The coal waste material that results from Douro Coalfield exploitation was analyzed by gas chromatography with mass spectrometry (GC-MS) for the identification and quantification of the 16 polycyclic aromatic hydrocarbons (PAHs), defined as priority pollutants. It is expected that the organic fraction of the coal waste material contains PAHs from petrogenic origin, and also from pyrolytic origin in burning coal waste piles. The results demonstrate some similarity in the studied samples, being phenanthrene the most abundant PAH followed by fluoranthene and pyrene. A petrogenic contribution of PAHs in unburned samples and a mixture of PAHs from petrogenic and pyrolytic sources in the burning/burnt samples were identified. The lowest values of the sum of the 16 priority PAHs found in burning/burnt samples and the depletion LMW PAHs and greater abundance of HMW PAHs from the unburned coal waste material relatively to the burning/burnt material demonstrate the thermal transformation attributed to the burning process. The potential environmental impact associated with the coal waste piles are related with the release of petrogenic and pyrolytic PAHs in particulate and gaseous forms to soils, sediments, groundwater, surface water, and biodiversity. (C) 2011 Elsevier B.V. All rights reserved.