Experimental Studies of the Solubility of Cassiterite and the Extraction of Tin from Granitic Melts

Experiments indicate that the solubility of cassiterite can be enhanced by increasing either acidity or alkalinity in hydrothermal solutions as a consequence of the duality of tin.The minimum solubility of cassiterite is found in neutral solutions.F-and CL-coordination compounds of Sn can alternate with hydroxyl coordination compounds with changing pH in the solutions.In this case,F^- and Cl^- and OH^- can be substituted with each other.The dissolution reaction of cassiterite is of reducing nature.High temperature and acidic reducing environment are favorable for the dissolution of cassiterite and the trans-port of Sn^2 compounds in fluids or solutions.High-temperature fluoride and chloride fluids can all dissolve,extract and enrich Sn to form F^- and /or Cl-coordination compounds,However,Fplays a more important role than Cl.F-coordination compounds are more stable and efficient than Cl-coordination compounds during the transport an enrichment of Sn in melts or solutions.The solubili-ty of cassiterite and the amount of Sn extracted from granitic melt depend not only on T,P,pH and Eh in the fluids or solutions,but also on the amounts of dissociated F^- and Cl^- in the fluids.     

The combined effects of ƒO2 and melt composition on SnO2 solubility and tin diffusivity in haplogranitic melts

The diffusion profile method has been employed to measure tin diffusion coefficients and SnO₂ solubility in water-saturated, peralkaline to peraluminous haplogranitic melts at 850°C, 2 kbar, and log ƒ_O2 conditions ranging from FMQ - 0.57 to FMQ + 3.49. At reduced conditions cassiterite is highly soluble and tin is present dominantly as a Sn²⁺ species, whereas at oxidized conditions SnO₂ is much less soluble, and tin is present dominantly as a Sn⁴⁺ species. There is a strong melt composition control on SnO₂ solubility; solubilities are at a minimum at the subaluminous composition, increase strongly with alkali content in peralkaline compositions and weakly with Al content in peraluminous compositions. In the case of the latter, this increase can only be distinguished at reduced conditions, e.g., at a log ƒ_O2 of FMQ - 0.57 cassiterite solubility increases from 2.78 to 4.11 wt% SnO₂ for melt with Al/(Na + K)compositions (A.S.I.) of 1.0 and 1.2, respectively. At oxidized conditions SnO₂ solubility is 500 ppm for both the A.S.I. 1.0 and 1.2 compositions. By comparison Sn0₂ solubilities in the most peralkaline composition investigated range from 3.94 wt% to -10 wt% Sn02, for the most oxidized to the most reduced conditions, respectively. Thermodynamic modelling of the data indicates that the Sn⁴⁺/ΣSn ratio in the melt is also at a minimum at the subaluminous composition, ranging from 0.4 at log ƒ_O2 of FMQ + 3.49 to 0.01 at FMQ - 0.57. Over the same log foZ range the Sn⁴⁺/ΣSn ratio for the A.S.I. 0.6 composition ranges from 0.98 to 0.4 and for the A.S.I. 1.25 composition, from 0.8 to 0.02.Tin diffusivity is dependent on both f_O2 and melt composition. The effective binary diffusion coefficient of tin at reduced conditions is approximately 10^−7.5 cm²/sec for the peraluminous compositions and 10^−8.2 cm²/sec for the peralkaline compositions. At oxidized conditions these values decrease to approximately 10^−8.2 and 10^−9.0 cm²/sec, respectively. These are interpreted to reflect relatively fast diffusion where Sn²⁺ is the dominant valence and tin in this case behaves similar to a network modifier and relatively slow diffusion where Sn⁴⁺ is dominant and tin likely has a lower coordination number. Alternatively, the coordination of Sn²⁺ and Sn⁴⁺ is the same, but the bond strengths are different. At fixed f_O2 the faster diffusivity in the peraluminous compositions reflects the lower Sn⁴⁺/Sn²⁺ ratio. The fact the Sn⁴⁺/Sn²⁺ ratio in melts varies greatly with ƒ_O2 at redox conditions near FMQ suggests that the partitioning behaviour of tin possibly changes during the evolution of an igneous suite in general and of a peraluminous granite suite in particular.     

