of CO₂, and the volume increase offers a minor CO₂ sink. Carbonate-rich sandstone, therefore, can provide advantages for underground CO₂ storage especially when situated in the fringes of the reservoir. (2) Alkali-feldspar alteration due to the bleaching fluids is reflected in cathodoluminescence spectra predominantly by the modulation of a brown luminescence emission peak (~620 nm). This peak represents a newly discovered effect related to alkali-feldspar alteration not solely associated with bleaching. Its modulation by the bleaching is interpreted to be due to Na depletion or a lattice defect in the Si–O bonds of the SiO₄-tetrahedron. Alteration reflected by this luminescence feature has a destructive effect on the feldspars implying the possibility of diminished rock integrity due to bleaching and, hence, CO₂-rich fluids. Two further CL spectral changes related to bleaching occur, (a) decreased intensity between around 570 nm assigned to Mn-depletion, and (b) increased amplitude and wavelength shift of the red (~680 nm) band. Converging evidence from carbonate and feldspar diagenesis, stable carbon isotope data and analysis of fracture directions suggests that CO₂ fluids contributed to a significant extent to the bleaching phenomena and alteration in the studied Buntsandstein strata.     

Tracing high-pressure metamorphism in marbles: Phase relations in high-grade aluminous calcite–dolomite marbles from the Greek Rhodope massif in the system CaO–MgO–Al2O3–SiO2–CO2 and indications of prior aragonite

Four different types of parageneses of the minerals calcite, dolomite, diopside, forsterite, spinel, amphibole (pargasite), (Ti–)clinohumite and phlogopite were observed in calcite–dolomite marbles collected in the Kimi-Complex of the Rhodope Metamorphic Province (RMP). The presence of former aragonite can be inferred from carbonate inclusions, which, in combination with an analysis of phase relations in the simplified system CaO–MgO–Al₂O₃–SiO₂–CO₂ (CMAS–CO₂) show that the mineral assemblages preserved in these marbles most likely equilibrated at the aragonite–calcite transition, slightly below the coesite stability field, at ca. 720 °C, 25 kbar and a_CO2 ~ 0.01. The thermodynamic model predicts that no matter what activity of CO₂, garnet has to be present in aluminous calcite–dolomite-marble at UHP conditions.     

Carbonate chemistry of groundwater from chalk,Givendale, East Yorkshire

Precipitation, soil and spring waters from an outlier of Chalk were analysed over a one year period for field pH, and contents of Ca⁺², Mg⁺², HCO₃^? and other dissolved solids. Measured soil log PCO₂ (atm) varied between a minimum of ?2.60 and maximum of ?1.46, and could be predicted from measurements of soil temperature. Soil waters evolved under open system conditions with respect to soil CO₂, and were undersaturated with calcite during the winter recharge period.The chemistry of the springs is related to their topographic position. Group 1 springs, located below a feather edge of chalk, had both their minimum and maximum PCO₂s predicted by the soil CO₂ data, suggesting open system CO₂ evolution. Group 2 springs, located along the scarp slope had minimum PCO₂s predicted by the soil data, but maximum PCO₂s which could only be explained by a closed system evolution from the maximum soil CO₂ observed. Group 1 springs were close to calcite saturation, whereas Group 2 springs were significantly undersaturated with calcite. The two groups could be identified by linear discriminant analysis of measured Ca²⁺, pH and HCO₃^? concentrations.     

Cave air control on dripwater geochemistry, Obir Caves (Austria): Implications for speleothem deposition in dynamically ventilated caves

There are very few process studies that demonstrate the annual variation in cave environments depositing speleothems. Accordingly, we initiated a monitoring program at the Obir Caves, an Austrian dripstone cave system characterized by a seasonally changing air flow that results in a predictable pattern of high pCO₂ during summer and low pCO₂ in winter. Although similar seasonal changes in soil pCO₂ occur, they are not directly connected with the changes in the subsurface since the dripwaters are fed from a well-mixed source showing little seasonal variation. Cold season flushing by relatively CO₂-poor air enhances degassing of CO₂ in the cave and leads to a high degree of supersaturation of dripwater with regard to calcite. Forced calcite deposition during the cold season also gives rise to a pronounced pattern of synchronous seasonal variations in electrical conductivity, alkalinity, pH, Ca and δ¹³C_DIC which parallel variations recorded in δ¹³C_{cave air}. Chemical components unaffected by calcite precipitation (e.g., δD, δ¹⁸O, SiO₂, SO₄) lack a seasonal signal attesting to a long residence in the karst aquifer. Modeling shows that degassing of CO₂ from seepage waters results in kinetically-enhanced C isotopic fractionation, which contrasts with the equilibrium degassing shown from the Soreq cave in Israel. The Obir Caves may serve as a case example of a dripstone cave whose seepage waters (and speleothems) show intra-annual geochemical variability that is primarily due to chemical modification of the groundwater by a dynamic, bidirectional subsurface air circulation.     

