Ammonioalunite, ammoniojarosite and their solid-solution series found on a burning coal dump at Czerwionka, Upper Silesian Coal Basin, Poland, were examined using powder X-ray diffraction, electron probe microanalysis, inductively coupled plasma mass spectrometry, infrared spectroscopy and thermal analysis methods. The minerals occur as yellow, fine-grained crusts and botryoidal masses in the outer part of a sulphate crust found ∼1 m below the surface. The crust is composed mainly of godovikovite and tschermigite that formed by interaction of sour fire gases or solutions and waste materials beneath the surface of the burning coal dump at temperatures of at least 80–100°C. The crystals often reveal oscillatory zoning due to different Al and Fe contents in thin bands, from near end-members to extensive solid solutions. Our analyses suggest the existence in nature of a complete solid solution between ammonioalunite and ammoniojarosite. They also carry essential amounts of chlorine.