Chemical and thermodynamic constraints on the hydrothermal transport and deposition of tin: I. Calculation of the solubility of cassiterite at high pressures and temperatures

Estimation of equation of state parameters for Sn⁺⁺ and calculation of the thermodynamic properties of other aqueous species and dissociation constants for various stannous and stannic complexes as a function of temperature permit prediction of the high temperature solution chemistry of tin and calculation of the solubility of cassiterite in hydrothermal solutions. The results of these calculations indicate that in the absence of appreciable chloride and fluoride concentrations, Sn(OH)₂⁰ and Sn(OH)₄⁰ are the predominant tin species in H₂O up to 350°C at ~2 $\text{\$}\text{?}$pH $\text{\$}\text{?}$7.5. The calculations also indicate that chloride complexes of Sn⁺⁺ predominate by several orders of magnitude over their fluoride and hydroxide counterparts in 1–3 molal (m) NaCl solutions, except in the presence of geologically unrealistic concentrations of fluoride or a pH greater than ~3.5 at 250°C or ~5.0 at 350°C. At higher pH values, most of the tin in solution is present as hydroxide complexes, even at concentrations of NaCl as high as 3 m. Calculated values of the solubility of cassiterite at high temperatures compare favorably with experimental data reported in the literature. Depending on the fugacity of oxygen and solution composition, the solubility of cassiterite in hydrothermal solutions may exceed 100 ppm under geologically realistic conditions.     

Physicochemical model of tin behavior in weathering profiles

Numerical simulations of a weathering profile on granite containing 10^–8 mol/L Sn (whose average content in the Earth’s crust is 0.00025%) by the SELECTOR program package indicate that cassiterite SnO₂ solubility under both oxidizing and reducing conditions is no higher than 10^–10 mol/L within the pH range of 3 to 11. The only ion occurring in equilibrium with cassiterite is the neutral Sn(OH)_4(aq) ⁰ complex, which was detected in both oxidizing and reducing environments.     

Estimation of medium effects on equilibrium constants in moderate and high ionic strength solutions at elevated temperatures by using specific interaction theory (SIT): Interaction coefficients involving Cl, OH- and Ac- up to 200°C and 400 bars

In this study, a series of interaction coefficients of the Brønsted-Guggenheim-Scatchard specific interaction theory (SIT) have been estimated up to 200°C and 400 bars. The interaction coefficients involving Cl^- estimated include ε(H⁺, Cl^-), ε(Na⁺, Cl^-), ε(Ag⁺, Cl^-), ε(Na⁺, AgCl₂ ^-), ε(Mg²⁺, Cl^-), ε(Ca²⁺, Cl^-), ε(Sr²⁺, Cl^-), ε(Ba²⁺, Cl^-), ε(Sm³⁺, Cl^-), ε(Eu³⁺, Cl^-), ε(Gd³⁺, Cl^-), and ε(GdAc²⁺, Cl^-). The interaction coefficients involving OH^- estimated include ε(Li⁺, OH^-), ε(K⁺, OH^-), ε(Na⁺, OH^-), ε(Cs⁺, OH^-), ε(Sr²⁺, OH^-), and ε(Ba²⁺, OH^-). In addition, the interaction coefficients of ε(Na⁺, Ac^-) and ε(Ca²⁺, Ac^-) have also been estimated. The bulk of interaction coefficients presented in this study has been evaluated from the mean activity coefficients. A few of them have been estimated from the potentiometric and solubility studies. The above interaction coefficients are tested against both experimental mean activity coefficients and equilibrium quotients. Predicted mean activity coefficients are in satisfactory agreement with experimental data. Predicted equilibrium quotients are in very good agreement with experimental values. Based upon its relatively rapid attainment of equilibrium and the ease of determining magnesium concentrations, this study also proposes that the solubility of brucite can be used as a pH (pcH) buffer/sensor for experimental systems in NaCl solutions up to 200°C by employing the predicted solubility quotients of brucite in conjunction with the dissociation quotients of water and the first hydrolysis quotients of Mg²⁺, all in NaCl solutions.     

