Coal-waste dumps are sources of a variety of pollutants, especially when coal-waste material undergoes self-heating. For this research, representative samples were taken from four dumps (Welnowiec, Czerwionka-Leszczyny, Rymer and Anna) in the Rybnik region. The set of samples collected were divided into three subsets, namely, (1) expelled bitumen precipitated on coal waste, (2) thermally-affected coal waste and (3) highly-thermally affected coal waste from active-and inactive sites. To assess the characteristic features and impacts of self-heating, Rock Eval pyrolysis, measured random vitrinite reflectance (Rr %) and gas chromatography-mass spectrometry (GC-MS) of coal waste extracts were applied. Typical features of the bitumen expelled are elevated parameters of S-1, PI, BI, and Py. Generally, the bitumen appeared at lower T-max values. The self-heating in oxygen deficiency, i.e. under pyrolytic conditions caused thermal cracking of organic matter. Later the generated bitumen expelled from the self-heating zone, migrated and accumulated on colder coal-waste surfaces. This expelled bitumen, observed under fluorescence, shows irregular shapes and coats the organic particles with yellowish-greenish colours. Migrated bitumen is also found in highly-thermally affected, where T-max values are extremely high due to the oxidation and maturation of organic matter (overmatured). R-0 % values based on HI-T-max comparison and the measured Rr % values generally well correlate in the burning coal waste and in highly-thermally affected samples. The greatest quantities of phenols (mostly C-1-C-2) occur in the bituminous subset, samples in which 2-3 ring PAHs also dominate. In addition, high relative percentages of phenols (mostly C-1-C-2) characterize thermally-affected coal waste, together with heavier pyrolytical PAHs; these samples were closer to the heating zone. In totally burned-out porous waste, the presence of adsorbed short-chain n-alkanes and lighter PAHs, and higher CPI, Pr/n-C-17 and Pr/Ph values, reflect migration from an active self-heating zone. (C) 2016 Elsevier Ltd. All rights reserved.