Microwave-assisted acid digestion (MW-AD) followed by atomic spectrometries such as inductively coupled plasma-atomic emission spectrometry (ICP-AES) was examined for the determination of major and trace elements in coal fly ash (CFA). Effective digestion conditions were studied using four certified reference materials of CFA, with particular focus on the composition of acid mixture and the removal of HF after MW-AD. When MW-AD was conducted without using HF (HNO3 + H2O2), the tested elements yielded fairly poor recoveries. When MW-AD with HF (HNO3 + HF + H2O2) was carried out, two methods for HF removal were attempted, H3BO3 addition and evaporation of acids. In the former method, while the recoveries of major elements (Al, Ca, Fe, and Mg) were satisfactory, those of trace elements were not satisfactory; in particular, the recovery of Pb was fairly low. In the latter method, the recoveries of At, Ca, and Mg were extremely poor; however, those of other elements including the trace elements (Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn) were satisfactory. In this paper, the optimization of the digestion method for ICP-AES is discussed. Further, the advantages and limitations of ICP-AES in the determination of elements in CFA are assessed. (c) 2005 Elsevier Ltd. All rights reserved.