Modeling of the transport and deposition of tungsten in the scheelite-bearing calc-silicate gneisses of the Montagne Noire,France

Scheelite-bearing calc-silicate gneisses (CSG) oceur in the Montagne Noire within a series of dominant micaschists. Detailed petrographical and mineralogical studies reveal three successive stages of metamorphism and hydrothermal alteration: (1) stage 1, a regional metamorphism at 550°C and 4.5 kb where no mineralization is formed; (2) stage 2a, a hydrothermal alteration at 500 to 450°C and 4 to 3 kb which is characterized by an intense sericitization of feldpars and deposition of Sn in Sn-bearing cale-silicates; and (3) stage 2b, a hydrothermal alteration characterized by the crystallization of idocrasegrossular in CSG with concomittant precipitation of scheelite. Tungsten was transported through the micaschist environment and deposited as scheelite only in the CSG of stage 2b at relatively low pressures. To characterize the mechanism of tungsten transport, tungsten speciation at high P-T and scheelite solubility in aqueous solations buffered by the CSG and by the micaschists assemblages were calculated. It was found that H₂WO ₀ ⁴ , HWO _- ⁴ and WO _2- ⁴ are the dominant tungsten aqueous species in H₂O–NaCl (one molal) solutions at 500°C and 2–4 kb. Calculations also indicate that scheelite deposition is controlled by decreasing pressure and increasing activity of aqueous calcium in this system. This is consistent with the petrographical and mineralogical observations. The consequences of the presence of volatiles (N₂, CH₄, CO₂) in the regional fluids were examined by determining the effect of N₂ on tungsten speciation and scheelite solubility. The addition of N₂ (up to 10 mol%) to the mineralizing fluids results in a marked increase in H₂WO ₀ ⁴ and HWO _- ⁴ concentrations relative to WO _2- ⁴ and in a large decrease of scheelite solubility. This mechanism favours scheelite precipitation and accounts for the commonly observed association of W (and Sn) deposits with graphitic series generating mixed volatiles fluids.     

Speciation of metals in natural waters

The form or speciation of a metal in natural waters can change its kinetic and thermodynamic properties. For example, Cu(II) in the free ionic form is toxic to phytoplankton, while copper complexed to organic ligands is not toxic. The form of a metal in solution can also change its solubility. For example, Fe(II) is soluble in aqueous solutions while Fe(III) is nearly insoluble. Natural organic ligands interactions with Fe(III) can increase the solubility by 20-fold in seawater. Ionic interaction models that can be used to determine the activity and speciation of divalent and trivalent metals in seawater and other natural elements will be discussed. The model is able to consider the interactions of metals with the major (Cl^-, SO₄ ^2-, HCO₃ ^-, CO₃ ^2-, Br^-, F^-) and minor (OH^-, H₂PO₄ ^-, HPO₄ ^2-, PO₄ ^3-, HS^-) anions as a function of temperature (0 to 50 °C), ionic strength [0 to 6 m (m = mol kg-¹)] and pH (1 to 13). Recently, it has been shown that many divalent metals are complexed with organic ligands. Although the composition of these ligands is not known, a number of workers have used voltammetry to determine the concentration of the ligand [L ⁿ ] and the stability constant (K _ML) for the formation of the complex     

湖南香花岭矽卡岩中锡的矿物学行为与成矿过程

湖南香花岭矽卡岩型锡矿床是南岭地区一个重要的锡多金属矿床,发育有丰富的含锡矿物。在野外和显微镜下观察 基础上,文章利用电子探针技术系统分析了香花岭矽卡岩中含锡矿物的矿物学特征,探讨了锡的成矿过程、成矿流体以及 锡的来源。研究结果表明,香花岭矽卡岩中含锡矿物由锡矿物（锡石、尼日利亚石、孟宪民石等）和富锡矿物（韭闪石、 尖晶石、葡萄石、塔菲石等）组成。锡的成矿有三个阶段：矽卡岩早阶段,Sn进入尖晶石、韭闪石等造岩矿物中,形成富 锡矿物;氧化物阶段,锡矿物如锡石、尼日利亚石、孟宪民石等逐渐晶出;晚期热液阶段,早期含锡矿物热液蚀变原位析 出锡石,或富Sn热液交代早期矿物形成了富锡环边。矽卡岩中成矿流体富含F,CO2,Li等挥发组分,控制了Sn的富集、迁 移、结晶等过程。香花岭矽卡岩中Sn根本上来源于地层,锡的成矿过程反映了Sn在地壳中的地球化学循环过程。     

