Solid solutions in the system acanthite (Ag2S)–naumannite (Ag2Se) and the relationships between Ag-sulfoselenides and Se-bearing polybasite from the Kongsberg silver district, Norway, with implications for sulfur–selenium fractionation

  • Kåre KullerudEmail author
  • Jana Kotková
  • Vladimír Šrein
  • Milan Drábek
  • Radek Škoda
Original Paper


Sulfoselenides [Ag2(S,Se)] and Se-bearing polybasite have been discovered at the Kongsberg silver district. The selenium-bearing minerals occur in two samples from the northern part of the district, forming either single or polyphase inclusions together with chalcopyrite within native silver. The Ag-sulfoselenides show large chemical variations, covering nearly the complete compositional range between acanthite (Ag2S) and naumannite (Ag2Se). For the data presented here, there is no local maximum at the composition Ag4SSe attributed to the distinct phase called aguilarite, suggesting that this composition can be considered as one of many possible along the monoclinic Ag2S–Ag2S0.4Se0.6 solid solution series rather than a specific mineral phase. We present a model explaining the variations in the Se-content of Ag2(S,Se) as a result of gradual de-sulfidization of the rock under oxidizing conditions. During this process, sulfur from the Ag2S-component of Ag2(S,Se) oxidized and dissolved in the fluid phase as SO42−, resulting in the formation of native silver. The activity ratio \({a_{{{\text{S}}^{2 - }}}}/{a_{{\text{S}}{{\text{e}}^{2 - }}}}\) of the system gradually decreased due to the removal of SO42−, which resulted in the stabilization of a sulfoselenide with higher selenium content. As a result of reaction progress, grains of Ag2(S,Se) became gradually enclosed in newly formed native silver, and therefore isolated from further reactions with the grain-boundary fluid. Grains isolated early during the process show low content of Se reflecting high \({a_{{{\text{S}}^{2 - }}}}/{a_{{\text{S}}{{\text{e}}^{2 - }}}}\) of the equilibrium fluid, while grains showing high Se reflect the composition of late low \({a_{{{\text{S}}^{2 - }}}}/{a_{{\text{S}}{{\text{e}}^{2 - }}}}\) fluids. Analyses of Se-bearing polybasite show that selenium is preferentially partitioned into Ag2(S,Se) compared to polybasite. The model presented here demonstrates how oxidation of sulfoselenides leads to fractionation of sulfur and selenium.


Kongsberg silver district Selenides Acanthite Naumannite Aguilarite Se-bearing polybasite Oxidation De-sulfidization 



This research has been funded by the internal project 331100 of the Czech Geological Survey as a part of its Strategic research plan. Christian Berg is thanked for the photographs used in Fig. 2. Constructive comments from Galina Palyanova and Mathias Burisch improved the manuscript significantly. Chris Ballhaus is thanked for the editorial handling.


  1. Ahmed AH, Arai S, Ikenne M (2009) Mineralogy and paragenesis of the Co-Ni arsenide ores of Bou Azzer, Anti-Atlas, Morocco. Econ Geol 104:249–266CrossRefGoogle Scholar
  2. Andrews AJ, Owsiacki L, Kerrich R, Strong DF (1986) The silver deposits at cobalt and Gowganda, Ontario. I: geology, petrography, and whole-rock geochemistry. Can J Earth Sci 23:1480–1506CrossRefGoogle Scholar
  3. Armstrong JGT, Parnell J, Bullock LA, Perez M, Boyce AJ, Feldmann J (2018) Tellurium, selenium and cobalt enrichment in Neoproterozoic black shales, Gwna Group, UK: deep marine trace element enrichment during the second great oxygenation event. Terra Nova 30:244–253CrossRefGoogle Scholar
