665

Volume 45 August 2007 Part 4

The Canadian Mineralogist Vol. 45, pp. 665-708 (2007) DOI : 10.2113/gscanmin.45.4.665

MINERALS OF THE SYSTEM Bi–Te–Se–S RELATED TO THE TETRADYMITE ARCHETYPE: REVIEW OF CLASSIFICATION AND COMPOSITIONAL VARIATION

Nigel J. COOK§

Natural History Museum, University of Oslo, Boks 1172 Blindern, N–0318 Oslo, Norway

Cristiana L. CIOBANU

South Australian Museum, North Terrace, Adelaide, S.A. 5000, Australia and Department of Earth and Environmental Sciences, University of Adelaide, S.A. 5005, Australia

Thomas WAGNER

Institut für Geowissenschaften, Universität Tübingen,Wilhelmstr. 56, D–72074 Tübingen, Germany

Christopher J. STANLEY

Department of Mineralogy, The Natural History Museum, Cromwell Road, London SW7 5BD, United Kingdom Abstract

Our compilation of ~900 published results of analyses for minerals of the tetradymite series (tellurobismuthite, tetradymite, guanajuatite, paraguanajuatite, kawazulite, skippenite, tsumoite, hedleyite, pilsenite, laitakarite, ikunolite, joséite-A, joséite-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 compo- sitional 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–Bi4S3 subgroup. Several possible additional minerals or compositional variants of existing minerals would appear to exist in nature, including Bi4Te2Se, Bi4Te(Se,S)2, Bi3Te2Se and Bi3(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 Bi2 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

§ E-mail address: [email protected] 666 the canadian mineralogist 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.

Keywords: bismuth chalcogenides, tetradymite series, system Bi–Te–Se–S, systematics, electron-microprobe analysis. Sommaire

Notre compilation d’environ 900 résultats publiés d’analyses de minéraux de la série de la tétradymite (tellurobismuthite, tétradymite, guanajuatite, paraguanajuatite, kawazulite, skippenite, tsumoïte, hedleyite, pilsenite, laitakarite, ikunolite, joséite-A, joséite-B) nous permet de définir les champs compositionnels des composés naturels du système Bi–Te–Se–S. Nous fournissons des données nouvelles pour ingodite, laitakarite, pilsenite, kawazulite et tellurobismuthite qui étendent les limites composi- tionnelles établies. Dans la plupart des cas, les minéraux connus peuvent être convenablement classifiés selon le rapport Bi(+ Pb)/(Te + Se + S) en sous-systèmes (isoséries) Bi2Te3–Bi2Se3–Bi2S3, Bi4Te3–Bi4Se3–Bi4S3 et BiTe–BiSe–BiS. La plupart des minéraux font preuve de variations compositionnelles limitées, mais ces variations sont plus grandes dans les phases sélénifères, par exemple la laitakarite, et dans certains membres du système Bi–Te, par exemple hedleyite et tsumoïte. La substitution de faibles quantités de Pb au Bi est répandue, particulièrement dans le sous-groupe Bi4Te3–Bi4Se3–Bi4S3. Plusieurs phases minérales possibles et des variantes de minéraux connus semblent exister dans la nature, y inclus Bi4Te2Se, Bi4Te(Se,S)2, Bi3Te2Se et Bi3(Te,S,Se)4. Au sein des groupes, la stoechiométrie est remarquablement constante en termes de Bi(+ Pb)/(Te + Se + S), en accord avec les structures connues et dérivées dans lesquelles tous les composés (sauf ceux où le Pb est essentiel) seraient en fait des combinaisons de couches neutres de Bi2X3 à cinq atomes et des couches de Bi2 à deux atomes. Les écarts à la stoechiométrie en termes de Bi(+ Pb)/(Te + Se + S) dans les isoséries pourraient résulter de défauts d’empilement. Suite à la présence de plusieurs autres phases et autres stoechiométries dans les travaux expérimentaux dans le système Bi–Te–Se–S et ses sous-systèmes, et de la possibilité de séries d’homologues, un nombre important de minéraux nouveaux pourrait exister dans la nature, l’objet de découvertes futures. Plusieurs de ceux-ci ne pourront toutefois pas être identifiés par microanalyse seule.

(Traduit par la Rédaction)

Most-clés: chalcogénures de bismuth, série de la tétradymite, système Bi–Te–Se–S, systématique, analyse par microsonde électronique.

Introduction chiometry among some minerals, the often ambiguous correlation between data from synthetic experiments Mineral species of bismuth with tellurium, selenium and natural occurrences, and not least, by the typical and sulfur (bismuth chalcogenides) occur in a wide very small size of mineral grains, often precluding full range of magmatic, hydrothermal or metamorphogenic chemical or structural characterization. Many of these gold, copper–gold and polymetallic ores (Afifi et al. difficulties have been apparent in earlier treatments 1988b, Simon et al. 1997). Despite the publication of of the system or subsystems (e.g., Godovikov et al. several hundred papers over the past 100 years devoted 1971b, Zav’yalov & Begizov 1983b, Bayliss 1991, Gu to nomenclature, compositions and occurrences of these et al. 2001). compounds, the so-called tetradymite group of Strunz & Nickel (2001), a number of systematic relationships Objectives and Approach remain obscure, even in the simple Bi–Te or Bi–Se systems. Uncertainties exist about the extent of solid Unlike the Bi-dominant sulfosalts, for which enor- solution within subsystems (e.g., Bi4Te3–Bi4Se3–Bi4S3 mous progress has been achieved in recent years in and Bi2Te3–Bi2Se3–Bi2S3), the crystal chemistry and understanding the structural architecture of numerous compositional fields of some less well-characterized homologous and homeotypic series (e.g., Makovicky members of the group, and the extent of element order 1989, 1997a, b), tellurides and selenides have been or disorder that can be structurally accommodated into difficult to investigate at the same scale, owing to their minerals such as tsumoite, ingodite or nevskite. The invariably smaller grain-size and intergrown character. group of compounds in the four-component system Furthermore, the crystallochemical character of Bi tellu- Bi–Te–Se–S (and also the five-component system rides and selenides, involving (theoretically) zerovalent Bi–Pb–Te–Se–S) represents a particular challenge, not Bi2 layers, precludes application of a simple arithmetic least because the number of natural occurrences of these charge-balance calculation to check the quality of phases that have been comprehensively documented microanalyses. Therefore, there exists an imbalance remains limited. between the volume of microanalytical data available The above difficulties are compounded by the rarity for these phases and the degree of crystal-structural of some species, the varying quality of published micro- characterization. Whereas it is desirable to put a name analytical data, an apparent tendency toward non-stoi- to a mineral only once corroborative single-crystal X- minerals of the system bi–te–se–s related to the tetradymite archetype 667 ray data are available, this has only exceptionally been boundaries and define fields of solid solution. By doing the case among tellurides and selenides of Bi. Some so, we accept that the reader may receive an artificially species could thus be incorrectly identified or named skewed perception of compositional variation among in the literature. Bi tellurides and selenides. In reality, most published In this review, we also highlight the fundamental analytical data provide close-to-ideal compositions, and discrepancy between the compositional identity of accordingly plot on top of one another on the accom- naturally occurring tellurides and selenides of Bi, panying figures. and data from experiments. The formation of series A potential problem with this type of compilation is of structurally related compounds, in close composi- that we needed to take much of the published analytical tional proximity to one another, that can be potentially data at face value. Identifications and interpretations can stacked in a disordered manner, has been incorporated be amended on the basis of additional information since in descriptions of natural specimens only to a limited the time of publication, and some published data may degree. “Disorder”, in terms of exchange of the Bi and also be dismissed as pertaining to mixtures in the light Te positions (e.g., Bayliss 1991) among Bi telluride of new data, but the quality of analyses, standardization and selenide minerals, has been accepted to explain procedures, accuracy and precision, as well as calcula- nonstoichiometry, rather than any combinatorial inter- tion and reporting, have been the responsibility of the growth of series members (homologues) at the lattice original authors. or supra-lattice scales. We emphasize the necessity of Our review deals first with general aspects and structural characterization of natural Bi tellurides and problems common to all minerals of the tetradymite selenides at an appropriate scale, e.g., by high-resolu- group. This is followed by a treatment of the known tion transmission electron microscopy. The results will subsystems and, subsequently, a section that introduces help resolve issues that have implications not only for unnamed phases that may belong to other subsystems. classification, nomenclature and naming of new species in the future, but also for the understanding of the Crystal Structure, fundamental crystal-chemistry of this mineral group. Classification and Nomenclature The occurrence of Bi tellurides and selenides as acces- sories in gold–silver ores of various types, as much as In this contribution, we will demonstrate certain the material science interest in these compounds by flaws in the traditional way of classifying this mineral virtue of their thermoelectric properties, are both valid group (e.g., Bayliss 1991, Gaines et al. 1997, Strunz reasons to consider the present review as an interim & Nickel 2001). We will cite an underlying conflict status report that may stimulate further research. between the definition of tight compositional limits The motivation for this annotated compilation and according to stoichiometry and (a) the tendency of presentation of new data comes from the lack of a single atoms to substitute at different scales within and appropriate reference that can provide the essential facts between subseries, and (b) the layered and potentially and contemporary interpretation of these minerals; most homologous character of the compounds. standard texts on ore mineralogy are now outdated in this regard. Although thankfully the exception rather Crystal structure than the rule, use of incorrect formulae and inappro- priate or discredited nomenclature remains profligate in Unit-cell and space-group data on all minerals in this the literature. Further justification for this work stems group are summarized in Table 1, together with their from the huge interest given to Bi2Te3, Bi2Te3–xSex and classification in the Strunz system (Strunz & Nickel related compounds in recent years by material scientists, 2001). Ideal compositions are shown schematically in who are in many cases apparently unaware of their the ternary space Bi–Te–(S + Se) (Fig. 1). Bismuthinite natural analogues. and guanajuatite (isotypic with stibnite) are not in the As we draw on the compiled published data and tetradymite group, in which all minerals have R3m, or present new compositional data from several natural P3m1 symmetry. Idealized structures for Bi2Te3 (tellu- occurrences, our paper represents an attempt to clarify robismuthite), Bi2Te2S (tetradymite), BiTe (tsumoite) the current state of knowledge on the systematics and and Bi4Te3 (pilsenite) are shown in Figure 2. chemistry of minerals in the system Bi–Te–Se–S. A The layered atomic structure of all Bi–Se–Te–S future companion paper will address aspects of para- compounds contrasts with the structural arrangements genesis, conditions of formation and stability among of the Bi sulfosalts. The latter are recombination struc- the minerals, with an emphasis on the potential offered tures, but are based on rods, blocks or layers of simple by these minerals as tracers of ore genesis, with direct archetypal units (Makovicky 1997a), without anion– application to the study of gold deposits. In this review anion or cation–cation bonding. Structural features of of data published over the past four decades, we the Bi–Se–Te–S compounds are linked to their trigonal emphasize the unusual rather than the commonplace. layer structures, in which Bi is coordinated by S, Se, We deliberately place weight on compositional data Te in the form of a trigonal antiprism (Kupčík 1972). that deviate from the ideal, that extend compositional All compounds can be derived from just two structural 668 the canadian mineralogist the in italics) (in phases unnamed other and Schematic diagram illustrating the ideal compositions compositions ideal the illustrating diagram Schematic minerals

1. of system Bi–Te–Se–S, in terms of Bi–Te–(S + Se). in terms of Bi–Te–(S system Bi–Te–Se–S, Fig. minerals of the system bi–te–se–s related to the tetradymite archetype 669

Fig. 2. Schematic depiction of the structures of tellurobismuthite (Bi2Te3; Feutelais et al. 1993), tetradymite (Bi2Te2S; Harker 1934), pilsenite (Bi4Te3; Yamana et al. 1979) and tsumoite (BiTe; Yamana et al. 1979). Bismuth atoms are shown in red, tellurium in yellow, and sulfur in blue.

units: the zerovalent Bi2 and charge-balanced Bi2X3 these authors span the field from hedleyite to tellurobis- modules, where X represents Te, Se or S. However, muthite, and include some compositions not listed by the difficulty in establishing a universally accepted previous authors: Bi7Te3, Bi2Te, Bi4Te3, Bi6Te5, Bi8Te7, boundary between sulfides (selenides, tellurides) and Bi22Te21, BiTe, Bi32Te33, Bi14Te15, Bi26Te29, Bi8Te9 sulfosalts, that satisfies both chemical composition (synthesized also by Feutelais et al. 1993), Bi26Te30, and hierarchical crystal-chemistry, has led to those Bi6Te7, Bi32Te39, Bi4Te5, Bi38Te48, Bi2Te3. sulfotellurides (-sulfides, -selenides) that contain Pb Each of the phases can be considered as stacking (rucklidgeite, kochkarite, aleksite, etc.) being included variants within part of a single homologous series, the among sulfosalts (Moëlo & Makovicky 2006). name “bismuth–tetradymite homologous series” being In the system Bi–Se, numerous compounds with used for the entire family of minerals and synthetic variable Bi:Se ratio have been synthesized, each with compounds that may be derived from the tetradymite defined structures (Abrikosov & Stasova 1985, Sher structure (Moëlo & Makovicky 2006). Imanov & et al. 1986, Okamoto 1994, and references therein). Semiletov (1971) have shown that the structure of each These include Bi7Se3, Bi2Se, Bi5Se3, Bi3Se2, Bi4Se3, phase can be expressed in terms of Bi2X3 (“five-atom Bi6Se5, Bi8Se7, BiSe, Bi8Se9, Bi6Se7, Bi4Se5, Bi3Se4 unit” = tetradymite archetype) and Bi2 (“two-atom and Bi2Se3. A similar scenario, involving stacked layers unit”) layers (X = Te, Se, S), with various combinations of Bi2 and Bi2Te3, can be envisaged for the system over the compositional field in the central part of the Bi–Te (Abrikosov & Bankina 1958, Stasova 1967, system Bi–Se. Thus, Bi2X3 (Bi2Te3, etc.) has the regular Stasova & Karpinskii 1967, Abrikosov & Stasova “555” structure, each unit cell consisting of three Bi2X3 1985, Okamoto & Tanner 1990, Feutelais et al. 1993). units. In the case of BiX, a Bi2 unit is inserted between Alongside Bi7Te3 (hedleyite), Bi4Te3 (pilsenite), BiTe every second Bi2X3 unit (“552” structure). Bi4X3 has (tsumoite) and Bi2Te3 (tellurobismuthite), stacking the “52” structure, each Bi2Se3 unit separated by a Bi2 variants observed in products of syntheses include unit. More complex structures can be derived using the Bi2Te, Bi4Te5 and Bi6Te7. Shelimova et al. (2000) same principles, including subseries in which no named referred to the series as a homologous series of layered minerals presently exist, e.g., Bi3X2, which would have compounds nBi2•mBi2Te3. Phase compositions listed by a (252525252) structure. In Figure 3, we have illustrated 670 the canadian mineralogist minerals of the system bi–te–se–s related to the tetradymite archetype 671