Carbonate cements in Miller field of the UK North Sea: a natural analog for mineral trapping in CO<Subscript>2</Subscript> geological storage

Miller field of the North Sea has had high concentrations of natural CO₂ for ~70 Ma. It is an ideal analog for the long-term fate of CO₂ during engineered storage, particularly for formation of carbonate minerals that permanently lock up CO₂ in solid form. The Brae Formation reservoir sandstone contains an unusually high quantity of calcite concretions; however, C and O stable isotopic signatures suggest that these are not related to the present-day CO₂ charge. Margins of the concretions are corroded, probably because of reduced pH due to CO₂ influx. Dispersed calcite cements are also present, some of which postdate the CO₂ charge and, therefore, are the products of mineral trapping. It is calculated that only a minority of the reservoired CO₂ in Miller (6–24%) has been sequestrated in carbonates, even after 70 Ma of CO₂ emplacement. Most of the CO₂ accumulation is dissolved in pore fluids. Therefore, in a reservoir similar to the Brae Formation, engineered CO₂ storage must rely on physical retention mechanisms because mineral trapping is both incomplete and slow.     

Reconciling the elemental and Sr isotope composition of Himalayan weathering fluxes: insights from the carbonate geochemistry of stream waters

Determining the relative proportions of silicate vs. carbonate weathering in the Himalaya is important for understanding atmospheric CO₂ consumption rates and the temporal evolution of seawater Sr. However, recent studies have shown that major element mass-balance equations attribute less CO₂ consumption to silicate weathering than methods utilizing Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations. To investigate this problem, we compiled literature data providing elemental and ⁸⁷Sr/⁸⁶Sr analyses for stream waters and bedrock from tributary watersheds throughout the Himalaya Mountains. In addition, carbonate system parameters (P_CO2, mineral saturation states) were evaluated for a selected suite of stream waters. The apparent discrepancy between the dominant weathering source of dissolved major elements vs. Sr can be reconciled in terms of carbonate mineral equilibria. Himalayan streams are predominantly Ca²⁺-Mg²⁺-HCO₃⁻ waters derived from calcite and dolomite dissolution, and mass-balance calculations demonstrate that carbonate weathering contributes ∼87% and ∼76% of the dissolved Ca²⁺ and Sr²⁺, respectively. However, calculated Ca/Sr ratios for the carbonate weathering flux are much lower than values observed in carbonate bedrock, suggesting that these divalent cations do not behave conservatively during stream mixing over large temperature and P_CO2 gradients in the Himalaya.The state of calcite and dolomite saturation was evaluated across these gradients, and the data show that upon descending through the Himalaya, ∼50% of the streams evaluated become highly supersaturated with respect to calcite as waters warm and degas CO₂. Stream water Ca/Mg and Ca/Sr ratios decrease as the degree of supersaturation with respect to calcite increases, and Mg²⁺, Ca²⁺, and HCO₃⁻ mass balances support interpretations of preferential Ca²⁺ removal by calcite precipitation. On the basis of patterns of saturation state and P_CO2 changes, calcite precipitation was estimated to remove up to ∼70% of the Ca²⁺ originally derived from carbonate weathering. Accounting for the nonconservative behavior of Ca²⁺ during riverine transport brings the Ca/Sr and ⁸⁷Sr/⁸⁶Sr composition of the carbonate weathering flux into agreement with the composition of carbonate bedrock, thereby permitting consistency between elemental and Sr isotope approaches to partitioning stream water solute sources. These results resolve the dissolved Sr²⁺ budget and suggest that the conventional application of two-component Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations has overestimated silicate-derived Sr²⁺ and HCO₃⁻ fluxes from the Himalaya. In addition, these findings demonstrate that integrating stream water carbonate mineral equilibria, divalent cation compositional trends, and Sr isotope inventories provides a powerful approach for examining weathering fluxes.     

