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Bismuth and bismuth–antimony sulphosalts from Neogene vein mineralisation, Baia Borşa area, Maramureş, Romania

Published online by Cambridge University Press:  05 July 2018

Nigel J. Cook*
Affiliation:
Mineralogisches Institut der Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany

Abstract

Several complex Cu-Pb-Bi, Cu-Pb-Bi-Sb and Ag-Pb-Bi sulphosalt minerals have been identified in samples from hydrothermal vein mineralisation associated with the Toroiaga sub-volcanic body in the Baia Borşa area of Maramureş County, northwest Romania. This is the first chemically-documented report of Bi-sulphosalts in the Neogene metallogenic province around Baia Mare. The investigated samples contain abundant amounts of matildite solid solution within galena, the Cu-Pb/Bi sulphosalts aikinite, friedrichite, krupkaite, hammarite, lindströmite and gladite as well as nuffieldite and berryite. Within the Ag-Pb/Bi group, the majority of analysed grains can be regarded as members of the lillianite homologous series. Three distinct lillianite homologues were identified, which correspond to (i) phases along the lillianite-gustavite solid solution join (Pb3Bi2S6-AgPbBi3S6), (ii) phases within solid solution field of heyrovskyite, and (iii) compositions which best correspond to ‘schirmerite’, sensu Makovicky and Karup-Møller (1977b), but may represent disordered gustavite, vikingite or eskimoite. Some of the analysed lillianite homologues contain excess Cu, which may occupy interstitial sites. Furthermore, a large proportion of the lillianite homologues display significant substitution of Sb for Bi within the limits predicted by experimental investigations. Cosalite, also showing a range of compositions including Sb-rich varieties is recognised. Izoklakeite, Cu2Pb22(Sb,Bi)22S57, is an abundant phase throughout the analysed samples, its composition is in good agreement with previously published analyses, except for excess Cu and Fe beyond the limits previously reported. The description of several minerals from this new occurrence and compositional data on them, including the Sb-bearing varieties, provides valuable additional information on compositional limits in natural samples.

Type
Mineralogy
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1997

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References

Andronescu, A., Bădescu, I. and Duma, N. (1962) Contributţii la cunoašterea zăcămîntului Ilba-Handal. Revista Minelor 13, 393404.Google Scholar
Balitskaya, O.V., Vakh, A.S., Sivtsov, A.V. and Mozgova, N.N. (1987) Ultramicrointergrowths of sulphosalts of the Pb-Cu-Sb-Bi-S system. Miner. Journal, 9, 3545.(in Russian).Google Scholar
Bernhardt, H.-J. (1987) A simple fully-automated system for ore mineral identification. Mineral. Petrol., 36, 241-5.CrossRefGoogle Scholar
Berza, T., Borcoş, M., Ianc, R. and Bratosin, I. (1982) La succession des intrusions neogenes de la region Toroiaga-Ţiganul (Monts Maramureş). Dari de Seama ale Sedintelor, 67(Pt. 1), 1124.Google Scholar
