H2O in metamorphism and unexpected behaviour in the preservation of metamorphic mineral assemblages

The preservation of mineral assemblages that were fluid‐present during their prograde history is primarily related to the consumption of the fluid by growth of more hydrous minerals as the retrograde history begins. The range of behaviour relating to the preservation of mineral assemblages is examined using calculated phase diagrams for fluid‐saturated conditions, contoured for the H₂O content of the mineral assemblage. At equilibrium, as a mineral assemblage crosses contours of decreasing H₂O content along a pressure–temperature path, it dehydrates, the fluid being lost from the rock. If the assemblage crosses contours of increasing H₂O content, the mineral assemblage starts to rehydrate using any fluid on its grain boundaries. When the rock has consumed its fluid, the resulting mineral assemblage is that preserved in the rock. Conditions relating to the preservation of mineral assemblages are discussed, and examples of the consequences of different pressure–temperature paths on preservation in a metapelitic and a metabasic rock composition are considered on phase diagrams calculated with thermocalc .     

An empirical NaKCa geothermometer for natural waters

An empirical method of estimating the last temperature of water-rock interaction has been devised. It is based upon molar Na, K and Ca concentrations in natural waters from temperature environments ranging from 4 to 340°C. The data for most geothermal waters cluster near a straight line when plotted as the function $\text{log (}\text{Na}\text{K}\text{) + β log [ √}\text{(Ca)}\text{Na}\text{]}$ vs reciprocal of absolute temperature, where β is either $\text{1}\text{3}$ or $\text{4}\text{3}$ depending upon whether the water equilibrated above or below 100°C. For most waters tested, the method gives better results than the $\text{Na}\text{K}$ methods suggested by other workers. The ratio $\text{Na}\text{K}$ should not be used to estimate temperature if $\text{√ (}\text{M}{}_{\mathrm{Ca}}\text{)}\text{M}{}_{\mathrm{Na}}$ is greater than 1. The $\text{Na}\text{K}$ values of such waters generally yield calculated temperatures much higher than the actual temperature at which water interacted with the rock.A comparison of the composition of boiling hot-spring water with that obtained from a nearby well (170°C) in Yellowstone Park shows that continued water-rock reactions may occur during ascent of water even though that ascent is so rapid that little or no heat is lost to the country rock, i.e. the water cools adiabatically. As a result of such continued reaction, waters which dissolve additional Ca as they ascend from the aquifer to the surface will yield estimated aquifer temperatures that are too low. On the other hand, waters initially having enough Ca to deposit calcium carbonate during ascent may yield estimated aquifer temperatures that are too high if aqueous Na and K are prevented from further reaction with country rock owing to armoring by calcite or silica minerals.The Na-K-Ca geothermometer is of particular interest to those prospecting for geothermal energy. The method also may be of use in interpreting compositions of fluid inclusions.     

Fluid-mineral equilibria in a hydrothermal system,Roosevelt hot springs,Utah

The availability of fluids and drill cuttings from the active hydrothermal system at Roosevelt Hot Springs allows a quantitative comparison between the observed and predicted alteration mineralogy, calculated from fluid-mineral equilibria relationships. Comparison of all wells and springs in the thermal area indicates a common reservoir source, and geothermometer calculations predict its temperature to be higher ($\text{288°C ± 10°}$) than the maximum measured temperature of 268°C.The composition of the deep reservoir fluid was estimated from surface well samples, allowing for steam loss, gas release, mineral precipitation and ground-water mixing in the well bore. This deep fluid is sodium chloride in character, with approximately 9700 ppm dissolved solids, a pH of 6.0, and gas partial pressures of O₂ ranging from 10^?32 to 10^?35 atm, CO₂ of 11 atm, H₂S of 0.020 atm and CH₄ of 0.001 atm.Comparison of the alteration mineralogy from producing and nonproducing wells allowed delineation of an alteration pattern characteristic of the reservoir rock. Theoretical alteration mineral assemblages in equilibrium with the deep reservoir fluid, between 150° and 300°C, in the system Na₂O-K₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-H₄SiO₄-H₂O-H₂S-CO₂-HCl, were calculated. Minerals theoretically in equilibrium with the calculated reservoir fluid at $\text{>240°C}$ include sericite, K-feldspar, quartz, chalcedony, hematite, magnetite and pyrite. This assemblage corresponds with observed higher-temperature ($\text{>210°C}$) alteration assemblage in the deeper parts of the producing wells. The presence of montmorillonite and mixed-layer clays with the above assemblage observed at temperatures <210°C corresponds with minerals predicted to be in equilibrium with the fluid below 240°C.Alteration minerals present in the reservoir rock that do not exhibit equilibrium with respect to the reservoir fluid include epidote, anhydrite, calcite and chlorite. These may be products of an earlier hydrothermal event, or processes such as boiling and mixing, or a result of errors in the equilibrium calculations as a result of inadequate thermochemical data.     