Fig. 3. Schematic depiction of the atomic arrangement of atoms in Bi2X3 (“555”), BiX (“552”) and Bi4X3 (“525252”) structures, using the schematic style of Gaudin et al. (1995), following Imanov & Semiletov (1971). At right, hypothetical structural solutions are depicted for Bi3X4 (“555525555”), Bi2X (“252252252”) and Bi7X3 (“2522253”) 3 3, one possible solution for the hedleyite structure).

these structures using the schematic style of Gaudin which we will describe in a subsequent section. Imanov et al. (1995), and also Bi3X4 (“555525555”), Bi2X & Semiletov (1971) gave structural solutions for Bi7X9, (“252252252”) and Bi7X3 (“2522252” 3 3), the latter Bi4X5, Bi8X9 and Bi8X7 using the same approach, and being one possible solution for the hedleyite structure. demonstrated how the space group and unit-cell dimen- The difficulty in inserting regular, successive Bi2 units, sions can be calculated for any given composition. exemplified by Bi7Te3, and the potential this offers for The idea of a homologous series derived from order–disorder and stacking faults, go some way toward tetradymite is not new. The concepts behind a layered explaining the variation in Bi:Te ratio in hedleyite, structure grew from the crystal-structure description of 672 the canadian mineralogist tetradymite (Harker 1934; see also Wyckoff 1964, and Gaudin et al. (1995) demonstrated that 26% of the the later discussion by Pauling 1975). Indeed, in their Bi atoms in the Bi2 layer are replaced by Se atoms, report on telluride phase-relations, Afifi et al. (1988a) implying a complexity beyond the simple model. stated “Telluribismuth (sic) is the tellurium-rich end of Excellent conductivity within the layers, but not a homologous series of bismuth tellurides which include across them, in these and closely related compounds, hedleyite…, unnamed Bi2Te…, and tsumoite”. Strunz has attracted much interest from materials science for (1963) considered a series of “more or less homeotypic application in thermoelectric devices (e.g., Kuznetsova layered structures” extending from native bismuth, et al. 2000, Touzelbaev et al. 2001, Venkatasubrama- synthetic Bi2Se2, synthetic Bi2Se3 with tetradymite nian et al. 2001). As summarized by Shelimova et al. and tellurobismuthite, synthetic Bi3Se4 with ikunolite, (2001), the quest for the most effective thermoelectric laitakarite and joséite-A, paraguanajuatite [Bi4(Se,S)5; materials has led to the creation of various new ternary Strunz used the formula of Ramdohr (1948)] to hedleyite and quaternary compounds with complex structures, (Bi14Te6; Warren & Peacock 1945). Strunz (1963) also narrow band-gaps and electronic structures near the included the now discredited “platynite” (Pb4Bi7Se7S4; Fermi energy (e.g., Chung et al. 1997). Flink 1910). Despite errors in formulae, the principle of The proposed structure for Bi3X4 deserves comment, an expanding series of layers (3 3 2, 3 3 4, 3 3 5, 3 3 in that although the “555525555” solution is realistic 7, 3 3 9, 3 3 20) is still essentially true and is upheld for Bi3(Te,Se,S)4 compounds, a comparable, yet distinct by more recent studies (e.g., Okamoto 1994). seven-atom unit is proposed for rucklidgeite (PbxBi3–x The tetradymite series fulfills the requirements Te4) and other Pb-bearing compounds. A seven-atom of a homologous series with the general formula layer “X–Bi–X–Bi–X–Bi–X” does obey charge-balance n(Bi,Pb)2•mBi2(Te,Se,S)3 and shared tetradymite-type requirements (Gaudin et al. 1995), but substitution of architecture, in which all compounds with the same one Pb atom for Bi allows for PbBi2Te4 (rucklidgeite) n and m are related to the same homologous type. We to be optimally viewed as a “777” structure (Petrov argue, however, that variation in the stacking sequence & Imamov 1970, Imamov et al. 1970, Zhukova & as a function of (small) changes in chemical composi- Zaslavskii 1976, Frangis et al. 1989, 1990). It is tion underpins any structural model for the series. We therefore plausible that hierarchical series of Pb–Bi highlight the work of Lind & Lidin (2003), who consid- sulfotellurides are built around the same “tetradymite” ered compounds of the system Bi–Se (and, implicitly, five-atom unit as described above, but with involve- other constituent subsystems of the tetradymite series) ment of seven- and even nine-atom layers, with the as displaying a continuous and composition-dependent possibility of combinations between adjacent types of variation in stacking sequence, with all compounds, layers (see below). commensurate or incommensurate, describable in terms of structural modulation over an average structure. The Stability and solid solution same authors employ superspace formalism “onto (the) series (Bi–Se) of polytype compounds…. showing the To many investigators, the binary systems Bi–Te effectiveness of a single structural model on a series and Bi–Se have represented an effectively unlimited of related compounds with long periods and different solid-solution series extending from 30 to 60% atomic stacking sequences”. Se (Bi7S3 to Bi2Se3; cf. Brown & Lewis 1962). Solid The above use of the term “polytype” warrants solution plays an important role, especially at higher comment. The individual phases are not polytypes, and temperatures, as we will subsequently show, but in the the tetradymite series is not a polytypic series, in any Bi–Te and Bi–Se series, a large number of compounds defined sense e.g.( , Guinier et al. 1984; see also Mako­ and phases have been synthesized, many of which vicky & Hyde 1992). Like Imamov & Semiletov (1971), have no natural analogues. Imanov & Semiletov (1971) however, we consider that the n(Bi,Pb)2•mBi2(Te,Se,S)3 made the point that the entire Bi–Te or Bi–Se series compounds are “characteristic polytypical forms”, can be thought of as a solid solution, in the sense of albeit with variable composition because of the stacking an effectively continuous transition from the Bi2Te3- of the two distinct but internally unchanging structural type structure to the Bi structure via intermediate units. A polytypoid-type approach may be valid for compounds. The most likely compounds formed are the group [Lind & Lidin (2003) also considered this those with low-integer ratios of Bi2Te3 to Bi2. Each option], not least because of the considerable potential synthetic phase has been prepared at a set of specific for development of order–disorder, short- or long-range conditions, but their fields of stability are uncertain, polysomes and polytypes. and it is not clear if they can persist during prolonged Returning to charge balance among phases in the annealing over geologically realistic time-scales. In the group, Gaudin et al. (1995) have shown that a balance system Bi–Se, Bi2Se3, consisting of a continuous array in oxidation state for the layered structures can be of Bi2Se3 layers only, is the single stable phase at high proposed for all BixXy compounds. Importantly, the Bi2 contents of Se. However, Bi4Se3, with alternating Bi2 layers are theoretically zerovalent, and Bi4Te3 can thus and Bi2Se3 layers, is stable in Bi-rich bulk compositions. 0 3+ 2– be written (Bi )2(Bi )2(Te )3. In practice, however, Because Bi4Se3 commonly coexists with Bi, we may minerals of the system bi–te–se–s related to the tetradymite archetype 673 realistically conclude that other structures richer in Bi, prolonged annealing, if the starting composition is e.g., Bi5Se3, Bi2Se and Bi7Se3, are only exceptionally midway between two already close compositions, e.g., preserved in nature, if ever. Bi6Se5 and Bi8Se7. We shall return to this in the discus- Given the likely narrow stability-intervals of many sion, since the question of what constitutes a “phase” in phases, temperature controls play a significant role in the chemical sense has direct relevance to the identifica- defining natural compositions and assemblages. More- tion and naming of mineral species. As yet unpublished over, a temperature-constrained solid solution also exists results of HRTEM invesigations of natural specimens for some phases in the system. Shelimova et al. (2000) by two of us (CLC and NJC) confirm the validity of the reported a solid solution (b) from 33.3 to 36.6 atom % two-layer approach, and as well bear out the idea that Te (~Bi2Te), and a second, wider solid-solution (g) from stacking disorder between different arrangements of 44.7 to 58.1 atom % Te, centered on tsumoite, which the two types of layer is an important operator causing may help account for the extensive non-stoichiometry in variation in apparent chemical composition. these parts of the Bi–Te join. These data confirm those The ternary system Bi–Te–S was investigated by of Yusa et al. (1979), who demonstrated solid solution Yusa et al. (1979). Synthetic tetradymite (Bi2Te1.9S1.1) across the compositional range Bi57Te43–Bi43Te57 at and two compounds, Bi48Te21S31 and Bi5Te3S2, were 400°C. Since BiTe melts at temperatures as high as generated at 400°C. The latter were described as joséite- 554°C, a solid solution exists at temperatures typical A and joséite-B, but the cell dimensions given suggest of many magmatic or metasomatic ore deposits. The ingodite and sulphotsumoite. Nevertheless, a degree of roles played by rates of cooling, or chemical fluctuation non-stoichiometry in these compounds does suggest during cooling, are poorly constrained. that solid solution exists also in ternary compounds Extensive solid-solution has been invoked by at geological reasonable temperatures. More recently, Bayliss (1991) and termed “disorder”. Focusing on Ghoumari Bouanani et al. (1996) noted the importance tsumoite in particular, Bayliss argued for interchange- of solid-state unmixing in the system Bi2Se3–Bi2Te3, able occupancy of Bi and Te sites, causing extensive the coexisting phases having wide ranges of solid (isostructural) variation in Bi:Te ratio. The composi- solution. Additional crystal-structure determinations on tional range of tsumoite was said to encompass other natural ternary and quaternary phases will, however, be binary tellurides such as hedleyite and pilsenite. Such essential to evaluate the role of “disorder” in geological “disorder” has been since used to account for a wide specimens. variety of values of the Bi:Te ratio observed in natural Extensive solid-solution between S- and Se-bearing tellurides of Bi. Dobbe (1993) considered that his end-members can be documented in many series (e.g., suite of compositional data from Tunaberg, Sweden, tetradymite – kawazulite, joséite-B – Bi4Te2Se). There supported the idea of a single solid-solution, a tsumoite- is less evidence for direct interchangeability between type phase (bismuthian tsumoite) extending between Te and (S,Se). Other common substitutions involve values of the Bi:Te ratio of 1.35 to 2.61, i.e., including replacement of Bi by Pb (which is generally minor, the compositional range of both hedleyite and pilsenite. but can be significant, especially in the Bi4Te3 – Bi4Se3 Taken to its logical conclusion, this would mean that – Bi4S3 isostructural series), and modest replacement of it is impossible to name more or less any phase in the Bi by Sb. Substitution is limited by the need to conserve system Bi–Te without single-crystal X-ray data. The group symmetry. Several other elements (e.g., Ag, Cu, Bi Te solid solution may be real and significant in Fe, Co, Ni, Zn, Cd, As) are reported in analytical data some cases, perhaps very significant under conditions from the literature. In many situations, these elements of a rapid quench. Nevertheless, our own data, and appear attributable to interference from the immediate those that we have compiled, coupled with the more matrix. modest solid-solution ranges identified above (e.g., Yusa et al. 1979), suggest that most natural specimens Classification and nomenclature are not “disordered” (sensu Bayliss) to such an extent that they cannot be identified on the basis of compo- Each structural variant represents a homologue type. sitional data. All compounds related to a specific homologue type A further explanation of compositional variation are isotypic (or homeotypic) and represent an isoseries. in natural specimens is the suggestion (e.g., Gaudin Each isoseries may represent, in turn, a number et al. 1995) that Bi2 planes may be randomly incor- of (complete or partial) solid-solution series; e.g., porated (order–disorder) into BiX, and presumably Bi2(Te,Se,S)3, Bi3(Te,Se,S)4, Bi(Te,Se,S), Bi4(Te,Se,S)3, other structures, such as Bi7X3. The layered structure etc. For convenience, the minerals can be subdivided of bismuth chalcogenides offers considerable potential into subgroups according to stoichiometry (isoseries), for the development of order–disorder, short- or long- i.e., the ratio between Bi (+ Pb) and the non-metals S, range polysomes, yet this has, to our knowledge, not Se and Te, and, to some extent also in terms of crystal been investigated in any detail. Okamoto (1994) has structure (Table 1). Thus, we treat the minerals in terms raised the possibility of short-range fluctuations in of the following subgroups: (i) the system Bi–Te (with composition developing within a single “phase” during Bi–Se and Bi–S), (ii) the subsystem Bi2S3–Bi2Se3– 674 the canadian mineralogist

Bi2Te3, (iii) the subsystem Bi4S3–Bi4Se3–Bi4Te3, (iv) Bi3Te2 are discussed in the section “other stoichiom- phases with Bi:(Te,Se,S) 1. “Other stoichiometries”, etries”. In this superficially simple series, all phases ≈ including the subsystem Bi3S4–Bi3Se4–Bi3Te4, and except hedleyite, and to some extent, tsumoite, are well Pb-bearing Bi–Te–Se–S phases, are discussed in subse- defined, with generally limited compositional ranges. quent sections. Hedleyite The System Bi–Te Hedleyite is attributed the formula Bi7Te3, although Four distinct binary mineral species have been some authors have given the formula as Bi8Te3 or defined: hedleyite, pilsenite, tsumoite and tellurobis- Bi2 + xTe1–x, stressing the range of natural compositions muthite, with the ideal compositions Bi7Te3, Bi4Te3, (Fig. 4). The literature data for hedleyite (e.g., Warren BiTe and Bi2Te3, respectively (Table 1). A fifth mineral, & Peacock 1945, Nechelyustov et al. 1974, Eshimov Pb-free rucklidgeite, Bi3Te4, is discussed below. Two & Khamrabayeva 1974, Ishmurzin et al. 1975, Lindahl unnamed phases with compositions close to Bi2Te and 1975, Dobbe 1993, Meisser & Della Valle 1993, Losos

