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Among the Zn–Hg–S and Hg–Se–S series minerals, Hg-bearing sphalerite and metacinnabar are uncommon in ore deposits, but they are useful indicators of temporal variation of ore forming fluids, as well as presenting metallurgical implications for Hg-bearing deposits. To understand the Hg–Zn–Se mineralization system of the Tongren–Fenghuang Hg Belt (TFHB), the Zn–Hg–S and Hg–Se–S series minerals of the Chashula Hg–Zn and Dongping Hg–Ag–Se carbonate-hosted deposits were studied by microscopic observation, electron-probe microanalysis, and X-ray diffraction analysis. Observations show that the Chashula and Dongping deposits experienced two stages of mineralization (Stages 1 and 2). The pyrite, sphalerite I (Hg-poor sphalerite), and quartz formed in Stage 1, while the Zn-bearing cinnabar, sphalerite II (Hg-bearing sphalerite), cinnabar, selenium metacinnabar, and Ag minerals formed in Stage 2. The Hg-bearing sphalerite, containing 13.36–22.26 wt % Hg (average 18.73 wt % Hg), replaces sphalerite I (0.00–1.31 wt % Hg). The Hg-bearing sphalerite of the Dongping Hg–Ag–Se deposit contains lower Hg (10.12–14.67 wt % Hg) than that of the Chashula deposit. The unit cell a of the Hg-bearing sphalerite gradually increases with increasing Hg content. The texture of the Zn-bearing cinnabar shows it is not stable and easily breaks down to Hg-bearing sphalerite and cinnabar through the chemical reaction: (Hg,Zn)S → (Zn,Hg)S + HgS. Selenium metacinnabar intergrowths with tetrahedrite and miargyrite were found only in the Dongping deposit. The selenium metacinnabar contains 76.57–83.97 wt % Hg, and extensive isomorphic substitution of Se and S (6.81–19.21 wt % Se, 4.14–10.32 wt % S). Based on our mineralogical studies, the Zn, Hg, Hg–Zn, and Hg–Se mineralization styles in the TFHB are interpreted as the product of different stages in the mineralization process

Mineralogy of Zn–Hg–S and Hg–Se–S Series Minerals in Carbonate-Hosted Mercury Deposits in Western Hunan, South China