Partition of trace elements in co-existing biotite,muscovite and potassium feldspar of granitic rocks,northern Portugal

Chemical analyses are given for Na, K, and trace elements of muscovite and potassium feldspar of granitic rocks. The distribution of trace elements in co-existing minerals suggests that equilibrium was attained and that muscovite is a primary mineral. These observations and the comparison of the trace-element chemistry of megacrysts and groundmass potassium feldspars of porphyritic rock types lead to the conclusion that the megacrysts are in face phenocrysts which crystallized in equilibrium with the other minerals of the rock.The ranges of values of the distribution coefficients K_D(Rb/K) and K_D(Cs/K) in mineral pairs confirm other observations on the equilibrium among various minerals. However, application of experimental data on the temperature effect on K_D leads to results conflicting with the petrologic observations. The possible influence of other factors on K_D is analyzed and among these factors the composition of the feldspar and the solidus-liquidus temperature interval may play a dominant role.     

Constraints of the formation of carbonatites in the Chernigovka Massif,Azov Region,Ukraine

Data on compositions of coexisting minerals in the graphite-bearing carbonatites of the Chernigovka massif are reported. Thermodynamic analysis of these results made it possible to establish that the temperature of equilibrium between graphite, dolomite, calcite, magnetite, and olivine for silica activity buffered by the (zircon + baddeleyite) assemblage is approximately 600°C. The minimal pressure of formation of these mineral assemblages is approximately 0.2 GPa, which is consistent with estimates of the erosion depth for the Chernigovka massif. The oxygen fugacity typical of the graphite-bearing carbonatite is 0.6–0.8 log units below the quartz-magnetite-fayalite buffer. Such values are typical of magmatic systems, e.g., basalts of the mid-ocean ridges (MORB). At 600°C, the gas phase in the C-H-O system equilibrated with the mineral assemblage of the carbonatite studied is dominated by CO₂ and H₂O, whereas methane-rich fluids appear at lower temperatures.     

Hydrogeochemical and hydrogeological investigations of thermal waters in the Usak Area (Turkey)

Thermal waters of the Usak area have temperatures ranging from 33 to 63°C and different chemical compositions. These waters hosted by the Menderes Metamorphic rocks emerge along fault lineaments from two geothermal reservoirs in the area. The first reservoir consists of gneiss, schists, and marbles of the Menderes Metamorphic rocks. The recorded reservoir is Pliocene lacustrine limestone. Hydrogeochemical studies indicate that thermal waters were mixed with surface waters before and/or after heating at depth. The results of mineral equilibrium modeling indicate that all the thermal waters are undersaturated at discharge temperatures for gypsum, anhydrite, and magnesite minerals. Calcite, dolomite, aragonite, quartz, and chalcedony minerals are oversaturated in all of the thermal waters. Water from the reservoir temperatures of the Usak area can reach upto120°C. According to δ¹⁸O and δ²H values, all thermal and cold groundwater are of meteoric origin.     

The rare alkalies in hydrothermal alteration at Wairakei and Broadlands,geothermal fields,N.Z.