  4. Bastin ES (1939) The nickel–cobalt-native silver ore type. Econ Geol 34:1–40CrossRefGoogle Scholar
  5. Bindi L, Pingitore NE (2013) On the symmetry and crystal structure of aguilarite, Ag4SeS. Min Magn 77:21–31CrossRefGoogle Scholar
  6. Bindi L, Evain M, Spry PG, Menchetti S (2007) The pearceite-polybasite group of minerals: crystal chemistry and new nomenclature rules. Am Min 92:918–925CrossRefGoogle Scholar
  7. Bugge C (1917) Kongsbergfeltets geologi. Nor Geol Underst 82:272Google Scholar
  8. Bugge A (1932) Gammel og ny geologi ved Kongsberg Sølvverk. Nor Geol Tidsskr 12:123–148Google Scholar
  9. Bullock LA, Perez M, Armstrong JG, Parnell J, Still J (2018) Selenium and tellurium resources in Kisgruva Proterozoic volcanogenic massive sulphide deposit (Norway). Ore Geol Rev 99:411–424CrossRefGoogle Scholar
  10. Burisch M, Gerdes A, Walter BF, Neumann U, Fettel M, Markl G (2017) Methane and the origin of five-element veins: mineralogy, age, fluid inclusion chemistry and ore forming processes in the Odenwald,SW Germany. Ore Geol Rev 81:42–61CrossRefGoogle Scholar
  11. Cheilletz A, Levresse G, Gasquet D, Azizi-Samir MR, Zyadi R, Archibald DA, Farrar E (2002) The giant Imiter silver deposit: neoproterozoic epithermal mineralization in the Anti-Atlas. Morocco Miner Depos 37:772–781CrossRefGoogle Scholar
  12. Cocker HA, Mauk JL, Rabone SDC (2013) The origin of Ag-Au-S-Se minerals in adularia-sericite epithermal deposits: constraints from the Broken Hills deposit, Hauraki Goldfield, New Zealand. Miner Depos 48:249–266CrossRefGoogle Scholar
  13. Coleman RG, Delevaux M (1957) Occurrence of selenium in sulfides from some sedimentary rocks of the western United States. Econ Geol 52:499–527CrossRefGoogle Scholar
  14. Dill HG (2010) Authigenic heavy minerals a clue to unravel supergene and hypogene alteration of marine and continental sediments of Triassic to Cretaceous age (SE Germany). Sed Geol 228:61–76CrossRefGoogle Scholar
  15. Drebushchak VA, Pal’yanova GA, Seryoykin YV, Drebushchak TN (2015) Probable metal-insulator transition in Ag4SSe. J Alloys Compos 622:236–242CrossRefGoogle Scholar
  16. Franklin J, Kissin S, Smyk M, Scott S (1986) Silver deposits associated with the Proterozoic rocks of the Thunder Bay District, Ontario. Can J Earth Sci 23:1576–1591CrossRefGoogle Scholar
  17. Frigstad OF (1972) Naumannite from Kongsberg silver deposit, south Norway. Contribution to the mineralogy of Norway, No. 50. Nor Geol Tidsskr 52:273–285Google Scholar
  18. Gammon JB (1966) Fahlbands in the Precambrian of southern Norway. Econ Geol 61:174–188CrossRefGoogle Scholar
  19. Genth FA (1891) Contributions to mineralogy, No. 51. Am J Sci Ser 3 41:401–403. CrossRefGoogle Scholar
  20. Genth FA (1892) Contributions to mineralogy; No. 54. With crystallographic notes by S. L. Penfield. Am J Sci Ser 3 44:381–389. CrossRefGoogle Scholar
  21. Goldschmidt VM (1954) Geochemistry. Oxford University Press, London, 730 ppGoogle Scholar
  22. Goldschmidt VM, Hefter O (1933) Zur Geochemie des Selens. Nachr Ges Wiss Göttingen. Math-Physik Kl 1 H 2:245–252Google Scholar
  23. Hammer Ø, Svensen HH (2017) Biostratigraphy and carbon and nitrogen geochemistry of the SPICE event in Cambrian low-grade metamorphic black shale, Southern Norway. Palaeogeogr Palaeoclim Palaeoecol 468:216–227CrossRefGoogle Scholar
  24. Heier K (1953) Clausthalite and selenium-bearing galena in Norway. Nor Geol Tidsskr 32:228–231Google Scholar
