Calcination of Hg ores has resulted in serious contamination of mercury (Hg) in the environment. To understand the mobilization of Hg in the calcine pile, the speciation of Hg in a profile of a large calcine pile in the Wanshan Mercury Mine, SW China was investigated using the X-ray absorption spectroscopy (XANES), to understand the mobilization of Hg in the calcine pile. Higher concentrations of Hg were observed at the 30-50 cm depth of the profile, corresponding to a cemented layer. This layer is observed in the entire pile, and was formed due to cementation of calcines. Hg species in calcines include cinnabar (alpha a-HgS), metacinnabar (beta-HgS), elemental Hg(0), and minor mercuric chloride (HgCl2), but these Hg species show dramatic changes in the profile. Variations in Hg speciation suggest that extensive mobilization of Hg can occur during weathering processes. We show that the cemented layer can prevent the leaching of Hg and the emission of Hg(0) from the pile. High MeHg concentrations were found near the cemented layer, indicating Hg methylation occurs. This study provides important insights into the environmental risk of Hg in mining areas. (C) 2016 Elsevier Ltd. All rights reserved.