A scanning electron microscope (SEM) has been used to study the in situ accessory minerals in polished blocks and pellets of petrographically analysed samples of the Waynesburg coal (hvb). Individual grains from the low-temperature ash (LTA) of the same coal were also studied. The visual resolution of the SEM permitted the detection of submicron mineral grains, which could then be analysed by the attached energy-dispersive system. Emphasis was placed on the highly reflective grains in the carbominerite bands. Among the most abundant accessory minerals observed were rutile, zircon, and rare-earth-bearing minerals. Small (1–5 μm) particles of what may be authigenic iron-rich chromite and a nickel silicate form rims on quartz grains. The SEM also permits the observation of grain morphology and mineral intergrowths. These data are useful in determining authigenicity and diagenic alteration. Substances in density splits of LTA include authigenic, detrital, extraterrestrial magnetite, tourmaline, and evaporite (?) minerals, and a fluorine-bearing amphibole. This analytical approach allows the determination of specific sites for many of the trace elements in coals. In the Waynesburg coal, most of the chromium is in the iron-chromium rims, the fluorine is in the amphibole, and the rare-earth elements are in rare-earth-bearing minerals. The ability to relate trace-element data to specific minerals will aid in predicting the behaviour of elements in coal during combustion, liquefaction, gasification, weathering, and leaching processes. This ability also permits insight into the degree of mobility of these elements in coal and provides clues to sedimentological and diagenetic conditions.