Drillcores and waters from Wairakei and Broadlands geothermal areas New Zealand have been analyzed for Li, Rb, Cs, Na, K, Mg, Ca, Al, Ti, Mn, and Be. The drillcores were altered to various degrees at temperatures below 300°C in slightly alkaline chloride water, probably derived from rock-water interaction in untapped horizons at higher temperature. It changes its composition as it leaches Ca and Na from the rock and adds K, Rb, Cs and Li. Evaluation of these changes in relation to the dimensions of the altered zone under observation suggests that a high mass ratio of water to rock (e.g., 100) and a period of up to 1 million years are responsible for the present stage of alteration.Increase of K and Rb in the altered rocks is a result of the formation of abundant adularia in addition to illite. The $\text{K}\text{Rb}$ ratio of the rock decreases during alteration but remains higher than that of the fluid. Only clay materials and zeolites that preferentially absorb Rb give slightly lower $\text{K}\text{Rb}$ ratios than the fluid.The mineral phases responsible for the uptake of lithium during alteration are chlorite (300 ppm Li) and quartz (up to 430 ppm Li). Li uptake in quartz is considered to be the mechanism by which Al-rich quartz crystallises from alumino-silicates. $\text{Li}\text{Al}$ atomic ratios of 0.3–0.57 and Al concentrations up to 3000 ppm have been observed.Relatively small concentrations of Cs are found in potassic minerals (e.g. 10 ppm Cs in adularia, 44 ppm Cs in illite). However, 240 ppm Cs are found in wairakite from Wairakei equilibrated at 235°C. Lower equilibration temperatures may lead to higher cesium concentrations. This effect, in conjunction with a more concentrated hydrothermal fluid, could explain a content of 4500 ppm Cs in wairakite extracted from a drillcore taken in the El-Tatio geothermal field in Chile.     

Magnesium correction to the NaKCa chemical geothermometer

Equations and graphs have been devised to correct for the adverse effects of magnesium upon the Na-K-Ca chemical geothermometer. Either the equations or graphs can be used to determine appropriate temperature corrections for given waters with calculated NaKCa temperatures > 70°C and R < 50, where $\text{R = {}\text{Mg}\text{(Mg + Ca + K)}\text{} × 100}$ with cation concentrations expressed in equivalents. Waters with R > 50 are probably derived from relatively cool aquifers with temperatures approximately equal to the measured spring temperature, irrespective of much higher calculated Na-K-Ca temperatures.     

Rhondonite solubility and thermodynamic properties of aqueous MnCl2 in the system MnOSiO2HClH2O

The solubility of rhodonite, represented by the reaction MnSiO₃ (rhodonite) + 2HCl⁰ = MnCl₂⁰ + SiO₂ (quartz) + H₂O, was investigated experimentally in the temperature range 400°–700°C at 1 and 2 kbar by rapid-quench hydrothermal techniques and the Ag-AgCl buffer methods. Variations in the molalities of associated hydrogen chloride (m_HCl⁰) as a function of the molalities of total Mn indicate that Mn in the fluid in equilibrium with the assemblage rhodonite + quartz is predominantly associated as MnCl₂⁰. The Mn:Cl in the fluid ?2, indicating that Mn⁺² is the dominant oxidation state.The solubility data were used to calculate the equilibrium constant of the above reaction as a function of temperature, pressure, and the difference in Gibbs free energy of formation between MnCl₂⁰ and HCl⁰. The equilibrium constants of solubility for Mn minerals for which thermochemical data are available were also calculated. Calculated mineral solubilities were used in conjunction with the data of Frantz et al. (1981) to calculate the composition of supercritical fluids in equilibrium with Mn-bearing phases and assemblages. At 400°C and 1000 bars, supercritical fluids in equilibrium with olivines of compositions similar to those present in MORB tend to be enriched in Mn, despite the low mole fraction of tephroite in the olivine. Supercritical fluids in equilibrium with the assemblage quartz-hematite-rhodonite at 500° and 400°C and 1000 bars show high concentrations of Mn relative to Fe. Manganese concentrations in the fluids increase with decrease in the mole fraction of H, whereas Fe concentrations decrease. The data indicate that H fugacity plays a significant role in the separation of Mn from Fe in chloride-bearing hydrothermal fluids at supercritical temperatures.     

Thermal and redox equilibrium conditions of the upper-mantle xenoliths from the Quaternary volcanoes of NW Spitsbergen,Svalbard Archipelago