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。     

Thio complexes of gold and the transport of gold in hydrothermal ore solutions

The solubility of gold in aqueous sulphide solutions has been determined from pH_20°C ≈ 4 to pH_20°C ≈ 9.5 in the presence of a pyrite-pyrrhotite redox buffer at temperatures from 160 to 300°C and 1000 bar pressure. Maximum solubilities were obtained in the neutral region of pH as, for example, with m_NaHS = 0.15 m, pH_20°C = 5.96, T = 309°C, P = 1000 bar where a gold solubility of 225 mg/kg was obtained. It was concluded that three thio gold complexes contributed to the solubility. The complex Au₂(HS)₂S^2? predominated in alkaline solution, the Au(HS)₂^? complex occurred in the neutral pH region, and in the acid pH region, it was concluded with less certainty that the Au(HS)° complex was present. Formation constants calculated forAu₂(HS)₂S^2? and Au (HS)₂^? emphasize their high stability. In the temperature range from 175 to 250°C, values of pβ for Au₂(HS)₂S^2? vary from ?53.0 to 47.9 (±1.6) and from ?23.1 to ?19.5 ( ± 1.5) for Au(HS)₂^?. Equilibrium constante for the dissolution reactions, $\text{Au° + H}{}_2\text{S + HS}{}^{\mathrm{?}}\text{? Au(HS)}{}_2{}^{\mathrm{?}}\text{+}\text{1}\text{2}\text{H}{}_2$ and 2Au° + H₂S + 2H8^? ? Au(HS)₂^? + H₂ vary from pK_m = +2.4 to +2.55 (±0.10) for Au₂(HS)₂S^2? and from pK_n = + 1.29 to + 1.19 (±0.10) for Au(HS)₂^? over the temperature range 175 to 250°C. Enthalpies of these dissolution reactions were calculated to be ΔH_m° = ?5.2 ±2.0 kcal/mol and ΔH_n° = +1.7 ±2.0 kcal/mol respectively. It was concluded that gold is probably transported in hydrothermal ore solutions as both thio and chloro complexes and may be deposited in response to changes in temperature, pressure, pH, oxidation potential of the system and total sulphur concentration.     

Gibbsite solubility and thermodynamic properties of hydroxy-aluminum ions in aqueous solution at 25°C

Solubility curves were determined for a synthetic gibbsite and a natural gibbsite (Minas Gerais, Brazil) from pH 4 to 9, in 0.2% gibbsite suspensions in 0.01 M NaNO₃ that were buffered by low concentrations of non-complexing buffer agents. Equilibrium solubility was approached from oversaturation (in suspensions spiked with Al(NO₃)₃ solution), and also from undersaturation in some synthetic gibbsite suspensions. Mononuclear Al ion concentrations and pH values were periodically determined. Within 1 month or less, data from over-and undersaturated suspensions of synthetic gibbsite converged to describe an equilibrium solubility curve. A downward shift of the solubility curve, beginning at pH 6.7, indicates that a phase more stable than gibbsite controls Al solubility in alkaline systems. Extrapolation of the initial portion of the high-pH side of the synthetic gibbsite solubility curve provides the first unified equilibrium experimental model of Al ion speciation in waters from pH 4 to 9.The significant mononuclear ion species at equilibrium with gibbsite are Al³⁺, AlOH²⁺, Al(OH)⁺₂ and Al(OH)^?₄, and their ion activity products are $\text{1K}{}_{50}\text{= 1.29 × 10}{}^8$, $\text{1K}{}_{\mathrm{s1}}\text{= 1.33 × 10}{}^3$, $\text{1K}{}_{\mathrm{s2}}\text{= 9.49 × 10}{}^{\mathrm{?3}}$ and $\text{1K}{}_{\mathrm{s4}}\text{= 8.94 × 10}{}^{\mathrm{?15}}$. The calculated standard Gibbs free energies of formation (ΔG°_f) for the synthetic gibbsite and the A1OH²⁺, Al(OH)⁺₂ and Al(OH)^?₄ ions are ?276.0, ?166.9, ?216.5 and ?313.5 kcal mol^?1, respectively. These ΔG°_f values are based on the recently revised ΔG°_f value for Al³⁺ (?117.0 ± 0.3 kcal mol_?1) and carry the same uncertainty. The ΔG°_f of the natural gibbsite is ?275.1 ± 0.4 kcal mol^?, which suggests that a range of ΔG°_f values can exist even for relatively simple natural minerals.     