Reaction-induced fluid flow in synthetic quartz-bearing marbles

The reaction kinetics and fluid expulsion during the decarbonation reaction of calcite+quartz=wollastonite+CO₂ in water-absent conditions were experimentally investigated using a Paterson-type gas apparatus. Starting materials consisted of synthetic calcite/quartz rock powders with variable fractions of quartz (10, 20, and 30 wt%) and grain sizes of 10 µm (calcite) and 10 and 30 µm (quartz). Prior to reaction, samples were HIPed at 700 °C and 300 MPa confining pressure and varying pore pressures. Initial porosity was low at 2.7–6.3%, depending on pore pressure during HIP and the amount and grain size of quartz particles. Samples were annealed at reaction temperatures of 900 and 950 °C at 150 and 300 MPa confining pressures, well within the wollastonite stability field. Run durations were between 10 min and 20 h. SEM micrographs of quenched samples show growth of wollastonite rims on quartz grains and CO₂-filled pores between rims and calcite grains and along calcite grain boundaries. Measured widths of wollastonite rims vs. time indicate a parabolic growth law. The reaction is diffusion-controlled and reaction progress and CO₂ production are continuous. Porosity increases rapidly at initial stages of the reaction and attains about 10–12% after a few hours. Permeability at high reaction temperatures is below the detection limit of 10^–21 m² and not affected by increased porosity. This makes persistent pore connectivity improbable, in agreement with observed fluid inclusion trails in form of unconnected pores in SEM micrographs. Release of CO₂ from the sample was measured in a downstream reservoir. The most striking observation is that fluid release is not continuous but occurs episodic and in pulses. Ongoing continuous reaction produces increase in pore pressure, which is, once having attained a critical value (P_crit), spontaneously released. Connectivity of the pore space is short-lived and transient. The resulting cycle includes pore pressure build-up, formation of a local crack network, pore pressure release and crack closure. Using existing models for plastic stretching and decrepitation of pores along with critical stress intensity factors for the calcite matrix and measured pore widths, it results that P_crit is about 20 MPa. Patterns of fluid flow based on mineralogical and stable isotope evidence are commonly predicted using the simplifying assumption of a continuous and constant porosity and permeability during decarbonation of the rock. However, simple flow models, which assume constant pore pressure, constant fluid filled porosity, and constant permeability may not commonly apply. Properties are often transient and it is most likely that fluid flow in a specific reacting rock volume is a short-lived episodic process.Editorial responsibility: J. Hoefs     

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。     

Association of Electrum and Calcite and Its Significance to the Genesis of the Hishikari Gold Deposits, Southern Kyushu, Japan

Abstract. Mineral assemblage, precipitation sequence and textures of the gold‐bearing veins from the Hishikari epithermal vein‐type deposits, southern Kyushu, Japan, were examined. In addition, fluid inclusion microthermometry and carbon and oxygen isotopic compositions of calcite were determined. Calcite, and that replaced by quartz, were commonly observed throughout the precipitation sequence of the veins. Thus, calcite must be a more common gangue constituent initially than observed presently. Association of calcite and electrum is observed immediately subsequent to columnar adularia in some vein samples. In addition, close association of electrum with pseudo‐acicular quartz, and electrum with truscottite were observed. The initial coprecipitation of electrum and calcite might be a common phenomenon in the gold‐bearing veins at the Hishikari deposits. The Th (homogenization temperature) data from the Honko‐Sanjin deposits are generally higher than those from the Yamada deposit. Samples that show association of calcite and electrum yielded higher Th (206–217°C, average) than the Th data from calcite associated with low‐grade Au ore or barren (180–204°C, average). The measured Tm (temperature of last melting point of ice) range from ‐0.4 to 0.0°C. The result suggests that the salinity of the hydrothermal solution was low during the precipitation both of calcite associated with Au mineralization and of barren calcite. Fluid inclusion evidence suggestive of boiling of hydrothermal solution for the precipitation of calcite was not recognized in the present work. The δ¹³C and δ¹⁸O values of calcite range from ‐10.8 to —4.7 % and from +3.2 to +15.2 %, respectively. The δ¹³C value of H₂CO₃ and the δ¹⁸O value of H₂O in the hydrothermal fluids calculated assuming isotopic equilibrium with calcite using the temperature obtained by fluid inclusion microthermometry, range from ‐14.4 to ‐9.1 %, and from ‐6.2 to +5.5 %, respectively. Thus, the calculated δ¹⁸O values of H₂O for calcite further confirm the presence of the ¹⁸O‐enriched ore fluids during the mineralization at the Hishikari deposits. The hydrothermal solution isotopically equilibrated with the sedimentary basement rocks was responsible for the gold mineralization associated with calcite.     

