► Santa Catarina power plant is the largest capacity in South America. ► Diagnosis was conducted to check hazardous element mobility during coal combustion. ► Most elements are bound to organic matter and sulfides in coal. ► U, As, and Cr increased mobility, mainly in the easily-soluble fraction, in coal ashes. ► Dumping and use of coal ashes pose significant risks to environment and human health. This paper reports about changes in mobility of hazardous elements contained in coal during combustion at a power plant in Santa Catarina (Brazil) and the environmental impact potential of ashes. Total and mobile element concentrations were determined by digestion and sequential extraction. Comparison of results within the mobile fraction showed that after combustion, oxidizable elements bound to organic matter and sulfides in coal were mostly transformed into elements easily soluble in water or slightly acidic conditions and, hence, most readily bioaccumulative in the environment in ashes, mainly U, Cr, and As. Capacity of ashes as a source of mobile pollutants was quantified by combining sequential extraction and annual production. Just considering the easily soluble fraction, coal ashes could leach up to 839tons of Al, 144tons of Fe, 100tons of Mn, 4.6tons of Zn, 3.1tons of Cr, 1.7tons of As, 1.5tons of Cu, 490kg of U, and 20kg of Pb every year. Bottom ashes are disposed of in landfill sites close to the plant. Fly ashes are recycled as construction material. Diagnostic processes do not consider checking for these highly mobile hazardous elements. Hence, uncontrolled dumping and use of these by-products may pose significant risks to environment and human health.