Upper-mantle xenoliths in Cenozoic basalts of northwestern Spitsbergen are rocks of peridotite (spinel lherzolites) and pyroxenite (amphibole-containing garnet and garnet-free clinopyroxenites, garnet clinopyroxenites, and garnet and garnet-free websterites) series. The upper-mantle section in the depth range 50–100 km is composed of spinel peridotites; at depths of 80–100 km pyroxenites (probably, dikes or sills) appear. The equilibrium conditions of parageneses are as follows: in the peridotites—730–1180 °C, 13–27 kbar, and oxygen fugacity of − 1.5 to + 0.3 log. un.; in the pyroxenites—1100–1310 °C, 22–33 kbar. The pyroxenite minerals have been found to contain exsolved structures, such as orthopyroxene lamellae in clinopyroxene and, vice versa, clinopyroxene lamella in orthopyroxene. The formation temperatures of unexsolved phases in orthopyroxene and clinopyroxene are nearly 100–150 °C higher than the temperatures of the lamellae–matrix equilibrium and the equilibrium of minerals in the rock. The normal distribution of cations in the spinel structure and the equilibrium distribution of Fe^2 + between the M1 and M2 sublattices in the orthopyroxenes point to the high rate of xenolith ascent from the rock crystallization zone to the surface. All studied Spitsbergen rock-forming minerals from mantle xenoliths contain volatiles in their structure: OH⁻, crystal hydrate water H₂O_cryst, and molecules with characteristic CH and CO groups. The first two components are predominant, and the total content of water (OH– + H₂O_cryst) increases in the series olivine → garnet → orthopyroxene → clinopyroxene. The presence of these volatiles in the nominally anhydrous minerals (NAM) crystallized at high temperatures and pressures in the peridotites and pyroxenites testifies to the high strength of the volatile–mineral bond. The possibility of preservation of volatiles is confirmed by the results of comprehensive thermal and mass-spectral analyses of olivines and clinopyroxene, whose structures retain these components up to 1300 °C. The composition of hypothetic C–O–H fluid in equilibrium (in the presence of free carbon) with the underlying mantle rocks varies from aqueous (> 80% H₂O) to aqueous–carbonic (~ 60% H₂O). The fluid becomes essentially aqueous when the oxygen activity in the system decreases. However, there is no strict dependence of the redox conditions on the depth of formation of xenoliths.     

Ore minerals and geochemical characterization of the Dungash gold deposit,South Eastern Desert,Egypt

The Dungash historic gold mine is located in the South Eastern Desert of Egypt. The gold-bearing quartz veins are hosted by the metavolcanic and metavolcaniclastic rocks along an ENE–WSW trending shear zone. Alteration types recorded in the wall rocks are sericitization, silicification, carbonatization, chloritization, sulfidization, ferruginization, and listwanitization. The ore mineral assemblage comprises arsenopyrite, pyrite, native gold, pyrrhotite, sphalerite, chalcopyrite, and galena. The primary sulfide mineral assemblage formed during a hypogene hydrothermal stage whereas anglesite and goethite occur as secondary supergene phases. Microthermometric fluid inclusion analysis revealed that the auriferous quartz precipitated from a moderately saline (5 to 11.22 wt% NaCl_equiv) solution at temperatures above the recorded homogenization temperatures (T _h), which range from 380 to 177 °C. The minimum pressures of trapping are between 350 and 400 bars. The fluid evolution during mineralization is explained by mixing of a magmatic fluid with meteoric waters. Initially, the high temperature and moderately saline magmatic fluid dominated and progressively became diluted with meteoric waters. Highest gold content is recorded in the carbonatized zone and the quartz veins. However, gold content in the carbonatized zone of the footwall exceeds several times its content in the quartz veins and the carbonatized zone of the hanging wall.     

Experimental Study of the Melting Reaction and Genetic Mechanism of Mineral Phase Transformation in Granulite Facies Metamorphism

The high-temperature and high-pressure experiment on natural block rock indicates that dehydration-melting of hydrous biotite (Bi) and partial melting of felsic minerals in garnet-biotite-plagioclase gneiss are mainly controlled by temperature, while mineral phase transformation is not only controlled by temperature-pressure conditions but also genetically associated with hydrous mineral dehydration-melting and partial melting of felsic minerals. According to the characteristics of biotite dehydration-melting and garnet transformation reaction, three stages may be distinguished: (1) when the experimental temperature is 700℃, biotite transforms to ilmenite (Ilm) + magnetite (Mt) + H2O and garnet to magnetite (Mt); (2) when the temperature is 730-760℃, biotite is dehydrated and melted and transformed into K2O-rich melt + Ilm + Mt, and garnet, into hypersthene (Hy) + cordierite (Crd); (3) when the temperature is up to or higher than 790℃, biotite is dehydrated and melted and transformed into melt + Hy +     

