厌氧环境雌黄溶解产物形态的XAS研究

雌黄是砷的环境地球化学过程中的重要的次生矿物.雌黄的溶解性研究对于研究砷在水环境中的形态转化和环境归趋具有重要意义.环境中p H和硫化程度对于雌黄中的砷的形态变化及其稳定性有重要影响.通过室内模拟实验,结合同步辐射X射线近边吸收光谱(XANES)和扩展X射线吸收光谱(EXAFS)表征手段研究了近中性厌氧条件下,有硫和无硫体系中雌黄溶解产物中稳定存在的砷形态.结果表明,在p H中性条件下,雌黄在两种体系中均形成硫代砷和亚砷酸盐的混合物,有硫体系中硫代砷是以全硫代为主,而无硫体系中硫代亚砷酸盐是部分硫代为主.线性拟合分析确定在有硫体系中硫代亚砷酸盐形态占总砷形态的88.2%,亚砷酸盐形态占总砷形态的11.8%,而在无硫体系中,硫代三价砷形态占总砷形态的43.7%,亚砷酸盐形态占总砷形态的56.3%.可见亚砷酸盐的形成与砷硫比有关,提高硫砷比可以提高亚砷酸盐中硫取代的比例以及全硫代亚砷酸盐的形成.

XAS Analysis upon Dissolved Species of Orpiment in Anoxic Environment

The orpimentAs₂S₃(s)] is an important secondary mineral in the geochemical process of arsenic in the environment. The study upon orpiment dissolution is important to investigate the migration and transformation of arsenic in the environment. The environmental pH and sulfur content have vital influence on species changing and stability of arsenic species in orpiment. Here we analyzed the stable arsenic species of anoxic orpiment dissolution in sulfidic and the absence of sulfide solutions at neutral condition with simulation test via X-ray absorption near edge spectroscopy(XANES) and extended X-ray absorption fine structure(EXAFS). The results showed that orpiment dissolution contained a mixture of arsenite and thioarsenite species at neutral condition, and arsenic species in sulfidic solutions is mainly thioarsenic, while arsenic species in the absence of sulfide solutions is oxythioarsenic. The results of Linear Combination of Fits showed that arsenic species were arsenite (88.2%) and thioarsenite(11.8%) in sulfidic solutions, and there were arsenite (56.3%) and thioarsenite(43.7%) in the absence of sulfide solutions. Our results confirmed that the formation of arsenite was related to the total sulfur to total arsenic ratios, and the form of thioarsenite species could be enriched by increasing of the total sulfur to total arsenic ratio.