Fig. 4. Composition of minerals in the system Bi–Te in terms of Bi–Te–(S + Se). Data for tsumoite and hedleyite are from Warren & Peacock (1945), Eshimov & Khamrabayeva (1974, 1987), Nechelyustov et al. (1974), Ishmurzin et al. (1975), Lindahl (1975), Shimazaki & Ozawa (1978), Zav’yalov et al. (1978), Zav’yalov & Begizov (1983a), Lithoshko et al. (1984), Nysten & Annersten (1984), Criddle & Stanley (1986, 1993), Nysten (1990), Dobbe (1993), Banás et al. (1993), Spiridonov (1995, 1996), Clarke (1997), Wang (1997), Huang (1998), Losos et al. (1998), Vavřín & Fr´yda (1998), Fuertes-Fuente et al. (2000), and Krupenik et al. (2000). Data sources for tellurobis- muthite, pilsenite and rucklidgeite are given in the captions of Figures 5, 8 and 14, respectively. Green diamonds: “bismuthian tsumoite” of Dobbe (1993). Compositions of hedleyite from the Maiskoe deposit, Ukraine (this study) are shown as green squares in the magnified circle (top right of figure). minerals of the system bi–te–se–s related to the tetradymite archetype 675 et al. 1998, Fuertes-Fuente et al. 2000, Krupenik et al. As mentioned above, Bi-for-Te substitution has been 2000; Fig. 4) indicate that natural compositions may invoked by Bayliss (1991) and Dobbe (1993), among extend beyond Bi7Te3 (30 atom % Te) to Bi8Te3 (27.2 others, to explain the broad compositional ranges that atom % Te) and may approach Bi3Te (25 atom % Te) cover large parts of the system Bi–Te, overlapping with and even Bi7Te2 in some cases (Strakhovenko 1996). the compositions of hedleyite and pilsenite. Bayliss has The inappropriate term “bismuthian hedleyite” has cited corroborative experimental data (e.g., Godovikov been used to describe compositions richer in Bi than et al. 1966) to account for the wide range of Bi:Te Bi7Te3. Other compositions with lower values of the values observed in natural tellurides of Bi over the Bi:Te ratio have also been ascribed to hedleyite [e.g., years. Examples include the phase Bi2Te, reported Bi6.68–6.79Te3.21–3.32 of Meisser & Della Valle (1993); by several authors (e.g., Gamyanin et al. 1980, 1982, Bi7Te3.3 of Huang (1998)]. Goncharov et al. 1984, Huang et al. 1991, Gu et al. Our own experience is that hedleyite compositions 2001), which will be discussed further below, as well as are generally consistent over a certain range of Bi:Te the unnamed mineral of Aksenov et al. (1968c) with the within a given deposit, but tend to vary among deposits. formula (Bi0.58Te0.42)Te, and also the synthetic phase of An example, from the Maiskoe Au deposit, Ukrainian Godovikov et al. (1966), for which the crystal-structure Shield, is given in Table 2 and plotted in Figure 4. In model gives Bi(Te0.75Bi0.25). Bayliss (1991) concluded this deposit, SMe/(Te + Se + S) in hedleyite ranges that there exists a single solid-solution phase (bismuth- from 1.93 to 2.24, less than the ideal 2.33. Selenium rich tsumoite) extending between Bi:Te values of 1.35 substitution in hedleyite appears to be low and, in fact, to 2.61. Dobbe (1993) recommended crystallographic contents slightly above the 1 wt.% level in the data from characterization as essential for identification of phases Maiskoe (Table 2) appear to be the highest reported. within this compositional range. The extent of Pb substitution for Bi in hedleyite seldom Published compositions of tsumoite (e.g., Zav’yalov exceeds 1 wt. %. et al. 1978, Zav’yalov & Begizov 1983a, Lithoshko et We believe that there is a need to obtain crystal- al. 1984, Banás et al. 1993, Spiridonov 1995, Wang et logaphic data on specimens of natural hedleyite, in an al. 1997; Fig. 4) support a limited degree of Bi-for-Te effort to understand the reasons for variation in the Bi: substitution, but the available body of data suggests Te ratio. Two of us (CLC and NJC) have begun to use more limited solid-solution than implied by Dobbe HRTEM methods to investigate the stacking periodicity (1993). In fact, we are aware of only two studies in natural specimens with hedleyite-like compositions. showing extensive variation of Bi:Te within a single deposit or group of deposits: Dobbe’s (1993) docu- Tsumoite mentation of BixTey compounds in Tunaberg, Sweden, and the earlier work of Cabri & Laflamme (1976) Although perfectly stoichiometric in many individual demonstrating variance of Bi:Te in “wehrlite” (sic) from occurrences, tsumoite has generally been considered to Cu–Ni deposits of the Sudbury area, Ontario, Canada. display a degree of non-stoichiometry (variation in Bi: Without X-ray data, it is impossible to unequivocally Te). This is considered a common and characteristic deny the existence of a broad tsumoite solid-solution feature of other compounds in which Bi/(Te + Se + S) at Tunaberg; yet we would believe it plausible that is approximately equal to 1 (e.g., ingodite and nevskite; other BixTey phases, close but not identical to BiTe, are see below). recorded in Dobbe’s data. In fact, we speculate whether 676 the canadian mineralogist much of the non-stoichiometric “tsumoite” described on the basis of the observation that compositions “grad- in the literature might actually be discrete phases such ually change into pilsenite within the same grain”. as Bi8Te7, Bi22Te21, Bi32Te33, Bi14Te15, Bi26Te29 or Bi8Te9 (all known from synthesis experiment), which Tellurobismuthite are virtually impossible to distinguish from BiTe by electron-microprobe analysis alone. Tellurobismuthite, Bi2Te3 (as redefined by Frondel Our compilation shows that concentrations of S and 1940), is a common mineral that never appears to Se in tsumoite rarely exceed 1–2% (Fig. 4). Significant contain significant sulfur, but it does display a range of amounts of Pb substitution (as much as 4–5 wt.%) are Se-for-Te substitution, extending up to approximately noted in some cases (Fig. 4, inset). Bi2(Te2.7Se0.3). Many early authors (e.g., Wiese & “Wehrlite” (= “börzsönyite”) (Hout 1841) is discred- Muldawer 1960, LaChance & Gardner 1961, Nakajima ited as a mixture (Ozawa & Shimazaki 1982). Although 1963, Misra & Bever 1964) considered a continuous the majority of the original Hungarian “wehrlite” type- solid-solution series (Bi2Te3–xSex), with constant material was found to be a mixture, Nagy (1983) did variation of a and c with mol.% Bi2Se3. Misra & Bever nevertheless identify a phase with the composition BiTe (1964) discussed a transition from a disordered arrange- in a sample of “wehrlite” and gave lattice constants. ment of Te and Se atoms, i.e., occupying the Y(1) and Considerable confusion appears to persist in some Y(2) sites at random, to an ordered Bi2Te2Se compound textbooks as to the identities of “wehrlite” (given vari- with the Y(1) layer completely filled with Se atoms, ously as BiTe, Bi2Te, Bi3Te2, Bi4–xTe3+x and Bi2+xTe3–x), and the Y(2) sites with Te atoms. Dumas et al. (1987) as well as tsumoite and pilsenite (see Nagy 1983 for showed the phase diagram to have a more complex historical background). Wehrlite is a recognized name subsolidus pattern, “with two terminal solid solutions a of a rock; tsumoite and pilsenite are accepted minerals and a’, and a zone of demixion”, centered on Bi2Te2Se. with the formulae BiTe and Bi4Te3, respectively. There In their phase diagram, solid solution a (Bi2Te3) is is currently no named mineral with the composition limited to a range a little larger than that observed in Bi2Te or Bi3Te2. natural specimens (see also Carle et al. 1995). Most recently, Sokolov et al. (2004) have presented data for Pilsenite the Bi2Te3–Bi2Te2Se segment of the system, showing that the tellurobismuthite solid-solution extends up to 14 Pilsenite is the oldest recognized name for species mol.% Bi2Se3 (Bi2Te2.58Se0.42). At higher Se, Bi2Te2Se in the group [first described by Kenngott (1853) from (kawazulite) will coexist. Deutschpilsen (= Nagybörzsöny, Hungary)]. Although Published electron-microprobe data for tellu- various formulae have been given historically, pilsenite robismuthite (e.g., Lipovetskiy et al. 1977, 1979, is stoichiometric Bi4Te3. Like other members of the Zav’yalov & Begizov 1977, Arutyunyan & Eremin Bi4X3 isoseries, pilsenite shows little variation in Bi/(Te 1978, Harańczyk 1978, Spiridonov et al. 1978, Miller + S + Se), and the common presence of minor Pb. Some 1981, Gamyanin et al. 1982, Harris et al. 1983, Oen & S and Se may be present, although generally, limits of Kieft 1984, Eshimov & Khamrabayeva 1987, Stankovič substitution appear extremely low (Fig. 4). Published & Kozumplíkova 1987, McQueen 1990, McQueen compositional data for pilsenite from the “microprobe” & Solberg 1990, Çağatay et al. 1991, Dobbe 1991, era are remarkably few (e.g., Bao 1994, Simon & Maglambayan et al. 1998, Mikulski 1998) are plotted Alderton 1995, Spiridonov 1995, De Souza Lima et in Figure 4. Spiridonov et al. (1978) reported substan- al. 1996, Mikulski 1998, Gu et al. 2001), stressing the tial Sb-for-Bi substitution in tellurobismuthite from relative rarity of pilsenite compared to other binary northern Kazakhstan, up to (Bi1.12Sb0.88)2Te2.98, fully tellurides of Bi. consistent with experimental data for the ternary system We have described “selenian pilsenite” from Lega Bi–Sb–Te (e.g., Caillat et al. 1992). Dembi, Ethiopia (Cook & Ciobanu 2001b) and include We have investigated tellurobismuthite from the an analytical dataset on this material later in the present small Au–Ag–Cu–Te–Se deposit of Glava, Värmland, contribution. The compositions approach Bi4Te2Se. Sweden (Oen & Kieft 1984), in which it is the most Together with comparable data for ~Bi4Te2Se composi- common telluride in a complex association (Figs. 5a, tions from China and Korea (Gu et al. 2001, Shin et al. b) of several dozen tellurides and selenides. The dataset 2005), we choose to reappraise this “selenian pilsenite” (Table 3, Fig. 6) shows a pronounced Se-enrichment in as a derivative of joséite-B rather than pilsenite and tellurobismuthite, up to ~Bi2(Te2.65Se0.35). Tellurobis- discuss these compositions under that mineral below. muthite of such composition coexists with kawazulite, Contrary to the well-constrained Bi:Te ratio typical confirming the aforementioned data of Sokolov et of pilsenite, Gu et al. (2001) chose to regard a distinct al. (2004). We have also examined tellurobismuthite suite of compositions (~Bi5Te3; Bi:Te up to 1.80) from from the Orivesi (Kutemajärvi) gold deposit in central the Huangshaping deposit as bismuthian pilsenite Finland (Fig. 5d). The data (Table 4, Fig. 6) point to (rather than bismuthian tsumoite, cf. Bayliss 1991, close-to-ideal Bi2Te3, but with the persistent presence Dobbe 1993, or an independent unnamed Bi5Te3 phase), of 0.7 to 0.9 wt.% Sb. minerals of the system bi–te–se–s related to the tetradymite archetype 677

Fig. 5. Back-scattered electron images. (a) and (b) Association of tellurides from the Glava Au–Ag–Cu–Te–Se deposit, south- central Sweden. Tbs: tellurobismuthite, Hs: hessite, Pz: petzite, Vl: volynskite, Au: gold, Bn: bornite, TeO: tellurite. (c) Association of tetradymite (Ttd), tellurobismuthite (Tbs), unnamed PbBi4Te4S3 (Phase “C”; PhC), native bismuth (Bi) and galena (Gn) from the Clogau mine, Dolgellau gold belt, North Wales, U.K. [Section E1309, The Natural History Museum, London]. (d) Association of tellurobismuthite (Tbs), Se-bearing tetradymite (Ttd) and tsumoite (Ts) from gold ores of the Orivesi (Kutemajärvi) deposit, central Finland.

The systems Bi–S and Bi–Se structural model, were said to be either commensurate or incommensurate, and crystallize as layered structures In comparison to the binary system Bi–Te, minerals with either rhombohedral or trigonal symmetry. within the systems Bi–S and Bi–Se are less numerous. Synthetic work in the system Bi–S typically produced The following natural minerals are recognized: bismuth- only the single binary phase Bi2S3 (e.g., Schunk 1969). inite (Bi2S3), nevskite (BiSe, though rarely without In addition to Bi4S3, the literature contains references sulfur) and ikunolite (Bi4S3), guanajuatite [Bi2(Se,S)3] to other stoichiometries in the system Bi–S, including and paraguanajuatite (Bi2Se3), and laitakarite (Bi4Se3). BiS, Bi2S and Bi3S2 (e.g., Zachariáš et al. 2001). These will be discussed below. Compositions approximating to Bi3S5 and Bi3S4 are The system Bi–Se (e.g., Okamoto 1994) has many of reported from Kazakhstan (Pavlova & Kotelinikov the features of the system Bi–Te. Lind & Lidin (2003) 1988, Pavlova et al. 1988). Such phases require more have recently identified an extensive range of phases comprehensive documentation, including quantitative with compositions between Bi2Se3 and Bi4Se3. These microanalysis and X-ray data. compounds, for which the authors developed a general 678 the canadian mineralogist