The mobility of U and Th in subduction zone fluids: an indicator of oxygen fugacity and fluid salinity

The solubility of U and Th in aqueous solutions at P-T-conditions relevant for subduction zones was studied by trapping uraninite or thorite saturated fluids as synthetic fluid inclusions in quartz and analyzing their composition by Laser Ablation-ICPMS. Uranium is virtually insoluble in aqueous fluids at Fe-FeO buffer conditions, whereas its solubility increases both with oxygen fugacity and with salinity to 960 ppm at 26.1 kbar, Re-ReO₂ buffer conditions and 14.1 wt% NaCl in the fluid. At 26.1 kbar and 800°C, uranium solubility can be reproduced by the equation: log\textU = 2.681 + 0.1433logf\textO₂ + 0.594\textCl, \log {\text{U}} = 2.681 + 0.1433\log f{\text{O}}_{2} + 0.594{\text{Cl,}} where fO₂ is the oxygen fugacity, and Cl is the chlorine content of the fluid in molality. In contrast, Th solubility is generally low (<10 ppm) and independent of oxygen fugacity or fluid salinity. The solubility of U and Th in clinopyroxene in equilibrium with uraninite and thorite was found to be in the order of 10 ppm. Calculated fluid/cpx partition coefficients of Th are close to unity for all conditions. In contrast, D^fluid/cpx for uranium increases strongly both with oxygen fugacity and with salinity. We show that reducing or NaCl-free fluids cannot produce primitive arc magmas with U/Th ratio higher than MORB. However, the dissolution of several wt% of oxidized, saline fluids in arc melts can produce U/Th ratios several times higher than in MORB. We suggest that observed U/Th ratios in arc magmas provide tight constraints on both the salinity and the oxidation state of subduction zone fluids.     

多种矿物流体包裹体中液相阴阳离子的同时测定

地质流体研究是地球科学领域的研究热点,矿物流体包裹体中成分是认识地质流体的关键。群体包裹体液相成分分析的传统方法大多采用单通道离子色谱分析阴离子,原子吸收光谱或电感耦合等离子体原子发射光谱分析阳离子,分析方法适用矿物种类少,单矿物需要量大（3g以上）。本文使用双通道离子色谱仪,经过大量条件实验,优化了样品爆裂、提取等前处理分析条件,确认了不同矿物可检测的离子,并采用富集方法将样品需要量由常规的3.00g减少到300mg,实现了石英、方解石、萤石、闪锌矿、石榴子石、磁铁矿和黄铁矿等多种矿物流体包裹体液相成分中Li⁺、Na⁺、K⁺、Mg²⁺、Ca²⁺、F^-、Cl^-、Br^-、NO₂^-、NO₃^-、SO₄^2-等阴阳离子的同时分析。所建立的离子色谱同时分析矿物流体包裹体液相微量成分分析方法简便、快速,成本低,用样量少,扩大了矿物种类的分析范围,为成矿流体研究提供了更加直接、有效的信息。     

Genesis of the Xuebaoding W–Sn–Be Crystal Deposits in Southwest China: Evidence from Fluid Inclusions,Stable Isotopes and Ore Elements

The Xuebaoding crystal deposit, located in northern Longmenshan, Sichuan Province, China, is well known for producing coarse‐grained crystals of scheelite, beryl, cassiterite, fluorite and other minerals. The orebody occurs between the Pankou and Pukouling granites, and a typical ore vein is divided into three parts: muscovite and beryl within granite (Part I); beryl, cassiterite and muscovite in the host transition from granite to marble (Part II); and the main mineralization part, an assemblage of beryl, cassiterite, scheelite, fluorite, apatite and needle‐like tourmaline within marble (Part III). No evidence of crosscutting or overlapping of these ore veins by others suggests that the orebody was formed by single fluid activity. The contents of Be, W, Sn, Li, Cs, Rb, B, and F in the Pankou and Pukouling granites are similar to those of the granites that host Nanling W–Sn deposits. The calculated isotopic compositions of beryl, scheelite and cassiterite (δD, ?69.3‰ to ?107.2‰ and δ¹⁸O_H2O, 8.2‰ to 15.0‰) indicate that the ore‐forming fluids were mainly composed of magmatic water with minor meteoric water and CO₂ derived from decarbonation of marble. Primary fluid inclusions are CO₂? CH₄+ H₂O ± CO₂ (vapor), with or without clathrates and halites. We estimate the fluid trapping condition at T = 220 to 360°C and P > 0.9 kbar. Fluid inclusions are rich in H₂O, F^‐ and Cl^‐. Evidence for fluid‐phase immiscibility during mineralization includes variable L/V ratios in the inclusions and inclusions containing different phase proportions. Fluid immiscibility may have been induced by the pressure released by extension joints, thereby facilitating the mineralization found in Part III. Based on the geochemical data, geological occurrence, and fluid inclusion studies, we hypothesize that the coarse‐grained crystals were formed by: (i) the high content of ore elements and volatile elements such as F in ore‐forming fluids; (ii) occurrence of fluid immiscibility and Ca‐bearing minerals after wall rock transition from granite to marble making the ore elements deposit completely; (iii) pure host marble as host rock without impure elements such as Fe; and (iv) sufficient space in ore veins to allow growth.     