Bologa, V. and Udubaşa, G. (1995) Minerals and mineral varieties first described in the Baia Mare area. In: 3rd Symposium on Mineralogy: Excursion Guides (G. Udubaşa, ed.), Romanian Journal of Mineralogy, 77, Suppl. 2, 1115.Google Scholar
Borcoş, M. (1967) Studiul geotermometric al mineralizatei din masivul subvulcanic neogen Toroiaga-Ţiganul (Maramureş). Dari de Seama ale Sedintelor, 53 (Pt. 2), 219-40.Google Scholar
Borcoş, M., Anăfir, P., Andăr, A. and Berza, T. (1982) Geochimia mineralizaţiilor polimetalice din cîmpul minier Toroiaga (Baia Borşa, Munţii Maramureşului). Dari de Seama ale Sedintelor, 67 (Pt. 2), 5582.Google Scholar
Borodaev, Y.S. and Mozgova, N.N. (1975) Lead- bismuth-antimony sulphosalts of the Pocheknev deposit, eastern Transbaikal region. Geol. Rudn. Mesto Rozhd., 17, 4558.(in Russian).Google Scholar
Bortnikov, N.S., Kovalenker, V.A., Safanov, Y.G., Troneva, N.V., Laputina, I.P. and Razdolina, N.V. (1985) The characteristic assemblages and formation conditions of Cu-Ag-Pb-Bi sulfosalts in the Kanimansur ore field. lzv. Akad. Nauk. SSSR, 6, 6575 (in Russian).Google Scholar
Bortnikov, N.S. and Tsepin, A.N. (1987) (Sb,Bi)-sulfosalts from Srednegolgota deposit (East Transbaikalia). lzv. Akad. Nauk. SSSR Geol ser., 1, 8695 (in Russian).Google Scholar
Breskovska, V.V., Mozgova, N.N., Bortnikov, N.S., Tzepin, A.I. and Borodaev, Y.S. (1988) New data on the bismuth sulphosalts from the Bakadjik polymetallic deposit, Yambol district, Bulgaria. Annuaire de l'Université de Sofia “Kliment Ohridski”, Fac. Geol.-Geograph., 78, 182-90.Google Scholar
Chang, L.L.Y. and Hoda, S.N. (1977) Phase relations in the system PbS-Cu2S-Bi2S3 and the stability of galenobismutite. Amer. Mineral. 62, 346-50.Google Scholar
Chang, L.L.Y., Walia, D.S. and Knowles, C.R. (1980) Phase relations in the systems PbS-Sb2S3-Bi2S3 and PbS-FeS-Sb2S3-Bi2S3 . Econ. Geol., 75, 317-28.CrossRefGoogle Scholar
Chang, L.L.Y., Wu, D. and Knowles, C.R. (1988) Phase relations in the system Ag2S-Cu2S-PbS-Bi2S3 . Econ. Geol., 83, 405-18.CrossRefGoogle Scholar
Chen, T.T. and Chang, L.L.Y. (1974) Investigations in the systems Ag2S-Cu2S-Bi2S3 and Ag2-CuzS-Sb2S3.. Canad. Mineral., 12, 404-10.Google Scholar
Chioreanu, I., Fabricantu, M., Giurgiu, C., Groza, D., Radu, M., Răisescu, D. and Surducan, A. (1993) Lithogeochemical study of primary haloes related to some mineralizations in Toroiaga Massif. Third Geological Symposium Abstracts Volume, Baia Mare, October 1993, 8-9.Google Scholar
Clark, A.M. (1993) Hey's Mineral Index. 3rd Edition, Chapman and Hall, London, 852 pp.Google Scholar
Cook, N.J. (1995) Polymetallic massive sulphide deposits at Baia Borşa, Romania. In: Mineral Deposits.” from their Origin to their Environmental Impacts (Pašava, J., B., Kříek and K., Žák, eds.), Proc. 3rd SGA Meeting, Prague 1995, Balkema, Rotterdam, 851-4.Google Scholar
Cook, N.J. (in press) Sulphur-isotope characteristics of polymetallic sulphide ores at Baia Borşa, Maramureş, Romania. Romanian Journal of Mineralogy. Google Scholar
Cook, N.J. (submitted) Sulphide and sulphosalt mineralogy of Cambrian massive sulphide and superimposed Neogene mineralisation at Baia Borşa, Romania. Mineral. Deposita. Google Scholar
