In the region of Illapel, Chile, dioritic and andesitic rocks of Cretaceous to Paleocene age from the Unidad San Lorenzo Formation have suffered strong alteration resulting in the formation of a kaolin-rich zone, which is mined in the La Vanguardia open pit near Combarbalá. Detailed mineralogical and chemical investigations of channel samples from this mine, involving a combination of optical microscopy, XRD, SEM-EDX, XRF and TEM, permitted recognition of a zone of silicification and a zone of advanced argillic alteration, both of which contain alunite s.s. and aluminium-phosphate-sulphate (APS) minerals of the woodhouseite group with subordinate amounts of gorceixite, florencite and goyazite. These minerals are found to have originated from infiltration of meteoric waters. The passage from silicification into advanced argillic alteration was associated with an increase in sulphate activity as manifested by the increase of SO42— at the expense of PO43— in the alunite s.s. and by an increase of the Au content from 0.01 to 0.03 mg/kg Au. This high sulphidation type of wallrock alteration may be roughly compared with the Nansatu type of White (1991).