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.