苏北东海青龙山变斑状榴辉岩的变质演化

青龙山部分榴辉岩以含绿帘石、蓝晶石和滑石变斑晶为特征,但是其峰变质矿物组合由基质中细粒的石榴石+绿辉石+多硅白云母+柯石英+金红石+绿帘石构成,它们定向分布形成片理构造。相图中石榴石组成等值线温压计确定的峰变质组合为:石榴石+绿辉石+多硅白云母+蓝晶石+金红石+柯石英+硬柱石+滑石,与岩相学观察结果不符。这可能是超高压变质流体显著偏离计算相图假设的流体相为纯水所致。无定向的变斑晶切割片理,晚于峰变质组合结晶于弱剪切应力的环境。岩相学观察和相图模拟结果显示,变斑晶的形成顺序为蓝晶石-绿帘石-滑石。绿帘石在<2GPa大量生长形成变斑晶,它包含柯石英并不一定说明二者平衡共生,更可能是温压快速下降后峰变质组合被绿帘石变斑晶包含。由矿物组合限定的青龙山变斑状榴辉岩P-T路径为典型的"发卡式"。含水矿物出现于岩石的各个变质组合,并且沿退变质P-T路径陆续结晶数量增多,表明在退变质过程中不断有流体渗入岩石。     

Mineral-solution equilibria—V. Solubilities of rock-forming minerals in supercritical fluids

The solubility constants of sixty-nine rock-forming minerals have been computed for temperatures between 400 and 600°C at 1000 and 2000 bar pressure using the free-energy data for aqueous solutes presented in Parts I through IV of this series combined with the thermodynamic properties of minerals from Helgesonet al. (1978). An example describing solution compositions in equilibrium with a spilite is discussed. A computer program for calculating solution compositions in equilibrium with mineral assemblages is included as an appendix.     

http://www.sciencedirect.com/science/article/pii/S1674987112000643

Incipient charnockites represent granulite formation on a mesoscopic scale and have received considerable attention in understanding fluid processes in the deep crust.Here we report new petrological data from an incipient charnockite locality at Rajapalaiyam in the Madurai Block,southern India,and discuss the petrogenesis based on mineral phase equilibrium modeling and pseudosection analysis. Rajapalaiyam is a key locality in southern India from where diagnostic mineral assemblages for ultrahigh-temperature（UHT） metamorphism have been reported.Proximal to the UHT rocks are patches and lenses of charnockite（Kfs + Qtz + Pl + Bt + Opx + Grt + Ilm） occurring within Opx-free Grt-Bt gneiss（Kfs + Pl + Qtz + Bt + Grt + Ilm + Mt） which we report in this study.The application of mineral equilibrium modeling on the charnockitic assemblage in NCKFMASHTO system yields a p-T range of～820℃and～9 kbar.Modeling of the charnockite assemblage in the MnNCKFMASHTO system indicates a slight shift of the equilibrium condition toward lower p and T（～760℃and～7.5 kbar）. which is consistent with the results obtained from geothermobarometry（710—760℃,6.7—7.5 kbar）. but significantly lower than the peak temperatures（>1000℃） recorded from the UHT rocks in this locality,suggesting that charnockitization is a post-peak event.The modeling of T versus molar H₂O content in the rock（M（H₂O）） demonstrates that the Opx-bearing assemblage in charnockite and Opxfree assemblage in Grt-Bt gneiss are both stable at M（H₂O） = 0.3 mol%-0.6 mol%.and there is no significant difference in water activity between the two domains.Our finding is in contrast to the previous petrogenetic model of incipient charnockite formation which envisages lowering of water activity and stabilization of orthopyroxene through breakdown of biotite by dehydration caused by the infiltration of CO₂-rich fluid.T-X_Fe³⁺（= Fe₂O₃/（FeO + Fe₂O₃） in mole） pseudosections suggest that the oxidation condition of the rocks played a major role on the stability of orthopyroxene:Opx is stable at X_Fe³⁺ <0.03 in charnockite.while Opx-free assemblage in Grt-Bt gneiss is stabilized at X_Fe³⁺ >0.12.Such low oxygen fugacity conditions of X_Fe³⁺ <0.03 in the charnockite compared to Grt-Bt gneiss might be related to the infiltration of a reduced fluid（e.g.,H₂O + CH₄） during the retrograde stage.     