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.     

The solubility of calcite,strontianite and witherite in NaCl solutions at 25°C

The solubility of CaCO₃ (calcite), SiCO₃ (strontianite), and BaCO₃ (witherite) has been determined in NaCl solutions from 0.1 to 6 m at 25°C. Activity coefficients estimated from Pitzer's equations with higher order interaction terms (θ and Ψ) were used to extrapolate the results to infinite dilution. Thermodynamic values of $\text{pK}{}_{\mathrm{sp}}\text{= 8.46 ± 0.03,9.13 ± 0.03}$ and $\text{8.56 ± 0.04}$ were found, respectively, for CaCO₃, SrCO₃ and BaCO₃ at 25°C. These results are in reasonable agreement with literature data. Since Pitzer parameters for the interactions of CO₃^2? with Ca²⁺, Sr²⁺ and Ba²⁺ were not used, our results indicate that they are not necessary at low values of $\text{P}{}_{\mathrm{co2}}$.     

The solubilities of calcite,aragonite and vaterite in CO2-H2O solutions between 0 and 90°C,and an evaluation of the aqueous model for the system CaCO3-CO2-H2O

Calculations based on approximately 350 new measurements (Ca_T-PCO₂) of the solubilities of calcite, aragonite and vaterite in CO₂-H₂O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants K_C, K_A, and K_V respectively, for the reaction CaCO₃(s) = Ca²⁺ + CO^2?₃: $\text{Log K}{}_{\mathrm{C}}\text{= ?171.9065 ? 0.077993T +}\text{2839.319}\text{T}\text{+ 71.595 log T}$$\text{Log K}{}_{\mathrm{A}}\text{= ?171.9773 ? 0.077993T +}\text{2903.293}\text{T}\text{+71.595 log T}$$\text{Log K}{}_{\mathrm{V}}\text{= ?172.1295 ? 0.077993T +}\text{3074.688}\text{T}\text{+ 71.595 log T}$ where T is in ^oK. At 25°C the logarithms of the equilibrium constants are ?8.480 ± 0.020, ?8.336 ± 0.020 and ?7.913 ± 0.020 for calcite, aragonite and vaterite, respectively.The equilibrium constants are internally consistent with an aqueous model that includes the CaHCO⁺₃ and CaCO⁰₃ ion pairs, revised analytical expressions for CO₂-H₂O equilibria, and extended Debye-Hückel individual ion activity coefficients. Using this aqueous model, the equilibrium constant of aragonite shows no PCO₂-dependence if the CaHCO⁺₃ association constant is between 0 and 90°C, corresponding to the value logK_Cahco⁺3 = 1.11 ± 0.07 at 25°C. The CaCO⁰₃ association constant was measured potentiometrically to be between 5 and 80°C, yielding logK_CaCO⁰3 = 3.22 ± 0.14 at 25°C.The CO₂-H₂O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of K_H, K₁ and K₂ are $\text{log K}{}_{\mathrm{H}}\text{= 108.3865 + 0.01985076T ?}\text{6919.53}\text{T}\text{? 40.45154 log T +}\text{669365.}\text{T}{}^2$, $\text{log K}{}_1\text{= ?356.3094 ? 0.06091964T +}\text{21834.37}\text{T}\text{+ 126.8339 log T —}\text{1684915.}\text{T}{}^2$ and logK₂ = ?107.8871 ? 0.03252849T + 5151.79/T + 38.92561 logT ? 563713.9/T² which may be used to at least 250°C. These expressions hold for 1 atm. total pressure between 0 and 100°C and follow the vapor pressure curve of water at higher temperatures.Extensive measurements of the pH of Ca-HCO₃ solutions at 25°C and 0.956 atm PCO₂ using different compositions of the reference electrode filling solution show that measured differences in pH are closely approximated by differences in liquid-junction potential as calculated by the Henderson equation. Liquid-junction corrected pH measurements agree with the calculated pH within 0.003-0.011 pH.Earlier arguments suggesting that the CaHCO⁺₃ ion pair should not be included in the CaCO₃-CO₂-H₂O aqueous model were based on less accurate calcite solubility data. The CaHCO⁺₃ ion pair must be included in the aqueous model to account for the observed PCO₂-dependence of aragonite solubility between 317 ppm CO₂ and 100% CO₂.Previous literature on the solubility of CaCO₃ polymorphs have been critically evaluated using the aqueous model and the results are compared.     