The Subsystem Bi2S3–Bi2Se3–Bi2Te3 deposits. The historical background for tetradymite, (The “Tellurobismuthite” Isoseries) tellurobismuthite and related phases has been compre- hensively described by Peacock (1941). Tetradymite Minerals within this subgroup (Table 1) are among (Bi2Te2S), kawazulite (Bi2Te2Se), skippenite (Bi2Se2S), the most abundant Bi–Te–Se–S phases in nature: tetra­ tellurobismuthite (Bi2Te3) and paraguanajuatite (Bi2Se3) dymite and tellurobismuthite, in particular, are common have trigonal symmetry and the R3m space group. accessories in many telluride-bearing precious metal Tellurobismuthite, Bi2Te3, has been discussed in the minerals of the system bi–te–se–s related to the tetradymite archetype 679 section above. Tellurantimony, Sb2Te3 (Thorpe & A second characteristic of bismuthinite is the Harris 1973) is also a fully isostructural member of the tendency to incorporate Sb where it is available. Hayase isoseries. A compilation of published compositional (1955) introduced the name “horobetsuite” for composi- data for minerals in the subsystem Bi2S3–Bi2Se3–Bi2Te3 tions in the central part of the Bi2S3–Sb2S3 solid-solution is given in Figure 7. series (30 to 70 mol.% Sb2S3), after their occurrence in The simple sulfide, bismuthinite (Bi2S3), and the Horobetsu deposit, Japan. Springer (1969) showed guanajuatite, the dimorph of paraguanajuatite, are both that substitution of Sb for Bi in bismuthinite can orthorhombic with space group Pbnm, and are thus occur up to 42 mol.% in natural specimens [Hayase classified within the structurally distinct stibnite group (1955) had earlier proposed that solid solution up to (bismuthinite, stibnite, antimonselite, guanajuatite). 55 mol.% Sb2S3 was possible]. Rablovský & Krištín Thus Bi2S3 does not crystallize with trigonal symmetry (1975) reported the presence of “horobetsuite” from the (Kupčík & Veselá-Nováková 1970). Bismuthinite is Dúbrava deposit, Slovakia, including one sample with one of the two end members of the bismuthinite–aiki- a composition (Sb1.38Bi0.48)S1.86S3, suggesting more nite homeotypic series (e.g., Harris & Chen 1976, extensive solid-solution in natural samples than previ- Makovicky & Makovicky 1978, Topa et al. 2002). It ously reported. Other occurrences (e.g., Slim-Shimi et is nevertheless instructive to observe that bismuthinite, al. 1990, Chovan et al. 1998) also are documented. a widespread mineral, commonly found associated with other Bi–Te–Se–S minerals, may in some cases Paraguanajuatite and guanajuatite contain Se, up to concentrations of several wt.%, i.e., 0.10 < Se:(S + Se) < 0.20 [e.g., Falun, Sweden: Paraguanajuatite and guanajuatite are dimorphs. Karup-Møller (1970), Tennant Creek, N.T., Australia: Both were initially reported from the same type-locality Henley et al. (1975), Suttsu mine, Japan: Shimizu et (Santa Catarina mine near Guanajuato, Mexico; see al. (1995), Nevskii, Russia: Yefimov et al. (1988), Earley 1950, Ramdohr 1948, 1950). The compositions Mozgova et al. (1992)], especially where it is associ- of both minerals occupy a wide field along the Se end ated with other selenides and selenosalts. Extreme of the Bi2S3–Bi2Se3 join, extending from almost pure Se-enrichment appears more rarely, although Kucha & Bi2Se3 to compositions where Se and S are approxi- Mochnacka (1986) reported Bi2S2Se (12.27 wt.% Se) mately equal. Berry & Thompson (1962) gave the from southwestern Poland. Incorporation of tellurium formula for guanajuatite as Bi2(Se,S)3. More rarely, Te in the bismuthinite structure rarely exceeds a few tenths substitution is recognized in paraguanajuatite, giving, of a wt.%. for example, the tellurian sulfurian paraguanajuatite of

Fig. 6. Compositional plots for new data in the subsystem Bi2Te3–Bi2Se3–Bi2S3 from the Glava Au–Ag–Cu–Te–Se deposit, south-central Sweden (Se-bearing tellurobismuthite and kawazulite; red circles) and from the Orivesi (Kutemajärvi) deposit, central Finland (tellurobismuthite and Se-bearing tetradymite; blue circles). 680 the canadian mineralogist

Fig. 7. Projection of literature data of minerals in the Bi2S3–Bi2Se3–Bi2Te3 subsystem. Inset at upper left shows variation in terms of Bi( + Pb + Sb)–Te–(S + Se); inset at upper right shows Pb substitution. Purple diamonds: tellurobismuthite; red cir- cles: tetradymite–kawazulite; black stars: skippenite; blue squares: selenian bismuthinite. Guanajuatite and paraguanajuatite are indicated by black rhombs and green triangles, respectively. Literature sources: Muthmann & Schröder (1898), Aksenov et al. (1968b), Kato (1970), Guha & Darling (1972), Czamanske & Hall (1975), Lipovetskiy et al. (1977, 1979), Zav’yalov & Begizov (1977, 1978, 1985), Arutyunyan & Eremin (1978), Harańczyk (1978), Shimazaki & Ozawa (1978), Spiridonov et al. (1978, 1995), Miller (1981), Bortnikov et al. (1982), Gamyanin et al. (1982), Sztrókay & Nagy (1982), Harris et al. (1983), Nagy (1983), Nysten & Annersten (1984), Oen & Kieft (1984), Yushko et al. (1984), Criddle & Stanley (1986, 1993), Kovalenker (1986), Ren (1986), Eshimov & Khamrabayeva (1987), Johan et al. (1987), Chovan & Michálek (1988), Shimizu et al. (1988, 1995), Yefimov et al. (1988, 1990), Kovalenker et al. (1989, 1990), Nikitin et al. (1989), McQueen (1990), McQueen & Solberg (1990), Dobbe (1991), Banás et al. (1993), Bonev & Neykov (1990), Çağatay et al. (1991), Francis et al. (1992), Lowry et al. (1994), Marcoux et al. (1996), De Souza Lima et al. (1996), Ueno et al. (1996), Cioflicaet al. (1997), Kravchenko & Bondarenko (1997), Spry et al. (1997), Maglambayan et al. (1998), Mikulski (1998), Voicu et al. (1999), Cook & Ciobanu (2001a), Vanhanen (2001), Gu et al. (2001), Moloshag et al. (2002). Selected data for selenian bismuthinite are taken from Karup-Møller (1970) (Falun, Sweden), Shimizu et al. (1995) (Suttsu mine, Japan), and Yefimovet al. (1988) and Mozgova et al. (1992) (Nevskoe, Russia). Pink circles are tetradymite data from Cook & Ciobanu (2004).

Shimizu et al. (1988). Published data are not plentiful et al. 1984) and, in some studies, the presence of for either mineral (Aksenov et al. 1968a, Yushko et intermediate compounds with compositions close to al. 1984, Shimizu et al. 1988, Yefimov et al. 1988, Bi2Se2S and Bi2SeS2. Godovikov et al. (1966) indi- Nikitin et al. 1989), and unfortunately do not permit a cated the existence of a solid solution from Bi2S3 up comparison of the compositional ranges of one dimorph to 68% Bi2Se3, and from Bi2Se3 up to 17% Bi2S3 at versus the other. Guanajuatite is recognized as the high- temperatures above 500°C. This miscibility gap (Fig. 7) temperature form of Bi2Se3 (Atabaeva et al. 1973). increases with decreasing temperature down to 300°C Investigations of the system Bi2Se3–Bi2S3 indicate (Liu et al. 1995). extensive solid-solution from Bi2Se3 (e.g., Novotn´y minerals of the system bi–te–se–s related to the tetradymite archetype 681

Tetradymite tively sparse (Kato 1970, Guha & Darling 1972, Miller 1981, Kovalenker 1986, Pavlova & Kotelnikov 1988, Despite the fact that tetradymite is widespread, Willgallis et al. 1990, Dobbe 1991, Shimizu et al. 1995, there is some continuing (though commonly conve- Cook & Ciobanu 2001a). Nevertheless, continuous niently forgotten) uncertainty about the structural solid-solution between tetradymite and kawazulite is formula, which is now almost universally accepted as well established. Bi2Te2S (e.g., Bayliss 1991). Nevertheless, sulfur-rich New, additional compositional data for the kawa- tetradymite appears more chemically stable than stoi- zulite–tetradymite solid-solution series from other chiometric Bi2Te2S, and the formula Bi14Te13S8 given deposits, such as Orivesi (Kutemajärvi), Finland, and by Pauling (1975) appears valid for most examples of Glava, Sweden (Figs. 5a–b, d, 6), confirm the above natural tetradymite. Ciobanu & Cook (2000) described compositional trends, and also the tendency for only compositions resembling both the natural g (Pauling limited compositional variation in a given deposit. 1975) as well as the synthetic b (Te-rich) type (Glatz In general, deviation from the Bi2Te2S–BiTe2Se join 1967). An extensive compositional range is supported (Fig. 7) may be due either to analytical error, or to by experimental work in the system Bi2S3–Bi2Te3 at limited Se-for-Te substitution, as proposed by Bayliss higher temperature: 43–66 mol.% Bi2Te3 (Yusa et al. (1991). 1979), 47–68 mol.% Bi2Te3 (Cortellini & Chang 1980), both at 500°C. Yusa et al. (1979) were able to synthe- Skippenite size Bi2Te1.9S1.1 and showed tetradymite to be stable up to 638°C (or 609 ± 3°C according to Cortellini & Appreciably rarer than tetradymite–kawazulite Chang 1980). is skippenite, ideally Bi2Se2Te [but more generally A relatively large body of analytical data exists for Bi2Se(Se,Te,S)2 or Bi2(Se,Te,S)3, Bayliss 1991]. The tetradymite (e.g., Sarkar & Deb 1969, Guha & Darling mineral (Mineral B of Miller 1981) is known only 1972, Lipovetskiy et al. 1977, 1979, Harańczyk 1978, from a few localities (Johan et al. 1987, Kovalenker Shimazaki & Ozawa 1978, Spiridonov et al. 1978, et al. 1989, Spiridonov et al. 1995). Published data Zav’yalov & Begizov 1978, 1985, Bortnikov et al. indicate extensive solid-solution toward kawazulite, 1982, Sztrókay & Nagy 1982, Nagy 1983, Kovalenker e.g., unnamed Mineral C of Miller (1981), who gave 1986, Ren 1986, Eshimov & Khamrabayeva 1987, the formula Bi4Se3Te3. Bindi & Cipriani (2004) have Chovan & Michálek 1988, Bonev & Neykov 1990, given new structural data for the mineral. Willgallis et al. 1990, Dobbe 1991, Francis et al. 1992, Banás et al. 1993, Spiridonov 1995, De Souza Lima et Bi2SeS2 and Bi2TeS2 al. 1996, Cook & Ciobanu 2004, Marquez-Zavalia & Craig 2004). This database has allowed us to show the In the sulfur-rich portion of the subsystem Bi2S3– extent of natural compositions (Fig. 7), which mark a Bi2Se3–Bi2Te3, there are no trigonal phases with broad line between ideal tetradymite and kawazulite, the ideal compositions of Bi2SeS2 and Bi2TeS2. expressing simple Se-for-S substitution. The data also “Csiklovaite” was proposed as a species with formula express the extent of non-stoichiometry typical for Bi2Te(S,Se)2 by Koch (1948) from the Csiklova tetradymite (-kawazulite), yet do not show any preferred (Ciclova) skarn deposit, Romania. It had earlier been tendency toward Te-rich or Te-poor compositions in discovered and analyzed, but not named, by Sztrókay natural specimens. (1946). Csiklovaite was said to be isomorphous with Lead may enter the tetradymite structure. Some tetradymite, with which it coexists. A phase with similar higher Pb contents in published compositions (e.g., composition had been described from a limited number Plimer 1974) may, nevertheless, be attributable to of other occurrences (Plimer 1974, Harańczyk 1978). submicrometric inclusions of galena, an association “Csiklovaite” was officially discredited following typical for the mineral (e.g., in the Larga deposit, the work of Bayliss (1991), who conducted an X- Romania; Cook & Ciobanu 2004). In association with ray powder-diffraction study on eight specimens of the Pb–Bi tellurosulfides PbBi4Te4S3 and aleksite material used in the original description (Koch 1948). (Fig. 5c), we have documented (Cook et al. 2007) the “Csiklovaite” was shown to be composed of tetradymite presence of plumboan tetradymite that gives a range of (Bi2S1.1Se0.1Te1.8) containing fine lamellar intergrowths compositions extending up to PbBi4Te4S3, prompting of bismuthinite and galenobismutite. Bayliss concluded us to consider the presence of intergrown lattice-scale that a mixture of 60% tetradymite and 40% bismuthinite homologues. would account for the chemical formula proposed by Koch (1948). Bayliss further noted that a phase with the Kawazulite composition Bi2Te(S,Se)2 had never been synthesized in experiments in the system Bi–S–Te–Se (Glatz 1967, Although kawazulite, ideally Bi2Te2Se, is a rela- Kuznetsov & Kanishcheva 1970, Evdokimenko & tively widespread mineral, compositional data are rela- Tsepin 1971; see also Cortellini & Chang 1980). 682 the canadian mineralogist

The Subsystem Bi4S3–Bi4Se3–Bi4Te3 Laitakarite (the “Joséite” Isoseries) Laitakarite, Bi4(Se,S)3, is commonly found together Five mineral species are recognized (laitakarite, with other minerals of the subsystem Bi4S3–Bi4Se3– ikunolite, pilsenite, joséite-A and joséite-B; Table 1). Bi4Te3. Published data (e.g., Vorma 1960, Karup-Møller All share a trigonal symmetry and the R3m space 1970, Stanley & Vaughan 1982, Zav’yalov & Begizov group. Compositional variation is expressed on Figure 1983c, Kovalenker & Geynke 1984, Nechelyustov et 8. Pilsenite, Bi4Te3, has been discussed above. Compo- al. 1984, Kovalenker 1986, Nenasheva et al. 1988, sitions (Fig. 8) are invariably close to end-member Yefimov et al. 1988, Meisser 1994, Holtstam & Bi4Te3, with no compositional data to support solid Söderhielm 1999, Wagner & Jonsson 2001) show that solution toward joséite-B or Bi4Te2Se. laitakarite almost always contains variable amounts

