Abstract Most of the World’s large tungsten deposits are genetically related to fluorine-rich granitic magmas, their ores contain fluorine minerals, such as fluorite and topaz, and their host rocks have commonly undergone fluorine metasomatism to form greisens. In view of this evidence that tungsten ore fluids are enriched in fluorine, and the potential for fluoride to form stable complexes with hard acids (e.g., W6+), we investigated the solubility and speciation of tungsten in fluoride-bearing fluids at hydrothermal conditions. Experiments were conducted to measure the solubility of tungsten trioxide solid in fluoride-bearing aqueous fluids at temperatures between 100 and 250 °C and vapour-saturated water pressure. Based on the results of these experiments, tungsten is dissolved predominantly as H3WO4F2− in solutions containing 0.05–0.30 m HF at pH(T) values between 1.5 and 3.4. Significantly, the concentration of H3WO4F2− was up to two orders of magnitude higher than that of tungstate species in these experimental solutions. This species formed via the reaction WO3cryst + H2O + 2HF = H3WO4F2− + H+, logarithms of the equilibrium constants for which, vary from −4.39 ± 0.18 at 100 °C to −5.10 ± 0.17 at 250 °C. In solutions containing

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氟在花岗岩相关热液钨矿成因中的作用：实验和建模结果

摘要 世界上大多数大型钨矿床与富氟花岗岩岩浆成因有关，其矿石中含有萤石、黄玉等氟矿物，其母岩普遍经历氟交代形成灰岩。鉴于钨矿流体富含氟的证据，以及氟化物与硬酸（例如 W6+）形成稳定络合物的潜力，我们研究了钨在热液条件下含氟流体中的溶解度和形态。进行了实验以测量三氧化钨固体在 100 至 250 °C 之间的温度和蒸汽饱和水压下在含氟水性流体中的溶解度。根据这些实验的结果，钨主要以 H3WO4F2− 的形式溶解在含有 0.05–0 的溶液中。30 m HF，pH(T) 值介于 1.5 和 3.4 之间。值得注意的是，在这些实验溶液中，H3WO4F2− 的浓度比钨酸盐物种的浓度高两个数量级。该物种通过反应 WO3cryst + H2O + 2HF = H3WO4F2− + H+ 形成，其平衡常数的对数从 100 °C 时的 -4.39 ± 0.18 到 250 °C 时的 -5.10 ± 0.17。在含有