The effect of CO ratio on the condensation of planetary material

The condensation temperatures of refractory silicates and oxides in a gas of cosmic composition are strongly dependent on the $\text{C}\text{O}$ ratio. As the ratio increases from 0.4 to 0.9 (solar ~ cosmic ~ 0.6), condensation temperatures of compounds such as A1₂O₃, Ca₂Al₂SiO₇, MgAl₂O₄, Mg₂SiO₄ and MgSiO₃ decrease by 50–100°. As $\text{C}\text{O}$ increases from 0.9 to 1.0, these temperatures drop an additional 300–400°. Other chemical differences result when $\text{C}\text{O}\text{\$}\text{?}\text{0.9}$ include: a new suite of high temperature minerals appears (graphite, CaS, Fe₃C, SiC and TiN); the reaction CO + 3H₂ → CH₄ + H₂O proceeds to the right at higher temperatures; and iron, whose condensation temperature is unaffected, condenses at higher temperatures than any silicate or oxide.     

Estimation of the dielectric constant of H2O from experimental solubilities of quartz,and calculation of the thermodynamic properties of aqueous species to 900°C at 2 kb

Experimental quartz solubilities in H₂O (Anderson and Burnham, 1965, 1967) were used together with equations of state for quartz and aqueous species (Helgesonet al., 1978; Walther and Helgeson, 1977) to calculate the dielectric constant of H₂O () at pressures and temperatures greater than those for which experimental measurements (Heger, 1969; Lukashovet al., 1975) are available ($\text{0.001 ? P ? 5}\text{kb}$ and $\text{0 ? T ? 600°C}$). Estimates of computed in this way for 2 kb (which are the most reliable) range from 9.6 at 600°C to 5.6 at 800°C. These values are 0.5 and 0.8 units greater, respectively, than corresponding values estimated by Quist and Marshall (1965), but they differ by <0.3 units from extrapolated values computed from Pitzer's (1983) adaptation of the Kirkwood (1939) equation. The estimates of generated from quartz solubilities at 2 kb were fit with a power function of temperature, which was then used together with equations and data given by Helgeson and Kirkham (1974a,b, 1976) Helgesonet al. (1981), and Helgeson (1982b, 1984) to calculate Born functions, Debye Hückel parameters, and the thermodynamic properties of Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺, and other aqueous species of geologic interest at temperatures to 900°C.     