Dehydration veins in diagenetic and very-low-grade metamorphic rocks: features of the crustal seismogenic zone and their significance to mineral facies

Abstract Declining temperatures during decay of a hydrothermal system, or during uplift and erosion, tend to result in veins involving progressive hydration reactions, e.g. veins with laumontite cutting prehnitepumpellyite facies rocks, and stilbite veins cutting laumontite veins. In contrast, examples are described of analcime replacement of heulandite along fractures in heulanditized vitric tuff, of replacement of analcime by albite along fractures in quartz-analcime rock, of joint-controlled replacement of heulandite in tuff by laumontite + quartz + (Na, K)-feldspars, of replacement of laumontite by prehnite + quartz along fractures in alumontitized vitric tuff, and of laumontitebearing feldspathic sandstones cut by vein assemblages of quartz and prehnite ° Calcite. The vein mineral assemblage, sometimes with pumpellyite and/or epidote in the prehnite-bearing veins, tends to spread as a zone of dehydration into the adjacent country rock. Except perhaps for albite replacement of analcime, and for laumontite replacement of heulandite, these open-system reactions involve cation activity ratios in the fluid. All involve dehydration. They are favoured by an increase in temperature, and except under certain situations where P-T equilibrium curves have negative slopes, are favoured by a fall in P_H2O. Evidence indicates that in at least some cases the triggering mechanism was a drop in P_H2O; this may be a widespread phenomenon associated with brittle fracture in the seismogenic upper crust. This may cause fluid pressure to drop from values approaching lithostatic to nearer hydrostatic, and equilibrium may be displaced to yield a less hydrous assemblage that appears as a dehydration vein and vein verge. The dehydration vein assemblage may be diagnostic of a higher grade mineral facies and adds to the mineral complexity attributable to varying permeabilities and fluid pressures in upper crustal strata. Mineral facies are likely to be more uniformly distributed in higher grade rocks from below the brittle-ductile transition zone. Reactions involving complex solid solutions are inappropriate as facies boundaries.     

Crystallization of quartz dioritic magmas at 2 and 1 kbar: experimental results

Crystallization experiments were performed on quartz diorite (~55 wt.% SiO₂, 3.1–8.4 wt.% MgO) from the G?siniec Intrusion (Bohemian Massif, SW Poland) at 1?2 kbar, 750–850°C, various mole fractions of water and with fO₂ buffered by the NNO buffer. The two natural quartz diorites (leucocratic poikilitic quartz diorite - ‘LPD’ and melanocratic quartz diorite - ‘MD’) differ in whole rock and mineral composition with MD being richer in MgO and poorer in CaO than LPD, probably due to accumulation of mafic minerals or melt removal in MD. LPD represents melt composition and is used to reconstruct crystallization conditions in the G?siniec Intrusion. The crystallization history of LPD magma, deduced from experimental and natural mineral compositions, includes a higher pressure stage probably followed by emplacement at ~2 kbar of partly crystallized magma at temperatures ~850?800°C and quick cooling. The mineral assemblage present in LPD requires water contents in the magma of at least 5 wt% and oxygen fugacity below that controlled by the NNO buffer. The compositions of mafic minerals in the MD composition were equilibrated at temperatures below 775°C and at subsolidus conditions. The equilibration was probably due to the reaction between water-rich, oxidizing residual melt and the cumulatic-restitic mineral assemblage. MD is characterized by occurrence of the euhedral cummingtonite and increasing anorthite content in the rims of plagioclase. A similar reaction was reproduced experimentally in both LPD and MD compositions indicating that cummingtonite may be a late magmatic phase in quartz dioritic systems, crystallizing very close to solidus and only from water saturated magma.     

Fluorite solubility equilibria in selected geothermal waters

Calculation of chemical equilibria in 351 hot springs and surface waters from selected geothermal areas in the western United States indicate that the solubility of the mineral fluorite, CaF₂, provides an equilibrium control on dissolved fluoride activity. Waters that are undersaturated have undergone dilution by non-thermal waters as shown by decreased conductivity and temperature values, and only 2% of the samples are supersaturated by more than the expected error. Calculations also demonstrate that simultaneous chemical equilibria between the thermal waters and calcite as well as fluorite minerals exist under a variety of conditions.Testing for fluorite solubility required a critical review of the thermodynamic data for fluorite. By applying multiple regression of a mathematical model to selected published data we have obtained revised estimates of the pK (10,96), ΔG^o_f (?280.08 kcal/mole), ΔH^o_f (?292.59 kcal/mole), S° (16.39 cal/deg/mole) and C^o_P (16.16 cal/deg/mole) for CaF₂ at 25°C and 1 atm. Association constants and reaction enthalpies for fluoride complexes with boron, calcium and iron are included in this review. The excellent agreement between the computer-based activity products and the revised pK suggests that the chemistry of geothermal waters may also be a guide to evaluating mineral solubility data where major discrepancies are evident.     

