Systematic changes in mineralogy, enrichment and depletion of selected elements, and mineralogical speciation of selected elements in fly ash and bottom ash samples from the Lingan Power Plant were compared to run-of-mine and pulverized feed coal from the Sydney coalfield, Nova Scotia, eastern Canada. The analytical techniques used were an electron microprobe equipped with energy and wavelength X-ray dispersive spectrometers, X-ray diffraction, neutron activation, scanning electron microscopy with energy dispersive X-ray and incident light petrography. Three types of glasses (Fe/O-rich, Fe/Al/Si/O-rich and or Al/Si/O-rich) were identified in the combustion residues; they were formed as a result of the interaction of melted pyrite and clay minerals. Compared to the feed coal, most elements were enriched 10 to 20 times in the fly ask The concentration of the elements in both the fly ash and bottom ash are comparable to coal ash that is generated by the low temperature asher in the laboratory. Some chalcophile elements such as arsenic and lead occurred as a solid solution in pyrite in the feed cod and were concentrated in the float fraction (density: < 2.81 g/cm(3)) of the fly ash with non-crystalline Fe-oxides. X-ray mapping of arsenic in the fly ash and bottom ash indicates that arsenic was evenly distributed as oxide within the Fe/O- and Fe/Al/Si/O-rich glass and crystalline phases in the fly ash, possibly in solid solution. Arsenic is associated with Fe/O and Fe/S crystalline phases in the bottom ash.