This work is an investigation of the assemblages of supergene minerals occurring in hydrothermal REE–U–Au quartz-vein mineralisation at the Prakovce-Zimná Voda site, Slovakia. Heterogeneous uranyl arsenates and minor phosphates of the autunite group (nováčekite, kahlerite, threadgoldite, autunite, arsenuranospathite and chistyakovaite) together with scorodite and Sb–Bi-rich philipsbornite–segnitite-series minerals formed by oxidising fluids during decomposition and leaching of primary hypogene uraninite, brannerite and base-metal sulfides and sulfosalts. A progressive change of pH from acidic to near-neutral due to the gradual consumption of sulfides resulted in the formation of late phosphuranylite, pharmacosiderite and arseniosiderite. Goethite and other Fe oxides represent the latest hydrous ferric mineral phases and were formed after most of the As was already fixed in Fe arsenates. Antimony and Bi were taken up only into philipsbornite–segnitite and suggest unusual conditions during this process. X-ray absorption spectroscopy indicates that Sb in the philipsbornite–segnitite is fully oxidised (0.1–0.4 apfu Sb5+, octahedral coordination on the G site). Pentavalent Sb together with the presence of ferric oxides and arsenates and uranyl minerals suggest oxidative conditions during weathering. This study also indicates that hydrous ferric arsenates are dominant and stable secondary minerals in a supergene environment in a quartz vein rich in Fe and As accompanied by elevated concentrations of U, Pb, Sb, Bi, S, P, Ca and Ba under oxidising conditions.

The profile of the supergene zone of the Zapadno-Ozernoe massive sulphide Cu-Zn deposit differs from the classic model (Emmons, 1917) in that it includes a prominent dark sooty subzone rich in secondary sulphides. This subzone is situated above residual pyrite sands, which overlie the massive sulphide body and below quartz-baryte leached sands. It contains a diverse mineral assemblage which consists of secondary sulphides such as galena, sphalerite, metacinnabar, Se-bearing pyrite—dhzarkenite series, tiemannite, native Au, native S and native Se, and unidentified sulphosalts of Ag and Hg. The very light S isotope composition of the secondary sulphides (lowest values δ34S = —17.2‰ (VCDt) in comparison with primary pyrite ∼0‰ and baryte +18.4‰ is indicative of bacterial sulphate reduction. The overlying oxidized part of the supergene column contains minerals of the jarosite-beudantite- segnitite series. The maximum concentrations of Au, up to 150 ppm, occur in the lower part of the profile. The atypical structure, mineral assemblage and S isotope composition of the secondary sulphides in the dark layer of the supergene profile are indicative of particular geochemical conditions due to the existence of a stagnant water body that gave rise to intense bacterial activity, in turn controlled by fluctuations in the redox boundary.