| Summary: | A crystal-chemical study of historical specimens as well as new ones belonging to the jordanite–geocronite series from the Pollone baryte + pyrite ± (Pb-Zn-Ag) ore deposit (Valdicastello Carducci, Apuan Alps, Tuscany, Italy) has been performed. These crystals were collected in quartz extension veins embedded in three different occurrences: (i) baryte + pyrite orebodies; (ii) schist layers interbedded between baryte + pyrite orebodies; and (iii) schists at the contact with pyrite-poor baryte orebodies. Electron-microprobe data indicated the occurrence of three distinct groups of compositions within the sample suite. These correspond to As-bearing geocronite, Sb-rich jordanite, and Sb-bearing jordanite, with mean compositions Pb14Sb3.8As2.2S23, Pb14Sb2.9As3.1S23, and Pb14Sb2.6As3.4S23, respectively. Crystals representative of these different compositions have been investigated through single-crystal X-Ray diffraction studies and their crystal structures have been solved to R1 = 0.078, 0.069, and 0.033, respectively. The unit-cell volume decreases passing through As-bearing geocronite (V = 2149.5(3) Å3) to Sb-bearing jordanite (V = 2132.3(3) Å3). The As-to-Sb substitution takes place preferentially at the Sb4 site; through the increasing of the Sb content, Sb can substitute As also at the As6 site. According to the structural study of the ore deposit, formation of jordanite–geocronite is subordinated to a late Alpine deformative D2 stage, which permitted in situ remobilization of preexisting sulfide ore in small quartz extension veins. Such a local recrystallization would explain the variability of the As/(As + Sb) ratio of the members of the jordanite series, reflecting the heterogeneity of the orebody.
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