Speciation of antimony in representative sulfidic hot springs in the YST Geothermal Province (China) and its immobilization by spring sediments

As a well-known toxic element, antimony occurred in a wide range of concentrations in the geothermal waters discharging from Rehai and Daggyai, two representative hydrothermal areas in the Yunnan-Sichuan-Tibet Geothermal Province of China. Antimony speciation in different types of the hot springs in Rehai and Daggyai varied greatly as well, and tri- and tetrathioantimonate were detected in most neutral to alkaline Rehai hot springs. Neutral to alkaline pH, high sulfide concentrations, and high sulfide to antimony ratios were the critical factors promoting the formation of thioantimonates. The fact that no thioantimonates were detected in neutral to alkaline Daggyai hot springs is attributed to high concentrations of coexistent arsenic capable of inhibiting the thiolation of oxyantimony anions, because thioantimonates are kinetically more labile than thioarsenates. Upon discharge of the hot springs, both total aqueous antimony and arsenic decreased rapidly and substantially via immobilization to the sediments in the spring vents and their outflow channels. Some of the common iron-bearing minerals in the spring sediments, like pyrite and goethite, are known sinks for antimony and arsenic. Yet, an interesting difference was observed with antimony and iron contents in the sediment samples showing a significant correlation that was lacking for arsenic and iron contents. The explanation might be that for arsenic, sorption affinities are known to vary significantly with aqueous arsenic speciation and mineral phases. Typically, thiolation increases, and oxidation decreases arsenic mobility. Sorption experiments for antimony conducted in the present study, in contrast, showed that different antimony species were comparably sorbed to pyrite over a wide range of initial antimony concentrations and to goethite at relatively low initial antimony concentrations (but still covering the concentration range of antimony in common natural waters), so neither thiolation nor oxidation contributed significantly to the mobility of antimony in the hot springs investigated in this study.