Minerals of the system Bi-Te-Se-S related to the tetradymite archetype: Review of classification and compositional variation

Our compilation of similar to 900 published results of analyses for minerals of the tetradymite series (tellurobismuthite, tetradymite, guanajuatite, paraguanajuatite, kawazulite, skippenite, tsumoite, hedleyite, pilsenite, laitakarite, ikunolite, joseite-A, joseite-B) allows compositional fields among naturally occurring Bi-Te-Se-S compounds to be established. New compositional data for ingodite, laitakarite, pilsenite, kawazulite and tellurobismuthite extend previously known compositional limits. Recognized minerals can, for the most part, be satisfactorily and conveniently classified according to the ratio Bi(+ Pb)/(Te + Se + S), into the subsystems (isoseries) Bi2Te3-Bi2Se3-Bi2S3, Bi4Te3-Bi4Se3-Bi4S3 and BiTe-BiSe-BiS. Most minerals show limited compositional variation, but this is generally more extensive in the Se-bearing phases (e.g., laitakarite) and in certain members of the system Bi-Te, such as hedleyite and tsumoite. Substitution of minor Pb for Bi is widespread throughout the group, especially in the Bi4Te3-Bi4Se3-B-3 subgroup. Several possible additional minerals or compositional variants of existing minerals would appear to exist in nature, including Bi4Te2S3, Bi4Te(Se,S)(2), Bi3Te2Se and Bi-3(Te,S,Se)(4). Within the above groups, Bi(+ Pb)/(Te + Se + S) stoichiometry is remarkably constant, in accordance with known and derived structures in which all phases (except those in which Pb is essential) can be envisaged in terms of various combinations of nonvalent five-atom Bi2X3 and two-atom Bi-2 layers. Deviation from Bi(+ Pb)/(Te + Se + S) stoichiometry within the isoseries may be linked to stacking disorder. Noting the appearance of many other phases and stoichiometries in experimental work in the system Bi-Te-Se-S and its subsystems, as well as the homologous character of this series, we predict that a significant number of additional mineral phases exist in nature and will be discovered in the future. Many of these, however, cannot be identified by chemical microanalysis alone.