[en] The mineralogical composition of mining wastes deposited in countless dumps around the world is the key factor that controls retention and release of pollutants. Here we report a multi-method data set combining mineralogical (X-ray diffraction, electron microprobe and Raman microspectrometry) and geochemical (sequential extraction and pore water analysis) methods to resolve As mobility in two 50-years-old mining waste dumps. Originally, all of the As in the mining wastes selected for the study was present as arsenopyrite and with time it has been replaced by secondary As phases. At Jedová jáma mining area, the most of As precipitated as X-ray amorphous ferric arsenate (HFA). Arsenic is also accumulated in the scorodite and Fe (hydr)oxide (with up to 3.2 wt.% As_2O_5) that is particularly represented by hematite. Mining wastes at Dlouhá Ves contain only trace amount of scorodite. Arsenic is primarily bound to Pb-jarosite and Fe (hydr)oxides (especially goethite) with up to 1.6 and 1.8 wt.% As_2O_5, respectively. The pore water collected after rainfall events indicated high concentrations of As (~ 4600 μg·L"−"1) at Jedová jáma, whereas aqueous As at Dlouhá Ves was negligible (up to 1.5 μg·L"−"1). Highly mobile As at Jedová jáma is attributed to the dissolution of HFA and simultaneous precipitation of Fe (hydr)oxides under mildly acidic conditions (pH ~ 4.4); immobile As at Dlouhá Ves is due to the efficient adsorption on the Fe (hydr)oxides and hydroxosulfates under acidic pH of ~ 2.8. Taken together, As mobility in the ferric arsenates-containing mining wastes may significantly vary. These wastes must be kept under acidic conditions or with high aqueous Fe(III) concentrations to prevent the release of As from incongruent dissolution of ferric arsenates. - Highlights: • Two 50 years-old sulfide-rich mining waste dumps were studied. • Environmental stability of secondary arsenic mineral phases were assessed. • Different modes of As binding are responsible for different As mobility.