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It was extensively studied that combustion of coal for power generation is an important anthropogenic contributor of toxic elements to the environment. In present study the exposure of arsenic (As) from coal samples collected from two sites (III and V) of Thar coalfield before and after burning were evaluated. Meanwhile the proximate parameters and elemental composition of collected coal samples were also studied in detail. The quantitative analysis of As in coal samples and their ash were achieved by microwave-assisted acid digestion methods prior to analyze by MHS-15 hydride generation atomic absorption spectrometry. The contents of As in coal samples of site-III of Thar coalfield was found to be higher as compared to site-V, it may be due to difference in geocheinical mineral composition. The resulted data of ash indicated that during combustion of coal >88.5% of As can be released into the atmosphere. The evaluated moisture contents in coal samples of That coalfield indicated that the direct use of coal is not suitable for power generation and other activities. (C) 2015 Published by Elsevier B.V.