Tungsten from typical magmatic hydrothermal systems in China and its environmental transport

Abstract

Tungsten is of extraordinarily high concentrations in the geothermal waters discharging from several representative Tibetan magmatic hydrothermal systems (up to 1103 μg/L), which are also characterized by exceptionally high W/Mo molar ratios (up to 1182). The geochemical origins of the tungsten in these geothermal waters were investigated, with a comparison to those from Rehai, the sole magmatic hydrothermal system in Yunnan, which is another major part of the Yunnan-Sichuan-Tibet Geothermal Province of China. The results show that the lithology of reservoir host rocks is the primary factor controlling the tungsten concentrations of the geothermal waters, although the contribution of magmatic fluid input cannot be ruled out. In this study, the geothermal waters are generally rich in sulfide, and therefore the molybdenum in the reservoir fluids has been substantially precipitated as the form of molybdenite; in contrast, the reservoir fluids are well undersaturated with respect to tungstenite which is much more soluble than molybdenite. Thus the neutral/alkaline hot springs, i.e. the evolved reservoir fluids, have high W/Mo molar ratios as well. In the hot spring sediments, the distribution pattern of tungsten is quite different. The concentrations of tungsten are the highest in the sediments with high iron concentrations collected from the acid hot spring vents and outflow channels. The adsorption of aqueous tungsten onto iron-bearing minerals, like goethite or pyrite, is favorable at acid pH values and thereby responsible for the very high tungsten concentrations of these acid hot spring sediments. The proportions of thiotungstates in total tungsten are quite low for all the hot springs, as indicated by thermodynamic calculations, suggesting that thiolation of tungstate has little impacts on the environmental transport and fate of geothermal tungsten in the investigated hydrothermal areas. This is the first study to report the tungsten geochemistry of hot springs in mainland China.