Fig. 8. Projection of published literature data of minerals in the subsystem Bi4S3– Bi4Se3–Bi4Te3. Inset at upper left shows variation in terms of Bi(+ Pb + Sb)–Te–(S + Se). Orange circles: pilsenite, blue circles: joséite-B, red circles: joséite-A, dark green circles: ikunolite, light green circles: laitakarite, pale red circles: Bi4Se3 of Piestrzyński (1992). Other literature sources: Peacock (1941), Grasselly (1948), Vorma (1960), Markham (1962), Dunin-Barkovskaya et al. (1968), Mintser et al. (1968), Godovikov et al. (1970, 1971b), Karup-Møller (1970, 1973), Kerimov & Velizade (1974), Groves & Hall (1978), Nechelyustov et al. (1978, 1984), Zav’yalov et al. (1978, 1984), Boldyreva et al. (1979), Finashin et al. (1979), Pringle & Thorpe (1980), Zav’yalov & Begizov (1981b, 1983b), Bortnikov et al. (1982), Sztrókay & Nagy (1982), Stanley & Vaughan (1982), Nagy (1983), Kovalenker & Geynke (1984), Lithoshko et al. (1984), Soeda et al. (1984), Yushko et al. (1984), Bonev (1986), Criddle & Stanley (1986, 1993), Imai & Chung (1986), Kovalenker (1986), Ren (1986), Eshimov & Khamrabayeva (1987), Nenasheva et al. (1988), Yefimov et al. (1988), Nekrasov et al. (1989), Bergman & Sundblad (1991), Kojonen et al. (1991), Kontoniemi et al. (1991), Verryn et al. (1991), Dobbe (1993), Kato et al. (1994), Luukkonen (1994), Meisser (1994), Cioflica et al. (1995, 1997), Simon & Alderton (1995), Sheppard et al. (1995), Spiridonov (1995, 1996), Zhan et al. (1995), De Souza Lima et al. (1996), Horner et al. (1997), Lawrence et al. (1998), Mikulski (1998), Holtstam & Söderhielm (1999), Wagner & Jonsson (2001), Gu et al. (2001), Alechevskiy (2002), Moloshag et al. (2002) and Fomin et al. (2004). minerals of the system bi–te–se–s related to the tetradymite archetype 683

of S, typically within the range Bi4Se2.0–2.5S0.5–1.0. A re-investigation by two of us (CLC and NJC) Isolated examples attain Bi4Se1.5S1.5. Compositions of type specimens from Orijärvi, southwest Finland reported by Stanley & Vaughan (1982) are unique in (Laitakari 1934, Vorma 1960) has revealed that the type that they extend up to Bi4SeS2 (= Se-rich ikunolite). material contains laitakarite of varying composition. The mineral almost never corresponds to pure Bi4Se3. Most abundant is sulfur-bearing laitakarite with compo- Nenasheva et al. (1988) examined the modification of sitions in the range Bi4Se1.91–2.49S0.51–1.09 (Fig. 10). A the crystal structure as a function of chemical composi- lesser amount of a discrete close-to-end-member Bi4Se3 tion, confirming solid solution. mineral, also present, is typically associated with native Most previously reported natural compositions of bismuth. These two phases have been found to be laitakarite plot close to the Bi4Se3–Bi4S3 join, with Te distinct both chemically and in reflected light (corrobo- substitution for Se being typically less than 0.2 atoms rated by measurement of reflectance spectra). We note per formula unit (apfu; Fig. 8). An exception is the with interest that Piestrzyński (1992) reported a sulfur- dataset of Wagner & Jonsson (2001) from Boliden, free Bi4Se3 mineral from the Polish Kuperschiefer. Sweden, showing up to as much as 0.78 apfu Te. This phase contains 1.4 to 3.9 wt.% Cu and minor Ag, New electron-microprobe data for “laitakarite” and it is closely associated with covellite and selenian from the Lega Dembi Au deposit, Ethiopia (Figs. 9a–b, chalcocite. The Bi4Se3 phase, conspicuously without Pb, Table 5), have confirmed the earlier suggestion of two occurs intergrown with clausthalite in an ore type rather of us (Cook & Ciobanu 2001b) that in some cases, atypical for most natural occurrences of laitakarite. An there may be extensive solid-solution fields within the additional occurrence of “end-member” Bi4Se3 has entire lower half of the Bi4S3–Bi4Se3–Bi4Te3 triangle recently been reported by Fojt & Škoda (2005), asso- (Fig. 10). Our new compositional data, which show ciated with clausthalite in the Zalesi uranium deposit, little overlap with previously published data, depict a Czech Republic, and compositionally distinct from the broad range of “tellurian laitakarite” compositions that laitakarite in the same ores. could be considered as members of a solid solution between laitakarite and a point on the Bi4Se3–Bi4Te3 Ikunolite join (Bi4Se2Te?). Alternatively, these compositions, and possibly some of the Te-rich compositions of Wagner Ikunolite has only been recognized from a relatively & Jonsson (2001), could be members of a solid-solu- small number of localities (e.g., Kato 1959, Markham tion join beween joséite-A and Bi4Se2Te, rather than 1962, Nechelyustov et al. 1978, Finashin et al. 1979, laitakarite. Mechanisms of substitution between Te Bortnikov et al. 1982, Imai & Chung 1986). Although on the one hand, and (S + Se) on the other, are poorly appreciably less common than bismuthinite, the mineral understood. Several wt.% Pb appear characteristic for is nevertheless stable in several telluride- and selenide- laitakarite (0.15–0.25 apfu.; Fig. 9, inset). bearing deposits. In our experience, it is most stable 684 the canadian mineralogist

Fig. 9. Variation of Pb versus Bi in the analyses for minerals of the Bi4S3–Bi4Se3–Bi4Te3 subsystem (based on seven atoms in formula). Dataset and symbols as in Figure 8. Note the persistent presence of Pb in most laitakarite and ikunolite samples.

where pyrrhotite is the stable Fe-sulfide. Ikunolite may Compositional data show a range of compositions occur together with laitakarite, joséite-A or joséite-B, from end-member Bi4S3 to Bi4S2.5Se0.5. It is uncertain hedleyite, native bismuth and bismuthinite (Fig. 11d). whether there is complete solid-solution with laitakarite, minerals of the system bi–te–se–s related to the tetradymite archetype 685 or if there is a partial miscibility-gap between Bi4S2Se New data for the Lega Dembi deposit, Ethiopia and Bi4Se2S. The only dataset falling in this range is the (Table 5, Figs. 10, 11), echo these findings, with laitakarite of Stanley & Vaughan (1982). Compositional compositions (which we earlier referred to as “selenian data for ikunolite (Fig. 9) indicate very limited Te-for- pilsenite”; Cook & Ciobanu 2001b) also approaching (Se,S) substitution in most natural specimens. There Bi4Te2Se. Selenium seems to replace only S, analogous are numerous data-points plotting between ikunolite to the substitution trend observed between tetradymite and joséite-A, but we would favor an explanation based and kawazulite. Note that Bi4Te2Se is an end member of on the presence of submicroscopic intergrowths rather a solid-solution series, and phases in which the amount than solid solution between the two minerals. Like other of Se exceeds that of S, such as the Bi4(Te,Se,S)3 and minerals in the Bi4Se3–Bi4Se3–Bi4Te3 isoseries, both Bi4Te2Se phases recognized in Dataushan and Lega joséite minerals show significant Pb-for-Bi substitution, Dembi, probably correspond to what would be a new at levels comparable with those in laitakarite (Fig. 8, mineral, once the necessary corroborative data for inset). Bi4Te2Se become available. In the case of the selenian derivatives of joséite-A, the extent of solid solution is Joséite-A and joséite-B unclear, and may possibly extend beyond Bi4TeSSe to the aforementioned tellurian laitakarite. As mentioned Until publication of a paper by Gamyanin (1968), above, there appears to be extensive (but incom- showing the distinct optical and X-ray-diffraction plete ?) solid-solution between ikunolite and joséite-A. character of joséite-A and joséite-B, and the two review “Joséite-C”, Bi4.1Te0.7S2.2 of Godovikov et al. (1971a), papers by Zav’yalov & Begizov (1978, 1983b), “joséite” an unnamed phase from China, [(Bi3.5Te0.5)S2Te; Ren was the source of some confusion involving the inap- (1986)], and “joséite-C” of Alechevskiy (2002) lie along propriate or confusing use of “joséite” for a whole the Bi4S3–Bi4TeS2 join. Other joséite-like phases in the range of compositions, e.g., Bi7Te2(S,Se)2 (joséite of literature (e.g., joséite phases I to V of Rabone 1989) are Genth 1886), Bi7(Te0.74S5.26)S6 (Bi telluride of Koch more difficult to readily assign to known phases. 1948) or Bi7(Te2.68S2.29)S5 (joséite-B of Boldyreva et As is common in other members of the Bi4S3– al. 1979). Zav’yalov & Begizov (1978) gave electron- Bi4Se3–Bi4Te3 isoseries, Pb-for-Bi substitution in microprobe and X-ray data for joséite-A (Bi4TeS2) joséite-A and joséite-B (Fig. 9) is widespread, although and joséite-B (Bi4Te2S; so-called “tellurojoseite” in generally more limited than in laitakarite or ikunolite. the earlier Russian literature) showing that these are Bayliss (1991) suggested that Bi-for-Te substitution distinct phases, with only partial solid-solution between (“disorder”) may play a role in the “joséite” isoseries, them. The same authors later comprehensively reviewed contributing to the considerable solid-solution among published data on these phases (Zav’yalov & Begizov members of the series, even though he noted that the 1983b), showing that many of the names given to phases majority of phases in this system have generally good in the older literature bear little relation to their true or excellent “4:3” stoichiometry. Our compilation backs identity. In doing so, Zav’yalov & Begizov established, these claims and suggests that minerals in the Bi4S3– once and for all, the discrete nature of both joséite Bi4Se3–Bi4Te3 isoseries tend to have ordered structures. phases in the subsystem Bi4S3–Bi4Se3–Bi4Te3 and their A modest variation in Bi/(Te + Se + S) is, however, distinction from other tellurosulfides of Bi. Moreover, noted in all minerals of the isoseries (Fig. 8). the reviews by Zav’yalov & Begizov contributed to the characterization of the new minerals ingodite and The Subsystem BiS–BiSe–BiTe: rucklidgeite and to the recognition of the stoichiometric Phases with Bi:(Te,Se,S) 1 ≈ groups identified in the present paper. (the “Tsumoite” Isoseries) Published compositions of both joséite-A and joséite-B are abundant and show a considerable range Ingodite [Bi(S,Te)] and nevskite [Bi(Se,S)] can be along the Bi4Te3–Bi4S3 join, clustering around the considered as ternary phases in the systems Bi–Te–S and ideal compositions (Fig. 8). The data also show a Bi–Se–S, respectively. Both species display a similar considerable degree of Se-for-(S,Te) substitution in degree of nonstoichiometry, as has already been shown some specimens. In joséite-B, such a substitution can for tsumoite (see above). Published data for nevskite extend up to a selenian end-member, Bi4Te2Se, (e.g., and ingodite remain relatively few (Fig. 12). In the case in the Dataushan deposit; Gu et al. 2001; see also of ingodite, data in the original description (Zav’yalov Shin et al. 2005). Selenium substitution in joséite-A & Begizov 1981a) can be compared with additional may approach Bi4TeSSe, adding indirect evidence for data in a later paper, showing the extent of solid solu- the joséite-A – Bi4Se2Te join that we speculated upon tion (Zav’yalov et al. 1984). The same seems to apply above. We should not, however, rule out the analysis to nevskite (Nechelyustov et al. 1984, Yefimov et al. of fine-grained intergrowths in some of the datasets as 1988, Zhukova & Ordnets 1988). The other phases in an explanation for the strong variation in Se/Te seen in this rather loosely defined subgroup are sulphotsumoite both joséite-A and joséite-B. (Zav’yalov & Begizov 1983a) and the recently accepted 686 the canadian mineralogist

Fig. 10. Compositional plots for new data on the system Bi4Te3–Bi4Se3–Bi4S3. Grey shaded fields are from the literature, data given on Figure 8 for laitakarite, joséite-A, joséite-B and pilsenite. The bimodal composition of laitakarite in the type material from the Orijärvi deposit, southwest Finland (Bi4Se3 and Bi4(Se,S)3, simplified from Ciobanu et al. 2002), is shown by the orange- and pink-colored fields. Other symbols are: compositions of Te-bearing laitakarite (red circles) and Se-bearing joséite-B from the Lega Dembi deposit, Ethiopia (blue circles); joséite-A and joséite-B from Carrock Fell, Cumbria, U.K. (green circles) and joséite-B from the Maiskoe Au-deposit, Ukraine (blue squares).

telluronevskite (Řídkošil et al. 2001), neither of which tsumoite, Bi(Te,S), according to Bayliss. Zav’yalov et is so far known to occupy a broad compositional range al. (1984) reported a number of compositions of Pb- beyond Bi3TeS2 and Bi3TeSe2, respectively. bearing ingodite, the majority of which most closely resemble “phase C” of Lipovetskiy et al. (1977), Ingodite discussed below and by Cook et al. (2007). To illustrate the apparent nonstoichiometry, as well Zav’yalov & Begizov (1981a) formally described as the difficulties involved in microanalysis, we have ingodite as Bi(Te,S) (ideally Bi2TeS), although the re-examined ingodite from the Carrock Fell mine, existence of the phase had been mentioned in several Cumbria, U.K (polished specimens E817 and E819 earlier studies (Zav’yalov & Begizov 1978). Their data from samples BM 39768 and BM 35459, respectively, and subsequent information from other occurrences Natural History Museum, London, U.K., summarized in (e.g., Ren 1986, Shimizu et al. 1999) illustrate a degree Cooper & Stanley 1990). Ingodite is intimately associ- of nonstoichiometry [(Bi/(Se + S + Te) between 0.95 ated with joséite-A, joséite-B, tetradymite, bismuthinite and 1.08] and also variable but roughly equal Te and S and hedleyite (Fig. 13). Microanalytical data (Table 6, contents (Te:S ratio between 0.45 and 0.55). Although Fig. 14) illustrate the variation in Bi/(Te + S) from relatively few analyses for ingodite have been made, a 0.88 to 1.08 [between ~Bi5(S,Te)6 and ~Bi6(S,Te)5] number of compositions described as joséite, yet having and significant differences also in Te:S value. The Se Bi/(Te + S) 1, can be readily assigned to ingodite contents in ingodite are negligible. Although much ≈ (e.g., Turlychkin 1987). Bayliss (1991) re-appraised of the ingodite in sample E817 (BM 39768) is close compositional and X-ray powder-diffraction data given to stoichiometric Bi(S,Te), and has been confirmed by Zav’yalov & Begizov (1981a) and Zav’yalov et al. as such by X-ray powder diffraction (C.J.S., unpubl. (1984) and concluded that ingodite should be attributed data; see also Criddle & Stanley 1993), much of the a formula Bi(S,Te). Compositions in which Te > S (e.g., coarser, deformed ingodite in specimen E819 (BM no. 77 of Zav’yalov & Begizov 1981a) are, in fact, 35459) is chemically inhomogeneous, with composi- minerals of the system bi–te–se–s related to the tetradymite archetype 687