Rutile solubility and titanium coordination in silicate melts

The solubility of rutile has been determined in a series of compositions in the K₂O-Al₂O₃-SiO₂ system ($\text{K}{}^1\text{=}\text{K}{}_2\text{O}\text{(K}{}_2\text{O}$ + Al₂O₃) = 0.38–0.90), and the CaO-Al₂O₃-SiO₂ system ($\text{C}{}^1\text{=}\text{CaO}\text{(CaO + Al}{}_2\text{O}{}_3\text{)}\text{= 0.47–0.59}$). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the $\text{K}{}^1$ ratio. For example, at 1475°C the amount of TiO₂ required for rutile saturation varies from 9.5 wt% ($\text{K}{}^1\text{= 0.38}$) to 11.5 wt% ($\text{K}{}^1\text{= 0.48}$) to 41.2 wt% ($\text{K}{}^1\text{= 0.90}$). In the CAS system at 1475°C, rutile solubility is not a strong function of $\text{C}{}^1$. The amount of TiO₂ required for saturation varies from 14 wt% ($\text{C}{}^1\text{= 0.48}$) to 16.2 wt% ($\text{C}{}^1\text{= 0.59}$).The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K⁺ in excess of that needed to charge balance Al³⁺. The suggested stoichiometry of this complex is K₂Ti₂O₅ or K₂Ti₃O₇. In CAS melts, the data suggest that Ca²⁺ in excess of A1³⁺ is not as effective at complexing with Ti as is K⁺. The greater solubility of rutile in CAS melts when $\text{C}{}^1$ is less than 0.54 compared to KAS melts of equal $\text{K}{}^1$ ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K).TiK_β x-ray emission spectra of KAS glasses ($\text{K}{}^1\text{= 0.43–0.60}$) with 7 mole% added TiO₂, rutile, and Ba₂TiO₄, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba₂TiO₄, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules.     

Lead orthophosphates—II. Stability of cholopyromophite at 25°c

The conversion of secondary lead orthophosphate [PbHPO₄] into chloropyromorphite [Pb₅(PO₄)₃Cl] in ca. 10^?1 M NaCl solutions has been investigated at 25°C. From the composition of the supernatant solutions, the solubility product constant for Pb₅(PO₄)₃Cl has been calculated to be 10^?84.4±0.1, corresponding to $\text{ΔG}{}_{\mathrm{?}}\text{°}$ of ?906.2 kcal mol^?1. The solution equilibria and phase relationships in the system PbCl₂-PbO-P₂O₈-H₂O are discussed along with the geological implications.     

Use of Pitzer's equations to determine the media effect on the formation of lead chloro complexes

The spectrophotometric measurements of chloro complexes of lead in aqueous HCl, NaCl, MgCl₂ and CaCl₂ solutions at 25°C have been analyzed using Pitzer's specific interaction equations. Parameters for activity coefficients of the complexes PbCl⁺, PbCl₂⁰ and PbCl₃^? have been determined for the various media. Values of $\text{K}{}_1\text{= 30.0 ± 0.6}$, $\text{K}{}_2\text{= 106.7 ± 2.1}$ and $\text{K}{}_3\text{= 73.0 ± 1.5}$ were obtained for the cumulative formation constants. [$\text{Pb}{}^{\mathrm{2+}}\text{+ nCl}{}^{\mathrm{?}}\text{→ PbCl}{}_{\mathrm{n}}{}^{\mathrm{2?n}}\text{)}$]. These values are in reasonable agreement with literature data. The Pitzer parameters for the PbCl ion pairs in various media were used to calculate the speciation of Pb²⁺ in an artificial seawater solution.     

A note on the chemistry of seawater in the range 350°–500°C

The chemistry of seawater at conditions of 350° to 500°C, 220 to 1000 bars (22 to 100 MPa) is controlled by reactions involving magnesium hydroxide sulfate (MHSH) and anhydrite. During progressive heating from 350° to 500°C at 1000 bars (100 MPa), MHSH with a $\text{Mg}\text{SO}{}_4$ ratio of 1.25 is formed via precipitation from solution and via reaction of solution with pre-existing anhydrite. During adiabatic expansion the MHSH extracts additional SO₄ from seawater and converts to a stoichiometry in which $\text{Mg}\text{SO}{}_4\text{= 1.16}$. These reactions control and greatly change the concentrations of Ca, Mg, SO₄ in solution and produce significant ionizable hydrogen, attaining 11.7 mmoles kg^?1 at maximum conditions.     