滇西来利山与小龙河云英岩型锡矿成矿流体氧逸度特征对比

来利山锡矿床与小龙河锡矿床是滇西地区典型的云英岩型锡矿床。为揭示它们在成因上深层次的差异性,对来利山锡矿和小龙河锡矿的锡石进行了电子探针成分分析、镜下观察以及成矿环境对比分析。结果表明,锡石中的铁多以Fe~(3+)的形式与Sn~(4+)发生类质同象,氧逸度越高,锡石中Fe~(3+)越多,宏观上表现为锡石的颜色越深。来利山矿区锡石中Fe含量明显低于小龙河矿区,且锡石颜色明显比小龙河矿区颜色浅,反映了来利山锡矿成矿环境相对开放,成矿流体氧逸度偏低,流体中Sn络合物迁移能力较强,在花岗岩体外接触带的围岩裂隙中形成外云英岩型锡矿床;而小龙河锡矿成矿环境相对封闭,成矿流体氧逸度偏高,流体中Sn络合物迁移能力较弱,多在花岗岩体顶部的构造裂隙中形成内云英岩型锡矿床。     

Zn and Pb solubility and speciation in aqueous chloride fluids at T-P parameters corresponding to granitoid magma degassing and crystallization

The solubility of all possible Zn and Pb species in aqueous chloride fluids was evaluated by means of thermodynamic simulations in systems ZnO(PbO)-aqueous solution of NaCl (KCl, NaCl + HCl) within broad ranges of temperature (600–900°C), pressure (0.7–5 kbar), and chloride concentrations, under parameters corresponding to the crystallization and degassing of granitoid magmas in the Earth’s crust. Our simulation results demonstrate that the addition of Cl to the fluid phase in the form of Na(K)Cl and HCl significantly increases the concentrations of Cl-bearing Zn and Pb complexes and the total concentration of the metals in the solutions in equilibrium with the solid oxides. In Zn-bearing fluids, the Zn(OH) ₂ ⁰ , ZnOH⁺, and Zn(OH) ₃ ^? —hydroxyl complexes and the ZnCl ₂ ⁰ , and ZnCl⁺ chlorocomplexes, which are predominant at low Cl concentrations (C_Cl < 0.05–0.1 m) give way to ZnCl ₄ ^2? with increasing C_Cl, which becomes the predominant Zn species of the fluid at C_Cl > 0.1–0.5 m throughout the whole temperature range in question and pressures higher than 1 kbar. For Pb-bearing fluids, the T-P-X region dominated by the Pb(OH) ₂ ⁰ , and Pb(OH) ₃ ^? hydroxyl complexes is remarkably wider than the analogous region for Zn, particularly at elevated temperatures (≥700°C) in alkaline solutions. An increase in C_Cl is associated with an increase in the concentration and changes in the speciation of Pb chlorocomplexes: PbCl ₂ ⁰ → PbCl ₃ ^? → PbCl ₄ ^2? . The concentrations of Zn and Pb chlorocomplexes increase with increasing pressure, decreasing temperature, and decrease pH with the addition of HCl to the system. It is demonstrated that the solubility of ZnO at any given T-P-X in alkaline solutions with low chloride concentrations are lower than the solubility of PbO. The Zn concentration increases more significantly than with the Pb concentration with increasing C_Cl and decreasing pH, so that the Zn concentration in acidic solutions is higher than the Pb concentration over broad ranges of temperature, pressure, and Cl concentration. Chloride complexes of Zn (ZnCl ₂ ⁰ , and ZnCl ₄ ^2? ) and Pb (PbCl ₂ ⁰ , and PbCl ₃ ^? are proved to be predominant within broad T-P-X-pH ranges corresponding to the parameters under which magmatic fluid are generated. Our simulation results confirm the hypothesis that chlorocomplexes play a leading role in Zn and Pb distribution between aqueous chloride fluids and granitic melts. These simulation results are consistent with experimental data on the Zn and Pb distribution coefficients (D(Zn)^f/m and D(Pb)^f/m, respectively) between aqueous chloride fluids and granitic melts that demonstrated that (1) D(Zn)^f/m and D(Pb)^f/m increase with increasing Na and K chloride concentrations in the aqueous fluid, (2) both D(Zn)^f/m and D(Pb)^f/m drastically increase when HCl is added to the fluid, and (3) (D(Zn)^f/m is higher than D(Pb)^f/m at any given T-P-X parameters. The experimentally established decrease in D(Zn)^f/m and D(Pb)^f/m with increasing pressure (at unchanging temperature and Cl concentration) is likely explained by an increase in the alkalinity of the aqueous chloride fluid in equilibrium with granite melt and, correspondingly, a decrease in the Zn and Pb solubility in this fluid.     

