The data on the composition of metacinnabar and Hg-sphalerite with an isomorphous Cd admixture from some mercury and complex ore objects are summarized. There are two varieties of metacinnabar: (1) cadmium-rich (9.25–15.80 wt.%), with the minimum quantity of Zn admixture (0.67–3.94 wt.%), which has the idealized formula (Hg,Cd,Zn)S (Ulandu) and (2) with increased amounts of Zn (2.21–10.83 wt.%) and Cd (6.00–14.10 wt.%), having the formula (Hg,Zn,Cd)S (Arzak, Kadyrel’, Murzinskoe, Ravnou-1, Ravnou-2). The maximum content of isomorphous Cd (15.80 wt.%) was determined in the metacinnabar from the Ulandu ore occurrence. The Hg-sphalerites are compositionally divided into two groups: (1) with an increased Cd concentration (up to 7.96 wt.%) and (2) mainly with a low content of Cd admixture (0.0n–1.63 wt.%). The sphalerites of the first group are typical of mineral assemblages including Cd-Zn-enriched metacinnabar (Arzak, Kadyrel’, Murzinskoe, Sarasa). The sphalerite of the Sarasa deposit is included into this group arbitrarily, because it contains more cadmium than the sphalerites of the second group, which are constituents of parageneses only with Zn-metacinnabar or lacking it (Nikitovka, Khaidarkan, Dzhizhikrut, Bayan-Khan, Aktash). There are some Hg-bearing varieties of sphalerite with the idealized formulas (Zn,Hg,Fe)S, (Zn,Hg,Cd)S, (Zn,Cd,Hg,Fe)S, (Zn,Fe,Cd,Hg)S, (Zn,Hg,Cd,Fe)S, (Zn,Fe,Hg,Cd)S, and (Zn,Hg,Cu)S, which transforms into (Zn,Cu,Hg)S. The maximum Cd admixture (7.96 wt.%) was established in Hg-sphalerite from the Kadyrel’ ore occurrence. It is the highest content observed in natural Hg-bearing β-ZnS. The studied metacinnabar and sphalerite varieties are the only cubic phases of the natural system Zn–Hg–Cd–S, which is sometimes expanded because of minor admixtures of other metals. These varieties have a structure identical to the cubic phases of the synthetic systems Me–S and Me–Me–S, where Me = Zn, Cd, and Hg. None of Hg-bearing hexagonal solid solutions were found in the natural system Zn–Hg–Cd–S. The continuity of the natural isomorphous series ZnScub–HgScub has not been confirmed by finding of natural intermediate solid solutions at the series fragment between (Zn0.752Hg0.248)S and (Hg0.539Zn0.461)S. The metacinnabar varieties enriched in both Zn and Cd show no correlation between these elements. It is assumed that the host rocks with an increased content of cadmium compounds were the source of Cd for the formation of specific varieties β-HgS and β-ZnS.

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