Craig, J.R. (1967) Phase relations and mineral assemblages in the system Ag-Cu-Bi-Pb-S system. Mineral. Deposita 1, 278306.CrossRefGoogle Scholar
Czamanske, G.K. and Hall, W.E. (1975) The Ag-Bi-Pb Sb-S-Se Te mineralogy of the Darwin leadsilver-zinc deposit, southern California. Econ. Geol. 70, 1092-110.CrossRefGoogle Scholar
Damian, G. and Oşcan, E. (1993) Native gold in the hydrothermal ores of Toroiaga Massif (abstract). Romanian Journal of Mineralogy, 76 Suppl. 1, 1415.Google Scholar
Ertl, A., Libowitzky, E. and Pertlik, F. (1994) Chemische und Röntgenkristallographische Untersuchungen an Eskimoit (Ag7Pb10Bi15S36) und Heyrovskyit (AgPb10Bi5S18) vom “Rauriser Goldberg, Htittwinkeltal, Land Salzburg. Mitt. Osterr. Mineral. Ges. 139, 135-42.Google Scholar
Finashin, V.K., Litavrina, R.F., Romanenko, I.M. and Chubarov, V.M. (1981) On lillianite, gustavite and minerals of the lillianite-gustavite series from the stannous ores of Kavelerorovsky region. Zap. Vsez. Min. Obshch. 110, 304-10.(in Russian).Google Scholar
Foord, E.E. and Shawe, D.R. (1989) The Pb-Bi-Ag- Cu-(Hg) chemistry of galena and some associated sulfosalts: a review and some new data from Colorado, California and Pennsylvania. Canad. Mineral. 27, 363-82.Google Scholar
Goodell, P.C. (1975) Binary and ternary sulphosalt assemblages in the Cu2S-Ag2S-PbS-As2S3-Sb2S3-Bi2S3 system. Canad. Mineral., 13, 2742.Google Scholar
Götz, A., Damian, G. and Farbaş, N. (1990) Contribuţii la mineralogia bournonitul associat mineralizaţiilor din masivul Toroiaga-Baia Borşa. Revista Minelor 41, 467-71.Google Scholar
Gridan, T., Gurău, A. and Macaleţ, V. (1979) Consideraţii structural-genetice privind mineralizaţiile de sulfuri polimetalice din masivul subvulcanic Toroiaga, perimetrul Piciorul Ţiganului (Munţii Maramureş). Studii şi cercetari de Geol., Geof. Geogr., Seria Geol. 24, 6574.Google Scholar
Harris, D.C. and Chen, T.T. (1975) Gustavite: two Canadian occurrences. Canad. Mineral. 13, 411-4.Google Scholar
Harris, D.C. and Chen, T.T. (1976) Crystal chemistry and re-examination of nomenclature of sulphosalts in the aikinite-bismuthinite series. Canad. Mineral. 14, 194205.Google Scholar
Harris, D.C., Roberts, A.C. and Criddle, A.J. (1986) Izoklakeite, a new mineral species from Izok Lake, Northwest Territories. Canad. Mineral., 24, 15.Google Scholar
Helke, A. (1938) Die jungvulkanischen gold-silber Erzlagerstätten des Karpathenbogens. Archiv für Lagerstäittenforschung, 66.Google Scholar
Hoda, S.N. and Chang, L.L.Y. (1975) Phase relations in the pseudo-ternary system PbS-Cu2S Sb2S3 and the synthesis of meneghinite. Canad. Mineral. 13, 388-93.Google Scholar
Jambor, J.L. and Lachance, G.R. (1968) Bismuthian robinsonite. Canad. Mineral., 9, 426-8.Google Scholar
Karup-Møller, S. (1966) Berryite from Greenland. Canad. Mineral. 8, 414-23.Google Scholar
Karup-Møller, S. (1972) New data on pavonite, gustavite and some related sulphosalt minerals.. Neues Jahrb. Mineral. Abh. 117, 1938. Google Scholar