Solubility of the buffer assemblage pyrite + pyrrhotite + magnetite in NaCl solutions from 200 to 350°C

In the design of hydrothermal solubility studies it is important that the system be completely defined chemically. If the solubilities of minerals containing m metallic elements are to be determined in hydrothermal NaCl solutions, the phase rule requires that a total of m + 6 independent intensive parameters be controlled or measured in order to determine completely the system.In this study the solubility of the univariant assemblage pyrite + pyrrhotite + magnetite has been determined in vapor saturated hydrothermal solutions from 200 to 350°C for NaCl concentrations ranging from 0.0 to 5.0 molal. At any temperature, oxygen and sulfur fugacities were buffered by the chosen assemblage. System pH was determined from excess CO₂ partial pressures and computed ionic equilibria. Equilibrium constants were calculated by regression analysis of solubility data. The results show that more than 10 ppm of each mineral can dissolve in typical hydrothermal solutions under geologically realistic conditions. Solubilities were best represented by the species Fe²⁺ and FeCl⁺ at 200 and 250°C; Fe²⁺, FeCl⁺ and FeCl₂⁰ at 300°C; and Fe²⁺ and FeCl₂⁰ at 350°C. Ore deposition would occur by lowering temperature, diluting chloride concentration, or by raising pH through wall rock alteration reactions.     

Pressure dependence ot SrSO4 solubility

The solubilities of SrSO₄ in seawater, 0.65 M NaCl and and distilled water were measured as a function of pressure at 2°C. The thermodynamic solubility product was determined from the distilled water measurements and stoichiometric solubility products were determined from the seawater and Nad measurements. The equilibrium quotient for SrSO₄ dissolution at ionic strength of 0.65 was calculated from the NaCl measurements, using the known NaSO₄^? ionpairing association constant. For each of the solubility products values of $\text{Θ V}$ were determined. These experimental values were all $\text{11.0 ± 0.3}\text{ml}$ mole_? lower than the theoretical values based on anhydrous SrSO₄. This difference may be due to the equilibrating solid phase being a hydrated form of SrSO₄.     

Kinetic and thermodynamic factors controlling the distribution of SO32− and Na+ in calcites and selected aragonites

Significant amounts of SO₄^2?, Na⁺, and OH^? are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO₄^2?. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na⁺, but very low concentrations of SO₄^2?. The SO₄^2? content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na⁺ and SO₄^2? increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO₄^2? beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO₄^2? is the same as that of aragonite. Na⁺ appears to have very little effect on the solubility product of calcites. The amounts of Na⁺ and SO₄^2? incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient ($\text{D}$) of SO₄^2? in calcite at 25.0°C and 0.50 molal NaCl is described by the equation $\text{D = k}{}_0\text{+ k}{}_1\text{R}$ where $\text{k}{}_0$ and $\text{k}{}_1$ are constants equal to $\text{6.16 × 10}{}^{\mathrm{?6}}$ and $\text{3.941 × 10}{}^{\mathrm{?6}}$, respectively, and $\text{R}$ is the rate of crystal growth of calcite in mg·min^?1·g^?1 of seed. The data on Na⁺ are consistent with the hypothesis that a significant amount of Na⁺ occupies interstitial positions in the calcite structure. The distribution of Na⁺ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na⁺ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na⁺ contents of calcites are not very accurate indicators of environmental salinities.     

Cassiterite exsolution with ilmenite lamellae in magnetite from the Huashan metaluminous tin granite in southern China

Sn⁴⁺ is generally the dominant form of tin in magnetite-series granites as shown by the presence of cassiterite or its incorporation into Ti-bearing minerals such as biotite and titanite. Little is known about the behavior of tin in magnetite. The Huashan granite is an oxidized tin granite in the Nanling Range, southern China, where it contains magnetite as the dominant Fe oxide mineral. It is included in biotite as an early phase and also as interstitial grains spatially associated with ilmenite, cassiterite, Sn-rich titanite (SnO₂ up to 5.9?wt.%), fluorite and apatite. This association indicates that tin enrichment occurred during the late stage of magma crystallization. Ilmenite lamellae display a trellis structure consistent with features of the “oxy-exsolution” process of Sn-bearing titanomagnetite precursor. Micro-inclusions of cassiterite (<1?μm in size) are found only within ilmenite lamellae. This suggests that magnetite with cassiterite inclusions is likely an indicator mineral of oxidized tin granites. Although rare in nature, Sn-bearing magnetite from weathered granites where concentrated in stream sediments, may serve as a strategic tracer for tin exploration in granite districts and in placer deposits, in general.     

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.