Arsenic is one of the most concerned trace elements in coal because of its toxicity and environmental persistence. Little information about the transformation behavior of arsenic under pyrolysis conditions was reported. In this paper, the volatilization behavior of arsenic and the influence of coexisting mineral matters and additive CaO were investigated during pyrolysis of Yima coal in a fluidized-bed reactor at temperatures ranging from 350 to 900 degreesC. The modes of occurrence of arsenic in Yima raw coal and its two char samples are determined using four methods including density fractionation, demineralization, X-ray diffraction (XRD) and sequential chemical extraction. It is found that arsenic in Yima coal is mainly associated with pyrite, and changes greatly during coal pyrolysis. Staged volatility behavior of arsenic is observed during Yima coal pyrolysis. From 350 to 500 degreesC, arsenic volatility increases with increasing temperature, while it changes little from 500 to 800 degreesC. Arsenic behavior in Yimal) (demineralized sample of Yima) and CaO additive reveal that the vaporization of arsenic in Yima coal during pyrolysis is retarded by its coexisting mineral matters or added CaO to form thermally stable forms of arsenic. These forms might be generated through the formation of As-Ca complexes such as calcium arsenate, or through absorption and capture reactions with aluminosilicate mineral matters and trapped into their lattices. (C) 2003 Elsevier Ltd. All rights reserved.