Genesis of arsenic/fluoride-enriched soda water: A case study at Datong,northern China

The high As and F⁻ groundwaters from Datong Basin are mostly soda waters with a Na/(Cl+SO₄) (meq) ratio greater than unity, As and F⁻ up to 1550 μg/L and 10.4 mg/L, respectively, and with pH between 7.6 and 9.1. Geochemical modeling indicates that the waters are oversaturated with respect to calcite and clay minerals such as kaolinite, and undersaturated with respect to primary rock-forming minerals such as anorthite and albite. The water chemistry also is affected by evapotranspiration. The degree of evaporative enrichment is up to 85 in terms of Cl⁻. Results of the hydrogeochemical studies indicate that the occurrence of soda water at Datong is the result of incongruent dissolution of aluminosilicates at one stage of their interaction with groundwater when the water is oversaturated with respect to calcite and evapotranspiration-related salt accumulation is not too strong. Studying the genesis of soda waters provides new insights into mechanism of As and F⁻ enrichment in the aquifer system. Due to CaF₂ solubility control and OH⁻–F⁻ exchange reactions, F⁻ can be enriched in soda water. And the high pH condition of soda water favors As desorption from oxyhydroxide surfaces, thereby increasing the concentration of As in the aqueous phase.     

Dissolution kinetics and biodurability of tremolite particles in mimicked lung fluids: Effect of citrate and oxalate

The effect of citrate and oxalate on tremolite dissolution rate was measured at 37 °C in non-stirred flow-through reactors, using modified Gamble’s solutions at pH 4 (macrophages), 7.4 (interstitial fluids) and 5.5 (intermediate check point) containing 0, 0.15, 1.5 and 15 mmol L⁻¹ of citrate or oxalate. The dissolution rates calculated from Si concentration in the output solutions without organic ligands depend on pH, decreasing when the pH increases from −13.00 (pH 4) to −13.35 (pH 7.4) mol g⁻¹ s⁻¹ and following a proton-promoted mechanism. The presence of both ligands enhances dissolution rates at every pH, increasing this effect when the ligand concentration increases. Citrate produces a stronger effect as a catalyst than oxalate, mainly at more acidic pHs and enhances dissolution rates until 20 times for solutions with 15 mmol L⁻¹ citrate. However, at pH 7.4 the effect is lighter and oxalate solutions (15 mmol L⁻¹) only enhances dissolution rates eight times respect to free organic ligand solutions. Dissolution is promoted by the attack to protons and organic ligands to the tremolite surface. Magnesium speciation in oxalate and citrate solutions shows that Mg citrate complexes are more effective than oxalate ones during the alteration of tremolite in magrophages, but this tendency is the opposite for interstitial fluids, being oxalate magnesium complexes stronger. The biodurability estimations show that the destruction of the fibers is faster in acidic conditions (macrophages) than in the neutral solutions (interstitial fluid). At pH 4, both ligands oxalate and citrate reduce the residence time of the fibers with respect to that calculated in absence of ligands. Nevertheless, at pH 7.4 the presence of ligands does not reduce significantly the lifetime of the fibers.     