  25. Ihlen PM, Ineson PR, Mitchell JG, Vokes FM (1984) K-Ar dating of dolerite dykes in the Kongsberg-Fiskum district, Norway, and their relationship with the silver and base metal veins. Nor Geol Tidsskr 64:87–96Google Scholar
  26. Ineson PR, Mitchell JG, Vokes FM (1975) K-Ar dating of epigenetic mineral deposits: an investigation of the Permian metallogenic province of the Oslo Region, southern Norway. Econ Geol 70:1426–1436CrossRefGoogle Scholar
  27. Jacobsen SB, Heier KS (1978) Rb-Sr isotope systematics inmetamorphic rocks, Kongsberg sector, south Norway. Lithos 11:257–276CrossRefGoogle Scholar
  28. Ji C, Zhang Y, Zhang X, Wang P, Shen H, Gao W, Wang Y, Yu WW (2017) Synthesis and characterization of Ag2SxSe1 – x nanocrystals and their photoelectrochemical property. Nanotechnology 28:6Google Scholar
  29. Karakaya I, Thompson WT (1990) The Ag–Se (Silver–Selenium) system. Bull Alloy Phase Diagr 11:266–271CrossRefGoogle Scholar
  30. Kissin SA (1992) Five-element (Ni–Co–As–Ag–Bi) veins. Geosci Can 19:113–124Google Scholar
  31. Kotková J, Kullerud K, Šrein V, Drábek M, Škoda R (2018) The Kongsberg silver deposits, Norway: Ag–Hg–Sb mineralization and constraints for the formation of the deposits. Miner Depos Google Scholar
  32. Krivovichev VG, Charykova MV, Vishnevsky AV (2017) The thermodynamics of selenium minerals in near-surface environments. Minerals. Google Scholar
  33. Lipp U, Flach S (2003) Wismut-, Kobalt-, Nickel- und Silbererze im Nordteil des Schneeberger Lagerstättenbezirkes. Bergbau in Sachsen 10:1–210Google Scholar
  34. Markl G, Burisch M, Neumann U (2016) Natural fracking and the genesis of five-element veins. Miner Depos 51:703–712CrossRefGoogle Scholar
  35. Márquez-Zavalía MF, Bindi L, Márquez M, Menchetti S (2008) Se-bearing polybasite-Tac from the Martha mine, Macizo del Deseado, Santa Cruz, Argentina. Mineral Petrol 94:145–150CrossRefGoogle Scholar
  36. Misra K (2000) Understanding mineral deposits. Springer, New York 845 ppCrossRefGoogle Scholar
  37. Moore CR (1979) Geology and mineralization of the former Broken Hills gold mine, Hikuai, Coromandel, New Zealand. N Z J Geol Geophys 22:339–351CrossRefGoogle Scholar
  38. Neumann H (1944) Silver deposits at Kongsberg. Norges Geol Unders 162:133Google Scholar
  39. Ondruš P, Veselovský F, Gabašová A, Drábek M, Dobeš P, Malý K, Hloušek J, Sejkora J (2003) Ore-forming processes and mineral parageneses of the Jáchymov ore district. J Czech Geol Soc 48:157–192Google Scholar
  40. Øyvik M (1997) Structural development of the silver mines at Kongsberg (in Norwegian). Cand Scient thesis, Univ of OsloGoogle Scholar
  41. Pal’yanova GA, Chudnenko KV, Zhuravkova TV (2014) Thermodynamic properties of solid solutions in the system Ag2S–Ag2Se. Thermochim Acta 575:90–96CrossRefGoogle Scholar
  42. Pal’yanova GA, Kravtsova RG, Zhuravkova TV (2015) Ag2(S,Se) solid solutions in the ores of the Rogovik gold–silver deposit (northeastern Russia). Russ Geol Geophys 56:1738–1748CrossRefGoogle Scholar
  43. Petruk W, Owens DR, Stewart JM, Murray EJ (1974) Observations on acanthite, aguilarite and naumannite. Can Mineral 12:365–369Google Scholar
  44. Pingitore NE, Ponce BF, Moreno F, Podpora C (1992) Solid solutions in the system Ag2S–Ag2Se. J Mater Res 7:2219–2224CrossRefGoogle Scholar
  45. Pingitore NE, Ponce BF, Estrada L, Eastman MP, Yuan HL, Porter LC, Estrada G (1993) Calorimetric analysis of the system Ag2S–Ag2Se between 25 and 250 °C. J Mater Res 8:3126–3130CrossRefGoogle Scholar
