The present document represents an attempt to summarize the most important features of the different forms of ED-XFR as applied to the analysis of airborne particulate matter. It is intended to serve as a set of guidelines for use by participants in the IAEA`s own programmes, and other scientists, who are not yet fully experienced in the application of ED-XRF to airborne particulate samples, and who wish either to make a start on using this technique or to improve their existing procedures. The methodologies for sampling described in this document are of rather general applicability. Emphasis is also placed on the sources of errors affecting the sampling of airborne particulate matter. The analytical part of the document describes the different forms of ED-XRF and their potential applications. Spectrum evaluation, a key step in X-ray spectrometry, is covered in depth, including discussion on several calibration and peak fitting techniques and computer programs especially designed for this purpose. 148 refs, 25 figs, 13 tabs.