A combined EMPA and LA-ICP-MS study of Li-bearing mica and Sn–Ti oxide minerals from the Qiguling topaz rhyolite (Qitianling District,China): The role of fluorine in origin of tin mineralization

The Sn-rich Qiguling topaz rhyolite dike intrudes the Qitianling biotite granite of the Nanling Range in southern China; the granite hosts the large Furong Sn deposit. The rhyolite dike is typically peraluminous, volatile-enriched, and highly evolved. Whole-rock F and Sn concentrations attain 1.9 wt.% and 2700 ppm, respectively. The rhyolite consists of a fine-grained matrix formed by quartz, feldspar, mica and topaz, enclosing phenocrysts of quartz, feldspar and mica; it is locally crosscut by quartz veinlets. Lithium-bearing micas in both phenocrysts and the groundmass can be classified as primary zinnwaldite, “Mus-Ann” (intermediate member between annite and muscovite), and secondary Fe-rich muscovite. Topaz is present in the groundmass only; common fluorite occurs in the groundmass and also in a specific cassiterite, rutile and fluorite (Sn–Ti–F) assemblage. Cassiterite and rutile are the only Sn and Ti minerals; both cassiterite and Nb-rich rutile are commonly included in the phenocrysts. The Sn–Ti–F assemblage is pervasive, and contains spongy cassiterite in some cases; cassiterite also occurs in quartz veinlets which cut the groundmass. Electron microprobe and LA-ICP-MS compositions were used to study the magmatic and hydrothermal processes and the role of F in Sn mineralization. The presence of zinnwaldite and “Mus-Ann”, which are respectively representative of early and late mica crystallization during magma differentiation, also suggests a significant decrease in f(HF)/f(H₂O) of the system. Cassiterite included in the zinnwaldite phenocrysts is suggested to have crystallized from the primary magma at high temperature. Within the Sn–Ti–F aggregates, rutile crystallized as the earliest mineral, followed by fluorite and cassiterite. Spongy cassiterite containing inclusions of the groundmass minerals indicate a low viscosity of the late fluid. The cassiterite in the quartz veinlets crystallized from low-temperature hydrothermal fluids, which possibly mixed with meteoric water. In general, cassiterite precipitated during both magmatic and hydrothermal stages, and over a range of temperatures. The original fluorine and tin enrichments, f(HF)/f(H₂O) change in the residual magma, formation of Ca,Sn,F-rich immiscible fluid, decrease of the f(HF) during groundmass crystallization, and mixing of magma-derived fluids with low-saline meteoric water during the late hydrothermal stage, are all factors independently or together responsible for the Sn mineralization in the Qiguling rhyolite.     

Solubility of cassiterite in evolved granitic melts: effect of T, fO2, and additional volatiles

The aim of this experimental study was to determine the solubility of cassiterite in natural topaz- and cassiterite-bearing granite melts at temperatures close to the solidus. Profiles of Sn concentrations at glass–crystal (SnO₂) interface were determined following the method of (Harrison, T.M., Watson, E.B., 1983. Kinetics of zircon dissolution and zirconium diffusion in granitic melts of variable water content. Contributions to Mineralogy and Petrology 84, 66–72). The cassiterite concentration calculated at the SnO₂–glass interface is the SnO₂ solubility. Experiments were performed at 700–850 °C and 2 kbar using a natural F-bearing peraluminous granitic melt with 2.8 wt.% normative corundum. Slightly H₂O-undersaturated to H₂O-saturated melt compositions were chosen in order to minimize the loss of Sn to the noble element capsule walls. At the nickel–nickel oxide assemblage (Ni–NiO) oxygen fugacity buffer, the solubility of cassiterite in melts containing 1.12 wt.% F increases from 0.32 to 1.20 wt.% SnO₂ with an increasing temperature from 700 to 850 °C. At the Ni–NiO buffer and a given corundum content, SnO₂ solubility increases by 10% to 20% relative to an increase of F from 0 to 1.12 wt.%. SnO₂ solubility increases by 20% relative to increasing Cl content from 0 to 0.37 wt.% in synthetic granitic melts at 850 °C. We show that Cl is at least as important as F in controlling SnO₂ solubility in evolved peraluminous melts at oxygen fugacities close to the Ni–NiO buffer. In addition to the strong effects of temperature and fO₂ on SnO₂ solubility, an additional controlling parameter is the amount of excess Al (corundum content). At Ni–NiO and 850 °C, SnO₂ solubility increases from 0.47 to 1.10 wt.% SnO₂ as the normative corundum content increases from 0.1 to 2.8 wt.%. At oxidizing conditions (Ni–NiO +2 to +3), Sn is mainly incorporated as Sn⁴⁺ and the effect of excess Al seems to be significantly weaker than at reducing conditions.     

