Secondary minerals of weathered orpiment-realgar-bearing tailings in Shimen carbonate-type realgar mine, Changde, Central China

The formation and dissolution of arsenic minerals commonly controls the mobility of As in sulfide mines. Here, we present the results of research based on X-ray powder diffraction (XRD), Raman microprobe spectrum, scanning electron microscope (SEM), and transmission electron microscope (TEM) analyses, Scanning transmission X-ray microscope (STXM) and X-ray absorption fine structure (XAFS) analyses to further understand the weathering of orpiment- and realgar-bearing tailings from the Shimen realgar deposit, the largest realgar deposit in Asia. These analyses indicate that four different types of As-bearing secondary minerals are present in the tailings, including arsenic oxides, arsenates, As-gypsum, and As-Fe minerals, and that arsenic in the tailings is present in +3 and +5 valence states. The precipitation of arsenates is attributed to the interaction between As-enriched run-off waters and carbonate minerals. The Ca-arsenates in the tailings are dominantly weilite and pharmacolite, both of which have Ca/As atomic ratios of 1. In addition, SO4 (2-)/HAsO4 (2-) substitution in gypsum is another important mechanism of arsenic precipitation.