Karup-Møller, S. (1973) A gustavite-cosalite-galenabearing mineral suite from the cryolite deposit at Ivigtut, South Greenland. Meddelelser om Grønland 195, 139.Google Scholar
Karup-Møller, S. (1977) Mineralogy of some Ag-(Cu)-Pb Bi sulphide associations. Bull. geol. Soc. Denmark, 26, 4168.Google Scholar
Karup-Møller, S. and Makovicky, E. (1981) Ag- and Birich heyrovskyite from the Bi-W-Mo mineralization at Castlegar, British Colombia. Canad. Mineral. 19, 349-53.Google Scholar
Klomínský, J., Rieder, M., Kieft, C. and Mráz, L. (1971) Heyrovskýite, 6(Pb0.86(Ag,Cu)0.04S.Bi2S3) from Hfirky, Czechoslovakia, a new mineral of genetic interest. Mineral. Deposita 6, 133-47.CrossRefGoogle Scholar
Kovalenker, V., Jelěn, S. and Sandomirskaya, S. (1993) Minerals of the system Ag-Cu-Pb-Bi-S from the polymetallic veins of the Štiavnica-Hodruša ore field (Slovakia). Geologica Carpathica 44, 409-19.Google Scholar
Kupčik, V. (1983) Die Kristallstruktur des Minerals Eclarit, (Cu,Fe)Pb9Bi12S28 . Tschermaks Min. Petr. Mitt., 32, 259-69.CrossRefGoogle Scholar
Lee, C.H., Park, H.I. and Chang, L.L.Y. (1993) Sbcosalite from Dunjeon gold mine, Taebaeg City, Korea. Mineral. Mag. 57, 527-30.CrossRefGoogle Scholar
Lowry, D., Stephens, W.E., Herd, D.A. and Stanley, C.J. (1994) Bismuth sulphosalts within quartz veining hosted by the Loch Shin monzogranite, Scotland. Mineral. Mag., 58, 3947.CrossRefGoogle Scholar
Makovicky, E. and Karup-Møller, S. (1977a) Chemistry and crystallography of the lillianite homologous series (Part I: General properties and definitions).. Neues Jahrb. Mineral. Abh. 130, 264-87.Google Scholar
Makovicky, E. and Karup-Møller, S. (1977b) Chemistry and crystallography of the lillianite homologous series (Part II: Definition of new minerals: eskimoite, vikingite, ourayite and treasureite. Redefinition of schirmerite and new data on the lillianite-gustavite solid-solution series). Neues Jahrb. Mineral. Abh. 131, 5682.Google Scholar
Makovicky, E. and Makovicky, M. (1978) Representation of compositions in the bismuthinite- aikinite series. Canad. Mineral. 16, 405-9.Google Scholar
Makovicky, E. and Mumme, W.G. (1986) The crystal structure of izoklakeite Pb51.3Sb20.4Bi19.5Ag1.2Cu2.9Fe0.7S114. The kobellite homologous series and its derivatives. Neues Jahrb. Mineral. Abh. 153, 121-45.Google Scholar
Makovicky, E. and Nørrestam, R. (1985) The crystal structure of jaskolskiite, CuxPb2+x (Sb,Bi)2-xS5 (X 0.2), a member of the meneghinite homologous series. Zeits. Kristallogr. 171, 179-94.Google Scholar
Marcoux, E. and Moëlo, Y. (1993) Comparative mineralogy of massive and stringer sulphide ore deposits in southern Spain. In: Current Research in Geology Applied to Ore Deposits (Fenoll-Hach Ali, P. et al., eds.) Proc. 2nd SGA Meeting, Granada, Spain, 343-5.Google Scholar
Marcoux, E., Moëlo, Y. and Leistel, J.M. (1996) Bismuth and cobalt minerals as indicators of stringer zones to massive sulphide deposits, Iberian pyrite belt. Mineral. Deposita 31, 1-26.CrossRefGoogle Scholar
Matzat, E. (1979) Cannizzarite. Acta Crystallogr. 35, 133-6.CrossRefGoogle Scholar