The solubility of fluorite in hydrothermal solutions,an experimental study

The solubility of fluorite in NaCl solutions increases with increasing temperature at all ionic strengths up to about 100°C. Above this temperature, the solubility passes through a maximum and possibly a minimum with increasing temperature at NaCl concentrations of 1.0M or less, and increases continuously with increasing temperature at NaCl concentrations above 1.0M. At any given temperature, the solubility of fluorite increases with increasing salt concentration in NaCl, KCl and CaCl₂ solutions. The solubility follows Debye-Hückel theory for KCl solutions. In NaCl and CaCl₂ solutions, the solubility of fluorite increases more rapidly than predicted by Debye-Hückel theory: the excess solubility is due to the presence of NaF^c, CaF⁺, and possibly of Na₂F⁺. The solubility of fluorite in NaCl-CaCl₂ and in NaCl-CaCl₂-MgCl₂ solutions is controlled by the common ion effect and by the presence of NaF^c, CaF⁺, and MgF⁺. The solubility of fluorite in NaCl-HCl solutions increases rapidly with increasing initial HCl concentration; the large solubility increase is due to the presence of HF^c. It seems likely that complexes other than those identified in this study rarely play a major role in fluoride transport and fluorite deposition at temperatures below 300°C.     

The Mobility of Rare—Earth Elements During Hydrothermal Activity：A Review

The mobility of the rare-earth elements(REE)during hydrothermal activities is increasingly documented.Geological and experimental evidence suggests that REE may be mobile in solutions rich in F^-,Cl^-,HCO3^-,CO^2- 3,HPO4^2-,PO4^3-,or in combinations of the above ligands,even though little has been known about which ligand or which combination is most effective in mobilizing REE. The fractionation of REE resulting from hydrothermal activities is inconsistent.One set of field data implies the prererential mobility of the light rare-earth elements(LREE).whereas another set of field observations indicates the dominant mobilization of the heavy rare earth elements(HREE),and some theoretical prediction is comtradictory to the field evidence.The Eu anomalies due to hydrothermal activities are complex and plausible explanation is not available.The existing experimental approaches dealing with REE are not adequate for explanation ofREE behaviour in aqueous solutions.Systematic experimental approaches are suggested.     

Inclusions of magmatic fluids: P-V-T-X properties of aqueous salt solutions of various types and petrological implications

The P-V-T-X properties of H₂O-salt systems are compared depending on the solubility coefficient of compounds contained in these systems and the presence or absence of critical phenomena in the saturated solutions. Data on synthetic and natural inclusions captured in minerals at elevated temperatures and pressures and employed to discuss the principal features of phase diagrams of the H₂O-NaCl system (type I) and H₂O-NaF system (type II or P-Q type). It is demonstrated how characteristics of magmatic fluids of various types are manifested during the development of miarolitic pegmatites (Malkhan field in Transbaikalia) and during the crystallization of F-rich ongonitic melts (Ary-Bulak Massif in eastern Transbaikalia). Characteristics of solutions and gas-rich (gaseous) fluid inclusions in quartz phenocrysts from porphyritic ongonites (disappearance of the liquid regardless of its density and the overall salinity near the critical point of water, distinctive features of the dissolution of the crystalline phase, and the ability of the inclusions to withstand heating to 1400°C without decrepitation), and the richness of the fluid-magmatic system as a whole in F suggest that the ongonite melt crystallized in the presence of low-density NaF-bearing fluids of the P-Q type with a minor admixture of chlorides. It is important to identify the type of solutions in the fluid inclusions, because without knowing this type, it is impossible to accurately enough calculate the pressure at the temperatures of inclusion capture. For example, the unwarranted classification of solutions of type II (P-Q) in inclusions with the chloride system results in a significant overestimation of the calculated fluid pressures. A technique is proposed for studying the high-temperature immiscibility region in P-Q systems based on data obtained on gaseous fluid inclusions.     