Chemistry,isotope values (δD, δ18O, δ34SSO4) and temperatures of the water inflows in two Gotthard tunnels,Swiss Alps

Water inflows in the Gotthard Highway Tunnel and in the Gotthard Exploration Tunnel are meteoric waters infiltrating at different elevations, on both sides of an important orographic divide. Limited interaction of meteoric waters with gneissic rocks produces Ca–HCO₃ and Na–Ca–HCO₃ waters, whereas prolonged interaction of meteoric waters with the same rocks generates Na–HCO₃ to Na–SO₄ waters. Waters circulating in Triassic carbonate-evaporite rocks have a Ca–SO₄ composition. Calcium-Na–SO₄ waters are also present. They can be produced through interaction of either Na–HCO₃ waters with anhydrite or Ca–SO₄ waters with a local gneissic rock, as suggested by reaction path modeling. An analogous simulation indicates that Na–HCO₃ waters are generated through interaction of Ca–HCO₃ waters with a local gneissic rock. The two main SO₄-sources present in the Alps are leaching of upper Triassic sulfate minerals and oxidative dissolution of sulfide minerals of crystalline rocks. Values of δ³⁴S_SO4 < ∼+9‰ are due to oxidative dissolution of sulfide minerals, whereas δ³⁴S_SO4 >∼+9‰ are controlled either by bacterial SO₄ reduction or leaching of upper Triassic sulfate minerals. Most waters have temperatures similar to the expected values for a geothermal gradient of 22°C/km and are close to thermal equilibrium with rocks. However relatively large, descending flows of cold waters and ascending flows of warm waters are present in both tunnels and determine substantial cooling and heating, respectively, of the interacting rocks. The most import upflow zone of warm, Na-rich waters is below Guspisbach, in the Gotthard Highway Tunnel, at 6.2–9.0 km from the southern portal. These warm waters have equilibrium temperatures of 65–75°C and therefore constitute an important low-enthalpy geothermal resource.     

Geology and inclusion studies on the genesis of the Baolun gold deposit in Hainan Province,South China

The late Triassic Baolun gold deposit hosted by Silurian phyllites is a large‐scale high‐grade gold deposit in Hainan Island, South China. The ores can be classified into quartz‐vein dominated type and less altered rock type. Three mineralization stages were recognized by mineral assemblages. The early stage, as the most important mineralization stage, is characterized by a quartz–native gold assemblage. The muscovite?quartz?pyrite?native gold assemblage is related to the intermedium mineralization stage. In late mineralization stage, native gold and Bi‐bearing minerals are paragenetic minerals. Microthermometry analyses show that the early mineralization stage is characterized by two types of fluid inclusions, including CO₂‐rich inclusions (C‐type) and aqueous inclusions (W‐type). C‐type inclusions homogenize at 276–335°C with an averaged value of 306°C and have salinities of 1.0–10.0 wt% NaCl equivalent (mean value of 4.9 wt% NaCl equivalent). W‐type inclusions homogenize at 252–301°C (mean value of 278°C) with salinity of 4.0–9.7 wt% NaCl equivalent (mean value of 7.4 wt% NaCl equivalent). In intermedium mineralization stage, C‐type and W‐type inclusions homogenize at 228–320°C (mean value of 283°C) and 178–296°C (mean value of 241°C), with salinities of 2.4–9.9 wt% NaCl equivalent (mean value of 6.5 wt% NaCl equivalent) and 3.7–11.7 wt% NaCl equivalent (mean value of 7.7 wt% NaCl equivalent), respectively. No suitable mineral, such as quartz or calcite, was found for fluid inclusion study from late mineralization stage. In contrast, only aqueous inclusions were found from post‐ore barren veins, which yielded lower homogenization temperatures ranging from 168–241°C (mean value of 195°C) and similar salinities (2.6–12.6 wt% NaCl equivalent with averaged value of 7.2 wt% NaCl equivalent). The different homogenization temperatures and similar salinities of C‐type and W‐type from each mineralization stage indicate that fluid immiscibility and boiling occurred. The Baolun gold deposit was precipitated from a CO₂‐bearing mesothermal fluid, and formed at a syn‐collision environment following the closure of the Paleo‐Tethys.