  46. Ramdohr P (1969) The ore minerals and their intergrowths. Pergamon, New York, 1174 ppGoogle Scholar
  47. Robie RA, Bethke PM, Toulmin MS, Edwards JL (1966) X-ray crystallographic data, densities, and molar volumes of minerals. Geol Soc Amer Memoir 97:27–74CrossRefGoogle Scholar
  48. Rosana MF, Matsueda H (2002) Cikidang hydrothermal gold deposit in Western Java, Indonesia. Resour Geol 52:341–352CrossRefGoogle Scholar
  49. Rose G (1828) Über ein neues Selenerz vom Harz. Poggendorffs Annalen der Physik Chemie 14:471–473CrossRefGoogle Scholar
  50. Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A 32(5):751–767CrossRefGoogle Scholar
  51. Shikazono N (1978) Selenium content of acanthite and the chemical environments of Japanese vein-type deposits. Econ Geol 73:524–533CrossRefGoogle Scholar
  52. Škácha P, Sejkora J, Plášil J (2017) Selenide Mineralization in the Příbram Uranium and Base-Metal District (Czech Republic). Minerals Google Scholar
  53. Stanton RL (1972) Ore petrology. McGraw-Hill, New York, pp 713Google Scholar
  54. Starmer IC (1985) The evolution of the south Norwegian Proterozoic as revealed by the major and mega-tectonics of the Kongsberg and Bamle sectors. In: Tobi AC, Touret JLT (eds) The deep Proterozoic crust in the North Atlantic Provinces. Reidel, Dordrecht, pp 259–290CrossRefGoogle Scholar
  55. Staude S, Wagner T, Markl G (2007) Mineralogy, mineral compositions and fluid evolution at the Wenzel hydrothermal deposit, southern Germany: implications for the formation of Kongsberg-type silver deposits. Can Mineral 45:1147–1176CrossRefGoogle Scholar
  56. Staude S, Werner W, Mordhorst T, Wemmer K, Jacob DE, Markl G (2012) Multi-stage Ag–Bi–Co–Ni–U and Cu–Bi vein mineralization at Wittichen, Schwarzwald, SW Germany: geological setting, ore mineralogy, and fluid evolution. Miner Depos 47:251–276CrossRefGoogle Scholar
  57. Torgersen E, Viola G, Zwingmann H, Henderson IHC (2015) Inclined K– Ar illite age spectra in brittle fault gouges: effects of fault reactivation and wall-rock contamination. Terra Nova 27:106–113CrossRefGoogle Scholar
  58. Vaughan DJ, Craig JR (1978) Mineral chemistry of metal sulfides. Cambridge University Press, Cambridge, pp 493Google Scholar
  59. Viola G, Bingen B, Solli A (2016) Bedrock map: Kongsberg lithotectonic unit, Kongsberg–Modum–Hønefoss Scale 1: 100 000. Nor Geol UndersGoogle Scholar
  60. Warmada IW, Lehmann B, Simandjuntak M (2003) Polymetallic sulfides and sulfosalts of the Pongkor epithermal gold–silver deposit, West Java, Indonesia. Can Mineral 41:185–200CrossRefGoogle Scholar
  61. Wilkerson G, Deng QP, Llavona R, Goodell P (1988) The Batopilas mining district, Chihuahua, Mexico. Econ Geol 83:1721–1736CrossRefGoogle Scholar
  62. Xiao C, Xu J, Li K, Feng J, Yang J, Xie Y (2012) Superionic phase transition in silver chalcogenide nanocrystals realizing optimized thermoelectric performance. J Am Chem Soc 134:4287–4293CrossRefGoogle Scholar
  63. Yamamoto Y (1976) Relationship between Se/S and sulfur isotope ratios of hydrothermal sulfide minerals. Miner Depos 11:197–209CrossRefGoogle Scholar
  64. Zhuravkova TV, Palyanova GA, Kravtsova RG (2015) Physicochemical formation conditions of silver sulfoselenides at the Rogovik deposit, Northeastern Russia. Geol Ore Depos 57:313–330CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Norwegian Mining MuseumKongsbergNorway
  2. 2.Czech Geological SurveyPrague 1Czech Republic

Personalised recommendations