The aim of this work was to evaluate the stability of arsenic and selenium species retained in a lime/limestone mixture obtained by using limestone as a sorbent for gas cleaning in a coal gasification atmosphere. It was found that the stability of arsenic and selenium species produced by the gas-solid reactions with lime/limestone may be affected by their exposure to air and by their contact with water. The results confirm the conclusions of a previous work in which Ca(AsO2)(2) and CaSe was postulated as the products of the reaction between the arsenic and selenium species present in a coal gasification atmosphere with lime/limestone. Moreover it was proved that the compounds (Ca(AsO2)(2) and CaSe) may undergo transformations when the sorbents post-retention are stored or disposed of in air. From the results obtained by XAFS it was possible to identify the Ca-3(AsO4)(2) produced by the oxidation of the Ca(ASO(2))(2) on the sorbent surface. The XAFS results for selenium showed that the CaSe formed on the sorbent was transformed to form several species, but mainly elemental Se. These changes in the speciation of arsenic and selenium may explain the behavior of the sorbent post-retention during the water solubility test. Although the selenium compounds and the products that may originate from their decomposition in water are not toxic, in the case of arsenic, species like Ca(AsO2)(2) and Ca-3(AsO4)(2) may lixiviate, and generate toxic arsenic compounds in solution that could pose a risk when the sorbent is finally disposed of. (C) 2009 Elsevier B.V. All rights reserved.