Microbial dissolution of calcite at T = 28 °C and ambient pCO2

This study used batch reactors to quantify the mechanisms and rates of calcite dissolution in the presence and absence of a single heterotrophic bacterial species (Burkholderia fungorum). Experiments were conducted at T = 28°C and ambient pCO₂ over time periods spanning either 21 or 35 days. Bacteria were supplied with minimal growth media containing either glucose or lactate as a C source, NH₄⁺ as an N source, and H₂PO₄⁻ as a P source. Combining stoichiometric equations for microbial growth with an equilibrium mass-balance model of the H₂O-CO₂-CaCO₃ system demonstrates that B. fungorum affected calcite dissolution by modifying pH and alkalinity during utilization of ionic N and C species. Uptake of NH₄⁺ decreased pH and alkalinity, whereas utilization of lactate, a negatively charged organic anion, increased pH and alkalinity. Calcite in biotic glucose-bearing reactors dissolved by simultaneous reaction with H₂CO₃ generated by dissolution of atmospheric CO₂ (H₂CO₃ + CaCO₃ → Ca²⁺ + 2HCO₃⁻) and H⁺ released during NH₄⁺ uptake (H⁺ + CaCO₃ → Ca²⁺ + HCO₃⁻). Reaction with H₂CO₃ and H⁺ supplied ∼45% and 55% of the total Ca²⁺ and ∼60% and 40% of the total HCO₃⁻, respectively. The net rate of microbial calcite dissolution in the presence of glucose and NH₄⁺ was ∼2-fold higher than that observed for abiotic control experiments where calcite dissolved only by reaction with H₂CO₃. In lactate bearing reactors, most H⁺ generated by NH₄⁺ uptake reacted with HCO₃⁻ produced by lactate oxidation to yield CO₂ and H₂O. Hence, calcite in biotic lactate-bearing reactors dissolved by reaction with H₂CO₃ at a net rate equivalent to that calculated for abiotic control experiments. This study suggests that conventional carbonate equilibria models can satisfactorily predict the bulk fluid chemistry resulting from microbe-calcite interactions, provided that the ionic forms and extent of utilization of N and C sources can be constrained. Because the solubility and dissolution rate of calcite inversely correlate with pH, heterotrophic microbial growth in the presence of nonionic organic matter and NH₄⁺ appears to have the greatest potential for enhancing calcite weathering relative to abiotic conditions.     

Phase relations of talc and tremolite in metamorphic calcite-dolomite sediments in the southern portion of the Damara Belt (South West Africa)

The occurrence of talc and tremolite in a temperature gradient was investigated in siliceous calcite-dolomite sediments exposed along a strip in the southeastern part of the Damara Orogen. Five bivariant reactions may lead to the formation of talc and tremolite:

1. 3 dolomite+4 quartz+1 H₂O ? 1 talc+3 calcite+3 CO₂
2. 5 talc+6 calcite+4 quartz ? 1 tremolite+6 CO₂+2 H₂O
3. 2 talc+3 calcite ? 1 tremolite+1 dolomite+1 CO₂+1 H₂O
4. 5 dolomite+8 quartz+1 H₂O ? 1 tremolite+3 calcite+7 CO₂
5. 2 dolomite+1 talc+4 quartz ? 1 tremolite+4 CO₂.

The common paragenesis of four mineral assemblages tc+cc+dol+qtz¹ and tre+tc+ cc+qtz with increasing temperature over an extended area show that the reactions must have taken place along the equilibrium curve or when fluid pressure is not constant along the equilibrium plane of reactions (1) or (2). The described occurrence of the five mineral assemblage tre+tc+cc+dol+qtz can be stable only on the isobaric intersection point, or when P _f is variable on the univariant intersection curve of the equilibrium planes of all five reactions. The genetic relations of the described parageneses are illustrated with the help of a phase diagram. Minimum P-T conditions which prevailed during metamorphism in this part of the Damara Orogen have been estimated to be about 590° C and 5 kb.