Maurel, C. and Mo∼lo, Y. (1990) Synthèse de la nuffieldite dans te système Bi-Pb-Sb-Cu-S.. Canad. Mineral., 28, 745-9.Google Scholar
Moëlo, Y. (1989) Antimoine dans la nuffieldite associée à de la friedrichite (commune des Houches, Alpes de Haute-Savoie); redéfinition cristallo-chimique de la nuffieldite. Comptes Rendus Académie des Sciences Paris, Ser II, 309, 1959-64.Google Scholar
Moëlo, Y., Marcoux, E., Makovicky, E., Karup-Møller, S. and Legendre, O. (1987) Homotogues de la lillianite (gustavite, vikingite, heyrovskyite riche en Ag et Bi…) de I'indice à W-As-(Pb,Bi,Ag) de La Roche-Balue (Loire Atlantique, France), Bull. Mineral., 110, 4364.Google Scholar
Moëlo, Y., Roger, G., Maurel-Palacin, D., Marcoux, E. and Laroussi, A. (1995) Chemistry of some Pb-(Cu,Fe)-(Sb,Bi) sulfosalts from France and Portugal, Implications for the crystal chemistry of lead sulfosalts in the Cu-poor part of the Pb2S2-Cu2SSb2S3-Bi2S3 system. Mineral. Petrol. 53, 229-50.CrossRefGoogle Scholar
Mozgova, N.N. and Bortnikov, N.S. (1980) On the nonstoichiometry of kobellite. In: Sulphosalts, Platinum Minerals and Ore Microscopy, Proc, X1 Gen. Meeting Int. Mineral. Assoc., Novosibirsk, U.S.S.R., Nauka, Moscow, 3149.Google Scholar
Mozgova, N.N., Kuzmina, O.V., Organova, N.I., Laputina, l.P., Borodaev, Y.S. and Fornaseri, M. (1985) New data on sulphosalt assemblages at Vulcano (Italy). Rend. Soc. ltal. Mineral. Petrol., 40, 277-83.Google Scholar
Mozgova, N.N., Nenasheva, S.N., Borodaev, Y.S., Sivstov, A.V., Ryabeva, E.G. and Gamayanin, G.N. (1987) New mineral varieties in sulphosalts group.. Zap. Vses. Mineral. Obshch., 116, 614-28.(in Russian).Google Scholar
Mozgova, N.N., Nenasheva, S,N. and Borodaev, Y.S. (1990a) Antimony-bismuth sulphosalts. In: Geological-technological Assessment ∼)ie Ore Minerals, Samples and Deposits. All-Union Research and Design Institute of Mechanical Mining Processing, “Mechanov”, Leningrad, 99-108.Google Scholar
Mozgova, N.N., Nenasheva, S.N., Chistyakova, N.I., Mogilevkin, S.B. and Sivstov, A.V. (1990b) Compositional fields of minerals in the bismuthinite- aikinite series. Neues Jahrb. Mineral. Mh., 35-45.Google Scholar
Mozgova, N.N., Nenasheva, S.N., Borodaev, Y.S. and Yudovskaya, M.A. (1994) Nuffieldite from the Maleevskoe massive sulfide deposit, Russia. Canad. Mineral. 32, 359-64.Google Scholar
Mumme, W.G. and Watts, J.A. (1976) Pekoite, CuPbBi3S6, a new member of the bismuthiniteaikinite series. Its crystal structure and relationship with naturally and synthetically formed members. Canad. Mineral. 14, 322-33.Google Scholar
Mumme, W.G., Welin, W. and Wuensch, B.J. (1976) Crystal chemistry and proposed nomenclature for sulphosalts intermediate in the system bismuthiniteaikinite (Bi2S3-CuPbBiS3). Amer. Mineral., 61, 1520.Google Scholar
Nuffield, E.W. and Harris, D.C. (1966) Studies of mineral sulphosalts: XX. Berryite, a new species.. Canad. Mineral. 8, 407-13.Google Scholar
Ontoev, D.O., Druzhinin, A.V., Tsepin, A.I., Vyalsov, L.N. and Basova, G.V. (1980) Minerals of the series gustavite-litlianite from the Kti-Teberda deposit (N. Caucasus). Zap. Vses. Mineral. Obshch., 109, 322-34 (in Russian). Translation in. Int. Geol. Rev. 24, 659-70.CrossRefGoogle Scholar
