In situ, high-temperature energy-dispersive X-ray powder diffraction (EDXRD) data have been collected on synthetic and a natural sample of mercury sulphide (HgS). These measurements were made between temperatures of 295 and 798 K. Synthetic samples of HgS were prepared by reaction between sulphide and mercury in aqueous solution. In a subsequently dried and aged synthetic HgS sample, heated in vacuo, there is a change from a poorly crystalline pseudocubic material into a well crystalline cubic material in the temperature region 583–623 K. At higher temperature (748 K), there is evidence for a partial phase transition to the high temperature hypercinnabar HgS structure. In a neoformed synthetic sample, heated in a sealed Ti container, the initial ‘pseudocubic’ metacinnabar phase partially transforms to a previously unknown phase (XHgS) in the temperature range 467–522 K. This phase disappears at 527 K, and the metacinnabar phase changes to a well crystalline cubic phase; cinnabar develops at 542 K. The proportion of cinnabar continues to increase up to 647 K. Both metacinnabar and cinnabar phases are retained on cooling. No phase transitions were observed for the natural cinnabar sample.

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.