Arsenopyrite-rich wastes from abandoned tungsten and tin exploitations were studied to determine the composition and characteristics of the secondary phases formed under natural weathering conditions so as to assess their potential environmental risk. Representative weathered arsenopyrite-bearing rock wastes collected from the mine dumps were analysed using the following techniques: X-ray powder diffraction (XRD) analysis, polarizing microscopy analysis, electron microprobe analysis (EMPA) and microRaman and Mossbauer spectroscopies. Scorodite, pharmacosiderite and amorphous ferric arsenates (AFA) with Fe/As molar ratios in the range 1.2-2.5 were identified as secondary arsenic products. The former showed to be the most abundant and present in the different studied mining areas. Its chemical composition showed to vary in function of the original surrounding rock mineralogy in such a way that phosphoscorodite was found as the mineral variety present in apatite-containing geoenvirons. Other ever-present weathering phases were goethite and hydrous ferric oxides (HFO), displaying, respectively, As retained amounts about 1 and 20% (expressed as As2O5). The low solubility of scorodite, the relatively low content of AFA and the formation of compounds of variable charge, mostly of amorphous nature, with high capacity to adsorb As attenuate importantly the dispersion of this element into the environment from these arsenopyrite-bearing wastes. (c) 2010 Elsevier B.V. All rights reserved.