Fig. 11. Back-scattered electron images. (a) and (b) Inclusions of Te-bearing laitakarite (Ltk) within pyrrhotite (Po) in gold ores, Lega Dembi mine, Ethiopia. Hs: hessite, Bi: native bismuth. (c) Deformed lamellar intergrowths of laitakarite (Ltk) and wittite (Wit) from the Falun deposit, Bergslagen, central Sweden [Section E312, Specimen BM 1956,130, Natural History Museum, London]. (d) Coarse-grained joséite-B (JoB) with inclusions of hedleyite (Hed), native bismuth (Bi) and ikunolite (Iku) in the Maiskoe Au deposit, Ukraine. (e) Blebs of joséite-A (medium gray) exsolved in coarse, deformed joséite-B (light gray), Carrock Fell mine, Cumbria, U.K. Ing: ingodite. [Section E819, BM 35459, Natural History Museum, London]. (f) Coexisting coarse joséite-A, with lamellar exsolution of joséite-B (light gray) and coarser areas of joséite-B from Carrock Fell mine, Cumbria, U.K. [Section E820, BM 88363, Natural History Museum, London]. (g) Assemblage consisting of ikunolite (Iku), native bismuth (Bi) and bismuthinite (Bim) from the Sergeevske gold deposit, Ukraine. 688 the canadian mineralogist

tions deviating from Bi(S,Te). Significantly, we observe dered ingodite), we do not exclude the possibility that compositions ~Bi5(S,Te)6 immediately adjacent to other (structurally distinct) phases are present. Specifi- BiTe, distinguishable in back-scattered electron images cally, and because of the marked tendency toward Te (Fig. 13d). Although it may be convenient to describe < S in the Bi-rich “ingodite” (Fig. 14), we suspect that the bulk material as ingodite solid-solution (or disor- baksanite, Bi6Te2S3 (see below) may be present, neces- minerals of the system bi–te–se–s related to the tetradymite archetype 689

Fig. 12. Projection of published literature data for minerals and unnamed phases with Bi/(S + Se + Te) ~ 1, expressed in terms of Bi2Te2–Bi2Se2–Bi2S2. Literature sources for ingodite, nevskite, sulphotsumoite and telluronevskite from Aksenov et al. (1968b), Godovikov et al. (1970), Zav’yalov et al. (1978), Zav’yalov & Begizov (1981a), Nechelyustov et al. (1984), Criddle & Stanley (1986, 1993), Ren (1986), Yefimov et al. (1988), Zhukova & Ordynets (1988), Řídkošil et al. (2001). Source of tsumoite data is given in caption to Figure 4. Unnamed Bi(Se,Te) from Johan et al. (1987); unnamed Bi(S,Se) from Kudrina et al. (1986). sitating supplementary single-crystal examination of 1988). Variable Bi/(Se + S + Te) between 0.96 and this classic material. 1.12 and variation in Se/(Se + S + Te) within a wide Ingodite is described as the second most abun- range (0.61–1.00) appear characteristic of this phase. dant Bi–Te–(S) phase after tetradymite in the Băiţa Zhukova & Ordnets (1988) have also presented data Bihor skarn deposit, Romania, as well as others in for nevskite; one sample contains negligible sulfur, the Upper Cretaceous “banatitic” province (Ilinca & therefore suggesting the existence of a BiSe “end Makovicky 1999). Compositional ranges are said to member” (Fig. 12). This inference is supported by the be restricted within individual samples, but the entire BiSe composition reported by Yushko et al. (1984). The population varies across a broad range, with Bi/(Te + Te contents of nevskite seem to be negligible, except S) from ~0.7 to 1.25 and Te/S from ~0.4 to 0.6. Ilinca in the dataset of Yefimov et al. (1988). A degree of Pb- & Makovicky (1999) stated that their compositions for-Bi substitution [0.03 < Pb/(Pb + Bi) < 0.09] seems contain Pb and plot along the same line as reported by to be typical of nevskite. Zav’yalov et al. (1984), i.e., from Pb0.02Bi2Te0.86S1.12 to Pb0.24Bi1.38Te1.42S0.95. Sulphotsumoite

Nevskite Sulphotsumoite, Bi3Te2S, was accepted as a distinct mineral in 1982 (Zav’yalov & Begizov 1983a). The Nevskite, Bi(Se,S), was defined by Nechelyustov mineral has been little recognized from other localities, et al. (1984). Additional microanalytical data have in part no doubt owing to the difficulty in identifying subsequently been published (e.g., Yefimov et al. the phase by microanalysis, and distinguishing it from 690 the canadian mineralogist

Fig. 13. Back-scattered electron images showing the occurrence of ingodite from Carrock Fell, Cumbria, U.K. [Section E819, BM 35459, Natural History Museum, London]. (a) Coarse disordered ingodite (IngOD ~Bi5(S,Te)6) in a matrix of joséite-A (JoA). Note irregular boundaries and deformation of the assemblage. Bismuthinite (Bim) occurs within joséite-A. (b) Detail of central part of (a) showing bismuthinite (Bim) as an exsolution product from ingodite (IngOD). Tetradymite (Ttd) forms a halo around the bismuthinite, indicating a secondary, overprinting event. (c) Detail of ingodite (IngOD) displaying deformed lamellar textures, with inter-lamellar exsolution of cosalite (Cos). (d) At margin of the coarse, disordered ingodite (IngOD ~Bi5(S,Te)6), we note ordered ingodite with a perfect Bi(S,Te) stoichiometry within joséite-A (JoA), that is also exsolving joséite-B (JoB). ingodite. Apart from the type locality (Burgagylkan, Slovakia; Řídkošil et al. 2001). Compositions of an Magadan District, Russian Far East), for which the two unnamed Bi(Se,Te) phase given by Johan et al. (1987) published compositions led to the empirical formulae fall between telluronevskite and nevskite (Fig. 11). Bi3.08Te1.94(S0.92Se0.06)S0.98 and Bi2.97Te2.06S0.97, the only published data that we are aware of are those given Other compositions by Spiridonov (1995) and Gu et al. (2001). During re-examination of “wehrlite” type material, Telluronevskite Sztrókay & Nagy (1982) and Nagy (1983) identified a phase with the composition Bi3TeS2; the latter author Telluronevskite was recently accepted with the ideal proposed the name “sztrokayite”. The phase coexists formula Bi3TeSe2 and the empirical formula Bi2.92 with tsumoite, tellurobismuthite, joséite-B, tetradymite Pb0.02Te1.01Se1.73S0.32. The mineral has been reported and bismuthinite. The status of “sztrokayite” remains in only from the type locality (Vihorlat Mountains, doubt; it may correspond to ingodite or be an additional, minerals of the system bi–te–se–s related to the tetradymite archetype 691

S-dominant member of the subgroup. Compositions The Subsystem Bi3S4–Bi3Se4–Bi3Te4, published by Kudrina et al. (1986) seem to be similar Rucklidgeite and Poubaite to that of Sztrókay & Nagy (1982) and are similarly S-dominant (Fig. 12). Two phases are currently recognized in the We have encountered numerous, sub-10-mm grains subsystem, rucklidgeite, (Bi,Pb)3Te4, and poubaite, with compositions consistently close to Bi3Te2Se, (Bi,Pb)3(Se,Te)4 (Fig. 15). with only negligible S contents, in samples from the Rucklidgeite was originally defined as (Bi,Pb)3Te4 telluride- and selenide-bearing core portions of the by Zav’yalov & Begizov (1977). It was later estab- Ocna de Fier Fe–Cu–(Zn–Pb) skarn deposit, Romania lished that the Pb content is variable, up to one apfu, (Cook & Ciobanu 2001a), coexisting with tsumoite, and probably not essential (Kase et al. 1993). Lead- tellurobismuthite and kawazulite. Details of this phase, free members of a limited rucklidgeite solid-solution which would represent the selenian analogue of sulpho­ series (Bi3Te4–PbBi2Te4; inset to Fig. 15) have been tsumoite, will be reported elsewhere upon completion described from several localities (Rucklidge 1969, of the analytical work. Lipovetskiy et al. 1977, 1979, Zav’yalov & Begizov

Fig. 14. Compositional plots for Carrock Fell ingodite and co-existing tetradymite, bismuthinite, joséite-A and joséite-B. Note the wide compositional field for ingodite, extending from ~Bi5(S,Te)6 (tight cluster of points) through ideal Bi(S,Te) to compositions approaching ~Bi6(S,Te)5 (i.e., baksanite). See text for further discussion. 692 the canadian mineralogist

1977, Harańczyk 1978, Harris et al. 1983, Pašava et bearing rucklidgeite [(Pb0.82–0.87Bi2.11–2.16)S3(Te,Se,S)4], al. 1986, Sakharova et al. 1986, Spiridonov et al. 1989, in the same Larga–Trîmpoiele hydrothermal system, McQueen 1990, McQueen & Solberg 1990, Kase et Apuseni Mountains, Romania. Only minor S, but up to al. 1993, Maglambayan et al. 1998, Moloshag et al. 0.3 apfu Se, were determined in the latter Pb-bearing 2002). Both Zav’yalov & Begizov (1977) and Kase et variety. al. (1993) noted that Ag and minor Sb might also enter The possibility of an extensive solid-solution rucklidgeite. This is in agreement with the presence of series derived from rucklidgeite, with general formula Ag in a significant proportion of published composi- Bi3(Te,Se,S)4, has been raised in the description tions for the mineral (e.g., Criddle & Stanley 1986). of several possibly related compositions (Fig. 15). The apparent tendency for rucklidgeite to accommodate Unnamed Bi3(Te,S)4 has been described by Zav’yalov et other metals (unlike most other minerals under discus- al. (1978), Kojonen et al. (1991), Spiridonov (1995) and sion in this contribution) is amplified by the report of Moloshag et al. (2002). In addition, Bi3(Te1.67–2.21Se0.67– “Cu-rich rucklidgeite” by Pašava et al. (1986). 1.65S0.70–1.14)S4 is described from the Suttsu mine, Japan Recently, the present authors (Cook & Ciobanu 2004) (Shimizu et al. 1995). The absence of Pb was, however, contrasted low-Pb rucklidgeite (0.02 Pb apfu) in veins noted by these authors to support their contention that above porphyry-style mineralization containing Pb- this is not a derivative of rucklidgeite.

Fig. 15. Summary plots for rucklidgeite (red circles) and poubaite (purple rhombs) in the subsystem Bi3Te4–Bi3Se4–Bi3S4. Inset (upper right) shows correlation between Pb and Bi in rucklidgeite between Bi3Te4 and PbBi2Te4. Rucklidgeite data from Rucklidge (1969), Lipovetskiy et al. (1977, 1979), Zav’yalov & Begizov (1977), Harańczyk (1978), Harris et al. (1983), Sakharova et al. (1986), Criddle & Stanley (1986, 1993), Pašava et al. (1986), Spiridonov et al. (1989), McQueen (1990), McQueen & Solberg (1990), Kase et al. (1993), Maglambayan et al. (1998), Moloshag et al. (2002). Poubaite data from Čech & Vavřín (1978, 1979), Johan et al. (1987). Unnamed Bi3(Te,S)4 of Zav’yalov et al. (1978), Kojonen et al. (1991), Spiridonov (1995) and Moloshag et al. (2002) shown as blue circles. Unnamed Bi3(Te,Se,S)4 of Shimizu et al. (1995), probably a Pb-free poubaite, is shown as green rhombs. Unnamed Bi3(Te,Se,S)4 of Yefimov et al. (1989), also probably poubaite, is shown as orange rhombs. Mineral ‘C’ of Miller (1981) is marked by a blue rhomb. An unnamed Se-phase (Johan et al. 1987) is shown with gray rhombs. Grey areas on main plot and inset (right) are compositional fields for Pb-free and Pb-bearing rucklidgeite from Larga, Romania (Cook & Ciobanu 2004). minerals of the system bi–te–se–s related to the tetradymite archetype 693

