Toxic elements arsenic and selenium in coal are of great concern mainly because of their adverse effects on human health during coal combustion. This paper describes the concentration determination of As and Se in coal and coal combustion products (CCPs), performed by collision/reaction cell technology (CCT) of inductively coupled plasma mass spectrometry (ICP-MS; collectively ICP-CCT-MS) after closed vessel microwave digestion. The reagents for 50-mg coal sample digestion are 2-ml 40% (v/v) HF and 5-ml 65% (v/v) HNO3 but for the CCP samples, the reagents include 5-ml 40% HF and 2-ml 65% HNO3. To significantly diminish the argon-based interferences at mass to charge ratios (m/z) 75 ((ArCl)-Ar-40-Cl-35) and 78 ((ArAr)-Ar-40-Ar-38), a helium and hydrogen mixture was used in the optimized hexapole collision cell. The results showed that CCT technology can effectively diminish the spectral interferences of the Ar-based polyatomic ions (ArCl)-Ar-40-Cl-35 and (ArAr)-Ar-40-Ar-38 to As-75 and Se-78, respectively. The method detection limit of As and Se is 0.024 and 0.095 mu g/l, respectively, and their linearity of the calibration curves in the range 0-100 mu g/l has a determination coefficient r(2)> 0.9999. The determination of As and Se in NIST standard reference materials of coal and fly ash samples showed that ICP-CCT-MS plus closed vessel microwave digestion is a reliable method for concentration determination of the two elements in coal and CCPs. (C) 2014 Elsevier B.V. All rights reserved.