Electron microprobe study of individual macerals in low-rank coals of Permian to Tertiary age from Australia, New Zealand, Indonesia and Thailand has shown that measurable proportions of inorganic elements are consistently found in organic components, especially the vitrinite macerals, in which no minerals or mineral inclusions are visible under the microscope. The vitrinites of such coals have been found to contain up to around 0.5% Al, 1.5% Ca, 0.1% Mg, 0.7% Fe and 0.2% Ti. The Al occurs without measurable proportions of Si, and hence does not represent sub-micron clay minerals within the maceral components. Inertinite macerals in the coals, such as fusinite, typically contain lesser proportions of these elements, and often have no more than background (<0.05%) concentration levels. Except where soluble minerals such as carbonates are also present, the proportion of Ca, Al and Fe indicated from microprobe analysis in the macerals, especially in the vitrinites, is very close to the mobile proportion of the same elements indicated in previous studies from selective leaching techniques. This suggests that the elements occur as an inherent part of the organic structure in the macerals, possibly as a combination of exchangeable ions, carboxylates, chelates and other organometallic compounds; they may also be held by physical absorption and adsorption mechanisms, or may possibly represent inorganic nanoparticles. The proportions of Al, Ca and Fe in the vitrinites of the samples studied decrease with coal rank. Although there are exceptions, these and other non-mineral inorganic elements (Mg, Ti) are also not usually detected by the microprobe in higher rank coals (above 75% carbon in vitrinite or around 0.6% vitrinite reflectance). Their absence is probably a consequence of expulsion from the maceral structures during the progressive aromatization associated with rank advance, by processes such as dehydration, decarboxylation and dehydroxylation. (C) 2009 Elsevier B.V. All rights reserved.