In the Douro Coalfield anthracites were exploited for decades (1795-1994). Besides many small mines Douro Coalfield had two principal mining areas (S. Pedro da Cova and Pejao). Coal mining activities cause several impacts on the environment, one of which is the amount of discard or waste which was disposed of all over Douro Coalfield resulting in one of the most significant and severe impacts on the environment. Over 20 waste piles exist in the old mining areas, geographically dispersed, and three of them are presently burning. Their ignition was caused by forest fires during the summer of 2005. Samples from the burning and unburned zones of the waste piles were studied as were the gas from vents and the minerals resulting after combustion. Geochemical processes and mineralogical transformations in the burning coal waste pile were investigated. Microscopic analyses of the samples identified some particular aspects related with combustion: oxidation of pyrite, the presence of iron oxides, organic particles with cracks and rims with lowered (suppressed) Rr, devolatilization vacuoles and some char structures. The occurrence of vitreous (glassy) material as well as Fe-Al spinels in the burning coal waste provide evidences that the combustion temperature could have reached values above 1000 degrees C. Due to combustion, and as expected, the samples studied reported high ash yields. Samples taken from the burning zones reported an increase of As, Cr, Li, Nb, Ni, Pb, Rb, Sr and LREE concentrations and a decrease in Zr and HREE concentrations. Enrichment in Cs, Li and Rb was noted when comparing with the geochemical composition of black shales and world coals composition that is related with the contribution of granitic rocks in the sediments that originated the main lithologies of the Douro Coalfield (carbonaceous shale and lithic arenites). Cluster analyses (R-type and Q-type) were performed to understand the trend between the unburned and burning samples and it seems that some chemical variations are responsible for this separation. Elemental sulphur and salammoniac (ammonium salt) are the coal fire gas minerals neoformed on the surface of piles, near the burning zones. They were identified by different techniques, mainly SEM-EDX, XRD and FTIR. Relatively high concentrations of several aromatic compounds were detected in the gas collected at the studied areas, as well as aliphatic hydrocarbons. The highest concentrations of aromatic hydrocarbons were measured in gas samples from S. Pedro da Cova waste pile. The exposure to hazardous compounds present in the gas is a serious risk to human health and the environment. (C) 2009 Elsevier B.V. All rights reserved.