Poubaite, (Bi,Pb)3(Se,Te)4 [the formula has also (2001). Some of the “wehrlite” compositions of Cabri been given as PbBi2Se2(Te,S)2], is considered as & Laflamme (1976) and the “bismuthian tsumoite” of being isostructural with rucklidgeite, sharing trigonal Dobbe (1993) have similar compositions. Sulfur- and symmetry and the R3m space group. The mineral is selenium-bearing derivatives are Bi2(Te,Se,S) (Konto- rare: apart from the type locality (Oldřichov, Czech niemi et al. 1991) and Bi6(Te,Se)3 (Gu et al. 2001). In Republic; Čech & Vavřín 1978), we are aware of only the case of Bi2Te, the observations of Gu et al. (2001) two additional confirmed occurrences: Otish Mountains, are to be noted: “…. the consistent “2:1” stoichiometry Quebec (Johan et al. 1987) and a second, without and slight difference in optical properties compared to analytical data, the Kawazu mine, Rendaiji, Honshu, hedleyite, joséite-B or pilsenite, lead us to infer that Japan (Shikazono et al. 1990). The empirical formula this may be an independent mineral”. The small size of holotype poubaite is Pb1.11Bi1.94Cu0.10 (Se1.97Te1.37 of the grains (<10 mm) prevents further work aimed at S0.66)S4.00. Other Bi3(Te,Se,S)4 compositions, though establishing if this, and analogous Bi2(Te,Se)3 phases, differing compositionally from type poubaite (e.g., Čech are additional members of the group. Our own observa- & Vavřín 1979, Miller 1981, Yefimov et al. 1988) are tions are similar: Bi2Te is conspicuous within several also probably poubaite, as is possibly a further very of the Romanian skarn deposits, and in numerous other Se-rich phase also mentioned by Johan et al. (1987). reduced gold deposits, but it rarely exceeds a few mm All are plotted on Figure 15. The synthetic compound in diameter. We would further reason that the incidence PbBi2Se4 was studied by electron diffraction (Agaev of Bi2Te in nature and in synthetic studies (Abrikosov & Semiletov 1968) and seems to be isostructural with & Bankina 1958, Okamoto & Tanner 1990) is suffi- Bi3Se4 (Sn3As4 type). ciently great to suggest that a discrete mineral with this composition exists. Other Stoichiometries The phase Bi3Te2 has been reported by Kukovsky & Lazarenko (1959, cited by Zav’yalov et al. 1978), Baksanite, Bi6Te2S3 was described (Pekov et al. Sarkar & Deb (1969), Cabri & Laflamme (1976), 1996) from the type occurrence, the Baksan W–Mo Strozkay & Nagy (1982) and Garuti & Rinaldi (1986). skarn deposit, Tyrny’uaz, North Caucasus, Russian Sulfur-bearing derivatives include the phases Bi3TeS, Federation [empirical formula, (Bi5.77Pb0.16Sb0.22)S5.95 Bi3(Te1.33S0.67)S2 and Bi3(Te0.5S1.5)S2 reported by (Te1.77S3.27)S5.04]. The mineral has not been subse- Godovikov et al. (1970, 1971a, b; minerals L, K and quently described from other localities. Recently, a P, respectively) and Bi2.97(Te1.34S0.69)S2.03 (Alechevskiy Pb-bearing variety, (Bi4.94Pb0.96)S5.90(Te2.03S3.06), has 2002). To these can be added phases listed in the been described in a sample from the same deposit by reviews of Zav’yalov & Begizov (1978, 1983b) that Bindi & Cipriani (2003). These authors confirmed the are considered similar, but not identical, to joséite-A or trigonal (P3m1) symmetry of baksanite. A phase with a joséite-B. Such compounds are close to Bi3TeS or are similar stoichiometry, (Bi,Pb)6(Se,S,Te)5, is mentioned part of the series Bi3(Te,S)2, including Bi2.90–3.07(Te1.13– in a recent publication by Semenyak et al. (2005). 1.28S0.62–0.77)S1.88–2.01 of Ontoev et al. (1974). Lawrence Apart from the established stoichiometric groupings (1998) mentioned a phase with the empirical formula that we have discussed above, there exist numerous Bi10Te2S5. analytical data in the literature suggestive of additional, In the course of our own investigations of bismuth unnamed phases with alternative stoichiometries. tellurides in Băiţa Bihor and other Romanian skarns, Many of these can, however, be readily assigned to we have also noted Bi3Te2 as well as Bi3Te(S,Se). known phases. Examples include Bi8(Te7S5)S12 and In both cases, the compositions could be readily Bi8(Te7.15S4.48)S12.63 of Cioflica et al. (1997), which dismissed, invoking conventional thinking, as “disor- are most likely to be tetradymite. In other cases, the dered” members of the tsumoite – ingodite – nevskite compositions can be assigned to minerals that were series. The regularity of the stoichiometry, however, is approved and named after the data were originally an adequate reason not to discount the possibility of published (e.g., ingodite, rucklidgeite, telluronevskite); a subgroup of independent, stable minerals with this such cases have been included in the datasets discussed stoichiometry. above. Explanations for other data can be sought in We have also studied “wehrlite” from a locality in poor analytical quality, interference from adjoining the Ukrainian Transcarpathians (Ciobanu et al., in prep.) minerals, and other reasons. There do, nevertheless, and note three distinct phases with Bi3X2 stoichiometry: remain a small number of compositions that may well Bi3(S,Se)1.33Te0.67, Bi3Te1.33(S,Se)0.67 and Bi3Te(S,Se), pertain to possible new, as yet incompletely character- strongly suggesting the existence of ordered phases, ized minerals. Two stoichiometric groups stand out: with separation of Te and (S,Se) into specific structural Bi2(Te,Se,S) and Bi3(Te,Se,S)2. sites. In the first group, Bi2Te has been reported by “Protojoséite” is considered a questionable species Gamanyin et al. (1980, 1982), Goncharov et al. (1984), (Jambor 1984). Zav’yalov & Begizov (1983b) plotted Huang et al. (1991), Luukkonen (1994) and Gu et al. published compositions of “protojoséite”, which differ 694 the canadian mineralogist markedly from joséite-B and do not overlap with Discredited and Non-Accepted Minerals compositions of that mineral, with which it may coexist. The formula for “protojoséite” was given as Bi3(Te,S)2, The literature contains numerous references to but there is noticeable variation in Bi:(Te + S) value additional “minerals” and, not uncommonly, the unfor- in the dataset given by Zav’yalov & Begizov (1983b), tunate practice of using non-approved names to describe prompting the general formula Bi3+xTe1–x–yS1+y, where mineral compositions different from those of known –0.02 < x < 0.14 and –0.05 < y < 0.17. Although some minerals can be seen. This eclectic group includes authors have chosen to consider the phase as nonstoi- mixtures, insufficiently characterized minerals, possible chiometric joséite-B (or even joséite-A), the distinct nonstoichiometric “variants” of known minerals, and stoichiometry, close to 3:2 rather than 4:3, has contrib- also a number of phases of uncertain status. Some have uted to its status as a distinct but insufficiently defined already been discussed. The following are included here phase. X-ray data for “protojoséite” presented by for the sake of clarity and completeness. Zav’yalov & Begizov (1983b) from the “type locality” “Grünlingite” was first mentioned from Carrock of Băiţa Bihor, Romania, as well as additional material Fell, Cumbria, England by Rammelsberg (1853) and from the Malishevski Izumrydrye pit, Ural Mountains, later defined by Muthmann & Schröder (1898) as are not unequivocal either. The X-ray spectra closely having the composition Bi4TeS3. Examination of the resemble those of joséite-B, although they are not “type” material by Peacock (1941) proved inconclusive, identical. Bayliss (1991) assigned a P3m1 structure to but the phase was considered very close, if not identical “protojoséite” and attributed to it the probable formula to “joséite”. A similar composition was also described Bi5(Te,S)4, which is not consistent with the above by Koch (1948) and subsequently analyzed by Grasselly analytical data. (1948); these analyses also gave Bi4TeS3. The “type” Reported compositions that can be assigned to these material was re-examined by Zav’yalov & Begizov two subgroups have been summarized in Figure 16. (1981a, b, 1983b), but the presence of a bismuth We have chosen to plot “protojoséite” in the potential telluride with this stoichiometry was not confirmed. Bi3Te2–Bi3Se2–Bi3S2 isoseries, in part because we have The conclusion reached was that a discrete phase with observed a Bi3(Te,S)2 phase in specimens from Băiţa this composition does not exist, and the type material Bihor that is clearly distinct from joséite-B. is a mixture of two or more sulfotellurides of bismuth Whereas it is not difficult to consider the binary (joséite-A, ingodite), possibly also with admixed phases Bi2Te and Bi3Te2 as nonstoichiometric tsumoite bismuthinite. Subsequent electron-microprobe analysis or hedleyite [cf. overlap with datasets of “wehrlite” in of the material (summarized in Cooper & Stanley 1990) Cabri & Laflamme (1976) and “bismuthian tsumoite” in showed “grünlingite” to consist of a mixture of finely Dobbe (1993)], it is harder to explain the compositions intergrown joséite-A, joséite-B, ingodite and bismuthi- of the S- and Se-bearing compositions within these data- nite. The samples also contain krupkaite, cosalite and sets simply as substituted nevskite and ingodite, given native bismuth. Additional compositions of the same the consistent stoichiometry, with 60 and 66.6 mol.% material were given in Table 6. Given the nonstoi- Bi, respectively. The present authors wish to be neither chiometry seen in joséite-A at higher temperatures judge nor jury concerning the true identity of the phases (Bi4–xTe1+xS2; Yusa et al. 1979), it is plausible that the represented by these published compositions, but we “grünlingite” data may, in fact, represent the products of would suggest that natural phases within the subsystems decomposition of nonstoichiometric, high-temperature (isoseries) Bi2Te–Bi2Se–Bi2S and Bi3Te2–Bi3Se2–Bi3S2 joséite-A. Kudrina et al. (1986) published results of a probably exist; note that both stoichiometries have been single electron-microprobe analysis of a phase from synthesized experimentally (e.g., Okamoto & Tanner the Bayanskoye deposit in northern Kazakhstan, which 1990, Okamoto 1994). show a Bi: (Te + S + Se) stoichiometry between that of Vihorlatite, Bi8+x(Se,Te,S)11–x, was approved as a “grünlingite” (3:3) and joséite-A (4:3). new mineral species in 2000. The type locality is given “Platynite”, PbBi2(Se,Se)3 (Flink 1910), was long as Poruba, Vihorlat Mountains, Slovakia. A description considered a questionable species (Nikitin et al. 1989, was published by Skála et al. (2007), with the formula Bayliss 1991) and has subsequently been formally given as Bi24Se17Te4. This would appear to be the first discredited as a mixture of laitakarite and selenian member of a Bi8X7 isoseries. galena (Holtstam & Söderhielm 1999). Other stoichiometries reported include the Bi2Te5 “Oruetite”, Bi8TeS4, was described by Piña de (BiTe2?) phase of Aksenov et al. (1968a, c), interpreted Rubies (1919) from the Ronda massif, Spain, and later as “disordered” tsumoite by Bayliss (1991), but surely said to be identical to “grünlingite” (Garrido & Feo requiring re-examination. Okamoto & Tanner (1990) 1938). Although the name has been used more recently reported such a composition as a metastable phase in to describe a phase with such a composition (e.g., the binary system Bi–Te. The same applies to BiSe2Te Ontoyev et al. 1974), the original Spanish samples are (Nekrasov 1996). recognized as inhomogeneous (e.g., Peacock 1941). In minerals of the system bi–te–se–s related to the tetradymite archetype 695

a

c

b

Fig. 16. Summary plot for unnamed phases in the subsystems Bi2Te–Bi2Se–Bi2S and Bi3Te2–Bi3Se2–Bi3S2. (a) Plot of phases in both subsystems in terms of Bi(+ Pb + Sb)–(S + Se)–Te. (b) Bi2Te–Bi2Se–Bi2S subsystem. Data for Bi2Te from Gamyanin et al. (1980, 1982), Goncharov et al. (1984), Huang et al. (1991), Luukkonen (1994) and Gu et al. (2001); for Bi2(Te,Se,S) (green circles) from Kontoniemi et al. (1991) and for Bi2(Te,Se) (blue circles) from Gu et al. (2001). (c) Bi3Te2–Bi3Se2–Bi3S2 subsystem. Protojoseite from Zav’yalov & Begizov (1983b). Data for Bi3Te2 from Kukovsky & Lazarenko (1959) cited by Zav’yalov et al. (1978), Sarkar & Deb (1969) and Sztrozkay & Nagy (1982); data for Bi3(TeS)2 and Bi3(STe)2 from Godovikov et al. (1970, 1971b). the system Bi–Te–Se–S, however, unless such material Inasmuch as poubaite and plumboan rucklidgeite (see is clearly and unequivocally shown to be a mixture of above) are commonly Pb-bearing, and other minerals known minerals and can be discredited (e.g., “csik- (like tetradymite, laitakarite, joséite-A, joséite-B) may lovaite”; Bayliss 1991 or “platynite”; Holtstam & also contain significant Pb, a brief account of other Söderhielm 1999), it can remain extremely difficult to minerals of the subgroup containing essential Pb definitively prove that phases with other compositions belongs in the present contribution. or stoichiometries do not (or cannot) exist, and accord- The Pb–Bi compounds are structurally distinct from ingly expunge such names from the literature. the (ideally) Pb-free compounds. With the exception of the study by Zhukova & Zaslavskii (1971), however, Minerals with Variable Stoichiometry single-crystal X-ray studies are lacking for these and Containing Essential Pb compounds. Aleksite, PbBi2Te2S2 (Lipovetskiy et al. 1977, 1979, Spiridonov et al. 1989, Bevins & Stanley A group of tellurosulfide minerals contains essential 1990, De Souza Lima et al. 1996, Ueno et al. 1996) and Pb as well as Bi, and both Te and S. Although part saddlebackite, Pb2Bi2Te2S3 (Clarke 1997), together with of the tetradymite group (Strunz & Nickel 2001) and an additional compound, “phase C” of Lipovetskiy et sharing similar structures and mode of occurrence with al. 1977, 1979 (PbBi4Te4S3), are suggested to belong other minerals in the groups discussed formally above, to a single accretional chemical series with the general they qualify as sulfosalts (Moëlo & Makovicky 2006). formula PbnBi4Te4Sn+2 (Cook et al. 2007). “Phase C”, 696 the canadian mineralogist aleksite, Pb3Bi4Te4S5 and saddlebackite have previously gives the empirical formula Bi1.95Pb1.99Ag0.01Sb0.01 been reported as synthetic products (Phases D, E, F and S1.74Se1.30. The mineral has not been reported from J) in experiments at 500°C (Liu & Chang 1994). Unit- other deposits. cell data provided by Liu & Chang (1994) support the An unnamed phase, Pb5Bi5Te3S7, was reported to existence of a chemical series, but X-ray data on natural be associated with kochkarite from Kochkar (Spiri- specimens are required to validate the hypothetical donov et al. 1989). Selenium-bearing compounds with model proposed by Cook et al. (2007). In this model, compositions close to Pb2Bi2(S,Se)3 and (Bi,Pb)3(S,Se)4 the unit cell of aleksite comprises three seven-atom were reported by Sakharova et al. (1993). A synthetic layers (each Te–Bi–S–Pb–S–Bi–Te), and “phase C” compound with composition close to PbBi4Te3Se4, with consists of a combination of one five-atom tetradymite orthorhombic symmetry, was studied by Kichambare unit (as in the simple Bi–Te–Se–S compounds above) et al. (1997). and one seven-atom layer. Although no single-crystal data exist for saddlebackite, unit-cell data on phase J Discussion (Liu & Chang 1994) suggest that saddlebackite is a superstructure consisting of a single nine-atom layer, In this contribution, we have contrasted the need and Pb3Bi4Te4S5 may be regarded as a combination for a functional system of nomenclature and classi- of one seven-atom and one nine-atom layer. Investiga- fication based upon stoichiometry, with the inherent tions of complex sulfosalt-telluride assemblages from character of the Bi–Te–Se–S compounds to form a Iilijärvi, southwest Finland (Ciobanu et al. 2002, Cook number of (complete or partial) solid-solution series: et al. 2007) have revealed possible additional Pb-rich Bi2(Te,Se,S)3, Bi3(Te,Se,S)4, Bi(Te,Se,S), Bi4(Te,Se,S)3, members of this series, with compositions in the range etc., each derived from discrete variants in stacking between Pb5Bi4Te4S7 and Pb7Bi4Te4S9. Characteristic sequence (= homologue types). Although Bi-for-Te(Se) of all these minerals are fine intergrowths and lamellar substitution may yet be unequivocally demonstrated banding, resulting in poor stoichiometry. This may to play a significant role in natural specimens, we can readily be linked to the loss of periodicity and the still choose to regard each of the above as a discrete difficulty of building thick Pb-filled slabs. isoseries, each with unique integer values of N1 and Kochkarite, PbBi4Te7 (Spiridonov et al. 1989) corre- N2 in the general series BiN1(Te,Se,S)N2. sponds to the synthetic phase M of Liu & Chang (1994). Many of the numerous compounds successfully Synthetic PbBi4Te7 (and PbBi2Te4) were obtained in synthesized in the systems Bi–Te and Bi–Se appear to experiments of the system PbTe–Bi2Te3 by Chami et have no natural analogues. It is fair to say, however, al. (1983). The structure can be considered in terms of that it may be difficult or impossible to recognize alternations of seven-atom (Te–Bi–Te–Pb–Te–Bi–Te) many of these in nature, owing to overlapping ranges and five-atom (Te–Bi–Te–Bi–Te) layers (Petrov & of substitution and solid solution, the potential for Imamov 1970). Imai & Watanabe (2003) have satisfac- stacking disorder, precision of the electron-microprobe torily determined the electronic structure of PbBi4Te7, data and potential analytical error. This is compounded based on such a “75” structure. by the lack of single-crystal X-ray data. Such problems Although much of the early data favoring the seven- are particularly valid for the central parts of the system atom layer structure for PbBi2Te4 (rucklidgeite), with Bi–Se, where a large number of phases with individual possible extension to aleksite and other tellurosulfides, combinations of stacking could theoretically exist in is powder-diffraction data with typically high values nature, for example, Bi6Te5, Bi8Te7, Bi8Te9, Bi6Te7 and (>15%) of R (Petrov & Imamov 1970, Imamov et al. Bi4Te5. Although closely related, each of these will be 1970, Zhukova & Zaslavskii 1976), corroborative single structurally distinct from BiTe, in the same way that crystal and HRTEM data are available for the directly Bi2Te3 or Bi4Te3 also are distinct from BiTe, and would analogous and well-characterized nGeTe•mBi2Te3 therefore warrant distinct mineral status at a point in the compounds (Kuypers et al. 1988, 1989, Frangis et future when they can be completely characterized. Prag- al. 1989, Shelimova et al. 1996, 2000, 2001, 2004, matists may argue that identification of large numbers Karpinsky et al. 1998, Kuznetsova et al. 2000, Konstan- of new mineral phases, virtually indistinguishable from tinov et al. 2001). one another in terms of composition, may disrupt any Karpinsky et al. (2002) identified three addi- reasonable system of enforceable classification. Never- tional layered compounds, PbBi6Te10, PbBi8Te13 theless, we note that precedents have already been set, and Pb2Bi6Te11, and proposed that these belong to a for example, in the bismuthinite–aikinite series (e.g., homologous series nPbTe•mBi2Te3, with n = 1, 2, and Makovicky et al. 2001). In this series, well-defined m ranging from 1 to 4. compounds with stoichiometric formulae are identi- Babkinite was introduced as a new mineral with fied, but many natural samples give nonstoichiometric the formula Pb2Bi2(S,Se)3 (Bryzgalov et al. 1996). The compositions. Electron-microprobe data are not suffi- type locality is the high-temperature Nevskii Sn–W cient to name such compounds. Instead, a substitution deposit, Magadan District, Russia. Type babkinite coefficient is used to give the position of the analysis within the series. minerals of the system bi–te–se–s related to the tetradymite archetype 697

