Résumé : The application of a micro-characterization protocol coupled with a balance approach has allowed the relevant monitoring of a phosphation process for fly ash produced by municipal solid waste incineration. The three main steps of this process consist in removing the salts (chlorides, sulfates) by dissolution at basic pH, phosphation of the residue to trap metals, and its calcination to destroy dioxin-like compounds. The chemical and mineralogical balances compiled on the samples after each step of the process validate these main objectives and highlight the wide phosphorus distribution throughout the sample during the phosphation process, as well as the formation of apatite-type crystallized phosphates. During calcination, the increase in the proportion of crystallized phosphates apatite and whitlockite is largely attributable to the presence of an available calcium source, corresponding to the calcite formed during washing. The metals Pb and Zn, initially distributed in the silicate and carbonate phases, are broadly redistributed in the phosphate neoformations after carbonate dissolution, thus guaranteeing a more permanent stabilization. © 2002 Elsevier Science Ltd. All rights reserved.