A combination of geochemical and mineralogical methods was used to determine the concentrations, mobility, and sources of As in coal-combustion ashes and soils in the vicinity of a thermal power plant at Nováky, central Slovakia. Fresh lagooned ash, ashes buried under agricultural soils for 45 a, and the overlying soils, contain high concentrations of As ranging from 61 to 1535 mg/kg. There is no differences in the water extractable percentages of As between the fresh lagooned ash and buried ashes, which range from 3.80% to 6.70% of the total As. This small amount of As may perhaps reside on the surfaces of the ash particles, as postulated in the earlier literature, but no evidence was found to support this claim. Electron microprobe analyses show that the dominant primary As carriers are the aluminosilicate glasses enriched in Ca and Fe. The acid View the MathML sourceNH4+-oxalate extraction hints that the oxyhydroxides of Si, Al, and Fe are the most probable secondary carriers of labile As. The X-ray absorption spectroscopy (XAS) analyses show that As in the lagooned and buried ashes occurs mostly as As(V). The long-term burial of the coal-combustion ash under agricultural soil did not cause any major change of its chemical composition or As lability compared to the fresh lagooned ash.