The application of high-resolution transmission tion, including their application as redox indicators. electron microscopy to natural bismuth chalcogenides In a companion paper, we will address a number of of various compositions is needed to clarify many of these issues, at least in cases where reliable data can be the issues outlined here, as is high-precision single- established. In particular, we will address the common crystal X-ray data for natural minerals and problematic misconception that the tellurides of bismuth are typi- intermediate compositions. In their discussion of the cally “low-temperature” minerals. correlation between composition and structure of laita- In this review, we have illustrated the considerable karite, Nenasheva et al. (1988) noted that two phases advance in understanding these minerals that has been with slightly different stoichiometries (Bi6Se5, Bi8Se7), afforded by the application of modern investigative but otherwise similar to laitakarite, have larger unit- techniques. Nevertheless, very many uncertainties and cells, and thus are probably distinct from laitakarite (or incongruencies remain to be solved in the future. The indeed nevskite). evolution in our technical ability to fully characterize In nature, Bi2(Te,Se,S)3 minerals, especially tetrady- smaller and smaller grains may yet permit some of the mite and tellurobismuthite, are the most common statis- outstanding problems to be resolved. Results of such tically, closely followed by Bi4(Te,Se,S)3 minerals and, investigations may necessitate a revision of the way in then, by Bi(Te,Se,S) and Bi3(Te,Se,S)4 minerals. These which these mineral groups are classified. As mentioned have relatively simple structures in common, involving above, new ways to adequately describe the composi- low-integer combinations of Bi2 and Bi2(Te,Se,S)3 units. tions of these minerals may need to be developed. Some We have made a plausible case for the existence of two revisions to the nomenclature may be required. additional isoseries, Bi2(Te,Se,S) and Bi3(Te,Se,S)2. Lastly, given the frequent change of mineral names Minerals of the Bi4(Te,Se,S)3 isoseries, with alternating and formulae, redefinitions, uncertainty concerning Bi2 and Bi2Se3 layers, are stable at Bi-rich composi- various phases, and the common-place presence of tions and commonly coexist with native bismuth. microscopic to submicroscopic intergrowths among Other structures still richer in Bi, e.g., Bi3(Te,Se,S)2 Bi–Te–Se–S minerals, the labeling of specimens in or Bi2(Te,Se,S), appear to be only rarely preserved in many museum collections should be doubted unless nature. Similarly, minerals of the Bi2(Te,Se,S)3 isoseries corroborative microanalytical data are available. We are more stable than others at the Te-rich end of the are convinced that many of the uncertainties illustrated spectrum. in this contribution could be rectified if older, generally In this contribution, we have stressed that all phases coarser material is made available for restudy. in the system Bi–Te–Se–S, whether natural or synthetic, can be considered to belong to a single homologous Conclusions series built by variations of Bi2X3 and Bi2 units. When considering Pb-bearing compounds, we have intro- 1. We have demonstrated that the system of clas- duced the concept of seven- and even nine-layered sification used for the bismuth chalcogenides on a stoi- lamellae. Nevertheless, the introduction of seven- and chiometric basis is broadly correct, both with respect to even nine-layer units as structural defects into Bi2Te3 the underlying structures and in practice. Four principal or Bi2Se3 can be considered as plausible (Frangis et al. isoseries exist in nature and contain named minerals, 1989, 1990). Degrees of nonstoichiometry in synthetic Bi2Te3–Bi2Se3–Bi2S3, Bi4Te3–Bi4Se3–Bi4S3, BiTe– Bi2X3 compounds may be explained in terms of lattice BiSe–BiS and Bi3Te4–Bi3Se4–Bi3S4. Each of these is, in point-defects (antisite defects; e.g., Horák et al. 1990), turn, a stacking variant in a general homologous series impurities and vacancies, but with increased amounts BiN1(Te,Se,S)N2, where N1 and N2 are integer values. of excess Bi atoms, the incorporation of larger units can Cases can be made for the existence of further isoseries be invoked (e.g., Horák et al. 1992, Plecháček et al. in nature, Bi2Te–Bi2Se–Bi2S, Bi3Te2–Bi3Se2–Bi3S2, 2002). Investigators of synthetic compounds have also Bi3Te4–Bi3Se4–Bi3S4, Bi6Te5–Bi6Se5–Bi6S5, etc., documented atomic-scale diffusion of Se in Bi2Te3 by although further characterization, based in particular antisite defects and thermal vacancies (e.g., Scherrer on single-crystal X-ray-diffraction data, is essential to et al. 1988, Chitroub et al. 2000). The significance of verify this. these findings for compositional variation in natural 2. Solid solution is not unlimited within each specimens is unknown. isoseries, but is closely governed by a series of substitu- The basic data on the tellurides and selenides of tion mechanisms, governed by structural continuity. The bismuth have largely come from inorganic chemists Se S substitution is prevalent in all series, with well- or physicists interested in the compounds for their developed solid-solution series, e.g., between tetrady- thermoelectric properties. Geologists and mineralogists mite and kawazulite, joséite-B and unnamed Bi4Te2Se. need to address many of the open questions regarding The Te Se(S) substitution appears more restricted. the internal structures of natural phases, documentation Binary Bi-tellurides in each isoseries (tellurobismuthite, of solid solutions, the stabilities of these compounds, pilsenite, tsumoite, hedleyite) show only moderate Te their association, paragenesis and conditions of forma- Se substitution, and negligible Te S substitution. 698 the canadian mineralogist

There is no significant solid-solution betweene.g., tellu- Correlation Programme project 486, “Telluride and robismuthite and tetradymite, pilsenite and joséite-B. Selenide Deposits”. The Bi Te(Se,S) substitution (“disordering” in the Lastly, we should mention that in this review, we sense of Bayliss) may satisfactorily explain variations have attempted to take into account all published in Bi:(Te + Se + S) ratio in some minerals (hedleyite, compositional data on phases in the system. We recog- tsumoite), but stacking disorder is also an efficient nize that there may still be valuable data in conference mechanism to account for apparent nonstoichiometry. abstracts, in theses, and in publications, which we have 3. Several potential “new” mineral species can either not been aware of, or which were inaccessible to be identified in the known isoseries, e.g., Bi4Te2Se, us for reasons of language or other reasons. We, there- Bi4Te(Se,S)2, Bi3Te2Se and Bi3(Te,S,Se)4. A large fore, express our apologies to any authors who feel that number of additional “phases” have been synthesized their work has been ignored, and request that relevant or predicted in the binary systems Bi–Te and Bi–Se, information be forwarded to us. and many of these have no natural analogues. Others may exist, but have not been detected, owing to their References compositional proximity to named minerals, especially in the central region of the system with Bi/(Te + Se + Abrikosov, N.K. & Bankina, V.F. (1958): Study of phase S) values close to unity. There is a need for HRTEM diagram of the system Bi–Te. J. Inorg. Chem. USSR 3, and single-crystal X-ray work on natural specimens to 659-667. resolve such issues. Abrikosov, N.K. & Stasova, M.M. (1985): Solid solutions based in Bi–Te, Sb–Te and Bi–Se systems on bismuth and Acknowledgements antimony tellurides and bismuth selenides. Izv. Akad. Nauk. SSSR, Neorgan. Materialy 21, 2011-2015 (in Russ.). We gratefully acknowledge access to electron- microprobe facilities at a number of institutions: EU Afifi, A.M., Kelly, W.C. & Essene, E.J. (1988a): Phase Geochemical Facility, University of Bristol and the relations among tellurides, sulfides, and oxides. I. Ther- Natural History Museum, London, U.K. (European mochemical data and calculated equilibria. Econ. Geol. Community Access to Research Infrastructure action of 83, 377-394. the IHP Program), Adelaide, South Australia (with the Afifi, A.M., Kelly, W.C. & Essene, E.J. (1988b): Phase kind support of Allan Pring, South Australian Museum, relations among tellurides, sulfides, and oxides. II. Appli- and Adelaide Microscopy) and the Department of cations to telluride-bearing ore deposits. Econ. Geol. 83, Mineralogy, University of Salzburg, Austria, with the 395-404. kind support of Werner Paar and technical support from Dan Topa. Work on this manuscript began while Agaev, K.A. & Semiletov, S.A. (1968): Electron diffraction the first author was located at the Geological Survey study of the structure of PbBi2Se4. Kristallografiya 13, of Norway (NGU). The review would not have been 258-260 (in Russ.). possible without the support of library staff at NGU, as Aksenov, V.S., Inin, V.D., Litvinovich, A.N., Slyusarev, well as at the Natural History Museum, London, who A.P. & Kosyak, Y.A. (1968a): Selenium-bearing miner- helped us locate many “difficult-to-find” publications. als in ores of the Orlov pyrite polymetallic deposit in the We acknowledge discussions with many individuals Altai. Izv. Akad. Nauk. Kazakh. SSR, Ser. Geol. 5, 42-52 equally fascinated by tellurides and selenides of bismuth (in Russ.). during the past few years. In particular, we deeply appreciate comments from Vlad Kovalenker, Masaaki Aksenov, V.S., Kosyak, Y.A., Mergenov, S.K. & Rafikov, Shimizu and Emil Makovicky. A still larger number T.K. (1968b): New data on bismuth tellurides in the Altai. of persons are greatly appreciated for sharing sample Zap. Vses. Mineral. Obshchest. 97, 699-705 (in Russ.). material, knowledge and enthusiasm on the geology Aksenov, V.S., Kosyak, Y.A., Mergenov, S.K. & Rafikov, of individual localities, all of which has helped us T.K. (1968c): A new bismuth telluride – Bi2Te5. Dokl. compile this work. Special thanks are due to Krister Akad. Nauk. SSSR 181, 113-115. Sundblad for introducing us to Orijärvi, Finland, and Glava, Sweden, to Kari Kojonen for helping us with Alechevskiy, A.V. (2002): Minerals of tin, antimony and our work on the Orivesi deposit, and to Sergey Nechaev bismuth in the auriferous deposit of Kuchukashan (Mal- and Inna Mudrovska for furnishing us with material tanskiy stock): peculiarities of composition and genesis. from the Maiskoe deposit, Ukraine. We very much In Proc., Geology, Genesis and Problems of Developing appreciate the time invested by Yves Moëlo, Hans- Complex Deposits of Noble Metals (N.P. Laverov & V.V. Georg Förster and Robert F. Martin during review and Distler, eds.). IGEM–RAS, Moscow, Russia (in Russ., 257-260). editorial work on this lengthy contribution. The three sets of stimulating and encouraging comments helped Arutyunyan, G.A. & Eremin, N.I. (1978): Find of tellu- us to make significant improvements to our manuscript. rides in the ores of the Ankadzor copper-sulfide deposit This paper is a contribution to International Geological minerals of the system bi–te–se–s related to the tetradymite archetype 699

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Zav’yalov, Y.N. & Begizov, V.D. (1977): Rucklidgeite, (Bi, Pb)3Te4, a new mineral from the Zod and Kochkar gold-ore Received February 15, 2004, revised manuscript accepted deposits. Int. Geol. Rev. 19, 1451-1456. December 19, 2006.