Municipal solid waste of incineration (MSWI) bottom ashes are recycled as aggregates in civil engineering. These heterogeneous materials are composed of crystalline and glassy solid phases which contain trace metals, presenting a potential risk to the environment. Secondary ion mass spectrometry (SIMS) can provide quantitative chemical information, in particular the localisation of metals at trace level. Unstable glassy phases formed during incineration are present in relatively high proportions. Their analyses suggest a continuum between melilite-bearing glasses and dark glasses enriched in iron with abundant spinel aggregates. These primary glasses are enriched in zinc (~4500 ppm) but depleted in lead (~800 ppm) by comparison with the bulk chemical composition and reference materials. Heterogeneous cementing and encrusting admixtures on coarse grains are studied in a second step. SIMS imaging suggests a superposition of band zones including an intermediate layer enriched in iron oxyhydroxides and a superficial layer with calcium accumulation. A strong spatial association between lead and iron is systematically observed. Extended X-ray absorption fine structure (EXAFS) supports these observations by demonstrating that lead co-precipitation within iron oxyhydroxides, or sorption on their surfaces, may be a main containment process in the cementing and encrusting admixtures, whereas lead speciation is globally more complex in MSWI bottom ash.