Kaolin deposits extending over an area of ~10 km2 in the western and southern parts of Limnos Island, northeast Aegean Sea, Greece, were studied. The kaolin deposits are alteration products of volcanic rocks, mainly trachytes, trachyandesites, andesites and dacites. Study of the collected samples was carried out using X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), energy-dispersive scanning electron microscopy (SEM-EDS), Fourier transform Raman spectroscopy (FT-Raman), Fourier transform infrared (FTIR) techniques and inductively-coupled plasma (ICP) bulk rock chemical analyses for major, trace and rare earth elements. The extensive alteration of the parent rocks resulted from the circulation of hydrothermal fluids through faults and fractures. The development of the various assemblages depends not only on the temperature and composition of the hydrothermal fluids but also on the distance of the rock from the fault or the channel of the ascending hydrothermal fluids.

Kaolinite, dickite, halloysite, illite, smectite and mixed-layer illite-smectite and jarosite were detected in the altered volcanic rocks forming locally various alteration zones. Smectite-rich zones and illite-rich zones are relatively infrequent. In the halloysite-rich zones, the kaolinization of feldspars is accomplished in four stages. The kaolinizaton of feldspars in the kaolinite-dickite-rich zones follows five discrete stages. In the less altered rocks, thin layers of kaolinite are formed on the surface of feldspars. With increasing kaolinization, kaolinite is developed on the surface of feldspars forming extended parallel booklets of newly formed kaolinite. In the third stage, feldspar crystals are partially altered to kaolinite booklets. As kaolinization advances, kaolinite becomes well formed and, in the most altered rocks, feldspars are partially or completely altered to dickite books, depending on the temperature of the hydrothermal fluids.