In, Sn, Pb and Zn Contents and Their Relationships in Ore-forming Fluids from Some In-rich and In-poor Deposits in China

All the indium-rich deposits with indium contents in ores more than 100×10- 6 seems to be of cassiterite-sulfide deposits or Sn-bearing Pb-Zn deposits, e.g., in the Dachang Sn deposit in Guangxi, the Dulong Sn-Zn deposit in Yunnan, and the Meng'entaolegai Ag-Pb-Zn deposit in Inner Mongolia, the indium contents in ores range from 98×10-6 to 236×10-6 and show a good positive correlation with contents of zinc and tin, and their correlation coefficients are 0.8781 and 0.7430, respectively. The indium contents from such Sn-poor deposits as the Fozichong Pb-Zn deposit in Guangxi and the Huanren Pb-Zn deposit in Liaoning are generally lower than 10×10-6, i.e., whether tin is present or not in a deposit implies the enrichment extent of indium in ores. Whether the In enrichment itself in the ore -forming fluids or the ore-forming conditions has actually caused the enrichment/depletion of indium in the deposits? After studying the fluid inclusions in quartz crystallized at the main stage of mineralization of several In-rich and In-poor deposits in China, this paper analyzed the contents and studied the variation trend of In, Sn, Pb and Zn in the ore-forming fluids. The results show that the contents of lead and zinc in the ore-forming fluids of In-rich and -poor deposits are at the same level, and the lead contents range from 22×10-6 to 81×10-6 and zinc from 164×10-6 to 309×10-6, while the contents of indium and tin in the ore-forming fluids of In-rich deposits are far higher than those of In-poor deposits, with a difference of 1-2 orders of magnitude. Indium and tin contents in ore-forming fluid of In-rich deposits are 1.9×10-6-4.1×10-6 and 7×100-6-55×10-6, and there is a very good positive correlation between the two elements, with a correlation coefficient of 0.9552. Indium and tin contents in ore-forming fluid of In-poor deposits are 0.03×10-6-0.09×10-6 and 0.4×10-6--2.0×10-6, respectively, and there is no apparent correlation between them. This indicates, on one hand, that In-rich ore-forming fluids are the material basis for the formation of In-rich deposits, and, on the other hand, tin probably played a very important role in the transport and enrichment of indium.     

Partitioning behavior of chlorine and fluorine in the system apatite-silicate melt-fluid

The partitioning behavior of Cl among apatite, mafic silicate melt, and aqueous fluid and of F between apatite and melt have been determined in experiments conducted at 1066 to 1150 °C and 199-205 MPa. The value of D_Cl^apatite/melt (wt. fraction of Cl in apatite/Cl in melt) ≈0.8 for silicate melt containing less than ∼3.8 wt.% Cl. At higher melt Cl contents, small increases in melt Cl concentration are accompanied by large increases in apatite Cl concentration, forcing D_Cl^apatite/melt to increase as well. Melt containing less than 3.8% Cl coexists with water-rich vapor; that containing more Cl coexists with saline fluid, the salinity of which increases rapidly with small increases in melt Cl content, analogous to the dependency of apatite composition on melt Cl content. This behavior is due to the fact that the solubility of Cl in silicate melt depends strongly on the composition of the melt, particularly its Mg, Ca, Fe, and Si contents. Once the melt becomes “saturated” in Cl, additional Cl must be accommodated by coexisting fluid, apatite, or other phases rather than the melt itself. Because Cl solubility depends on composition, the Cl concentration at which D_Cl^apatite/melt and D_Cl^fluid/melt begin to increase also depends on composition. The experiments reveal that D_F^apatite/melt ≈3.4. In contrast to Cl, the concentration of F in silicate melt is only weakly dependent on composition (mainly on melt Ca contents), so D_F^apatite/melt is constant for a wide range of composition.The experimental data demonstrate that the fluids present in the waning stages of the solidification of the Stillwater and Bushveld complexes were highly saline. The Cl-rich apatite in these bodies crystallized from interstitial melt with high Cl/(F + OH) ratio. The latter was generated by the combined processes of fractional crystallization and dehydration by its reaction with the relatively large mass of initially anhydrous pyroxene through which it percolated.