Paar, W.H., Chen, T.T., Kupčik, V. and Hanke, K. (1983) Eclarit (Cu,Fe)Pb9Bi12S28, ein neues Sulfosalz von Bäirenbad, Hollerbachtal, Salzburg, Österreich. Tschermaks Min. Petr. Mitt. 32, 193210.CrossRefGoogle Scholar
Paar, W.H., Weidinger, J., Mrazek, R. and Heiss, H. (1993) Rotgülden: gold- und gustavit-Kristalle aus dem Salzburger Land. Lapis, 18, no. 5, 1328.Google Scholar
Pring, A. (1989) Structural disorder in aikinite and krupkaite. Amer. Mineral. 74, 250-5.Google Scholar
Pring, A. (1995) Annealing of synthetic hammarite, Cu2Pb2Bi4S9, and the nature of cation-Ordering processes in the bismuthinite-aikinite series. Amer. Mineral. 80, 1166-73.CrossRefGoogle Scholar
Pring, A. and Hyde, B.G. (1987) Structural disorder in lindströmite: A bismuthinite derivative. Canad. Mineral., 25, 393-9.Google Scholar
Radu, D. and Cook, N.J. (1995) The stratiform pyrite and base metal ore deposits hosted within the Tulghes Series in the Baia Borşa area, Maramure∼ Mountains. In: Third Symposium on Mineralogy: Excursion Guides (Udubaşa, G., ed.), Romanian Journal of Mineralogy, 77, Suppl. 2, 7997.Google Scholar
Sakharova, M.S. and Krivitskaya, N.N. (1970) Mineralogical and geochemical characteristics of Pb-Bi-Sb sutfosalts from gold deposits (Eastern Transbaikal). Geol. Rudn. Mest., 4, 5670.(in Russian).Google Scholar
Socolescu, M. (1954) Asupra geologiei regiunea Baia Borşa. D. S. Com Geol. 36, 178-86.Google Scholar
Socolescu, M., Butulescu, N., Popescu, T., Samoilă, I., Teodorescu, D. and Drăgilă, M. (1962) Contribuţii la cunoaşterea mineralizaţiei stanifere din minerul de la Baia Borşa - Burloaia. Revista Minelor, 13, no. 11, 481-7.Google Scholar
Syritso, L.F. and Senderova, V.M. (1964) The problem of the existance of lillianite. Zap. Vses. Mineral. Obshch., 93, 468-71.(in Russian),Google Scholar
Szöke, A. and Steclaci, L. (1962) Regiunea Toroiaga- Baia Borşa. Studiu Geologic, Petrogrctfic, Mineralogic şi Geochimic. Editura Academiei Republicii Populare Romîne, Bucharest, 240 pp.Google Scholar
Urabe, T. (1974) Mineralogical aspects of the Kuroko deposits in Japan and their implications. Mineral Deposita 9, 309-24.CrossRefGoogle Scholar
Vinigradova, L.G., Baranov, V.F., Semenova, T.F. and Yakovleva, O.A. (1992) Homogeneous heyrovskyite (Pb5.45Bi0.25Ag0.09)5.99(Bi1.97S0.03)2.00S9.00 from deposit Spokoinoe (East Transbaikal area. Mineral. Journal, 14, 4760.(in Russian).Google Scholar
Wagner, T. and Cook, N.J. (1996) Bismuth-antimony sulfosalts from siderite-hosted vein mineralization, Apollo mine, Siegerland, F.R.G. Neues Jahrb. Mineral. Abh., 171, 135-53.Google Scholar
Žák, L. (1980) Isomorphism and polymorphism in the bismuthinite-aikinite group. Neues Jahrb. Mineral. Mh., 440-8.Google Scholar
Zakrzewski, M.A. (1984) Jaskolskiite, a new Pb-Cu-Sb-Bi sulfosalt from Vena, Sweden. Canad. Mineral. 22, 481-5.Google Scholar
Zakrzewski, M.A. and Makovicky, E. (1986) lzoklakeite from Vena, Sweden, and the kobellite homologous series. Canad. Mineral., 24, 7-18.Google Scholar