Home Physical Sciences Physicochemical controls on bismuth mineralization: An example from Moutoulas, Serifos Island, Cyclades, Greece
Article
Licensed
Unlicensed Requires Authentication

Physicochemical controls on bismuth mineralization: An example from Moutoulas, Serifos Island, Cyclades, Greece

  • Michalis Fitros EMAIL logo , Stylianos F. Tombros , Anthony E. Williams-Jones , Basilios Tsikouras , Eleni Koutsopoulou and Konstantin Hatzipanagiotou
Published/Copyright: July 31, 2017
Become an author with De Gruyter Brill
Author Information
American Mineralogist
From the journal American Mineralogist Volume 102 Issue 8

Abstract

The 11.6 to 9.5 Ma Serifos pluton intruded schists and marbles of the Cycladic Blueschist unit, causing thermal metamorphism, the development of magnetite Ca-exo- and endo-skarns and the formation of low-temperature vein and carbonate-replacement ores. Potentially, the most important ores occur in the Moutoulas prospect where the mineralization in retrograde skarn and quartz veins culminated with the deposition of native bismuth. A combination of fluid inclusion microthermometry and isotope geothermometry suggests that the Moutoulas mineralization formed at a hydrostatic pressure of ~100 bars, from moderate-to-low temperature (~190–250 °C), and low-salinity (1.3–5.6 wt% NaCl equivalent) fluids. The calculated δ34SH2S compositions are consistent with the ore fluids having been derived from the Serifos pluton. Bismuth mineralization is interpreted to have occurred as a result of wall-rock interaction and mixing of a Bi-bearing ore fluid with meteoric waters. Native bismuth and bismuthinite deposited at ~200 °C, near neutral pH (6.5), low fS2 (<–16.5), and low fO2(<–44). Supergene alteration in Serifos led to the oxidation of native bismuth to bismite and bismutite.

Keywords: Native bismuth; retrograde skarn; supergene alteration; Moutoulas; Serifos

Special collection papers can be found online at http://www.minsocam.org/MSA/AmMin/special-collections.html.

Acknowledgments

We kindly thank D. Katsikis for his assistance with sampling in the Moutoulas mine. Critical comments from J. Mavrogenes, P. Voudouris, and the Associate Editor J. Roberge, as well as an anonymous reviewer, are gratefully acknowledged.

References cited

Afifi, A.M., Kelly, W.C., and Essene, E.J. (1988) Phase relations among tellurides, sulfides, and oxides: I. Thermochemical data and calculated equilibria. Economic Geology, 83, 377–294.10.2113/gsecongeo.83.2.377Search in Google Scholar

Altherr, R., Kreuzer, H., Wendt, I., Lenz, H., Wagner, G.A., Keller, J., Harre, W., and Hohndorf, A. (1982) A late Oligocene/Early Miocene high temperature belt in the Attico-Cycladic crystalline complex (SE Pelagonia, Greece). Geologisches Jahrbuch, 23, 971–164.Search in Google Scholar

Arnórsson, S., and Gunnlaugsson, E. (1985) New gas geothermometers for geothermal exploration-Calibration and application. Geochimica and Cosmochimica Acta, 49, 1307–1325.10.1016/0016-7037(85)90283-2Search in Google Scholar

Bakker, R.J. (2012) Package FLUIDS. Part 4: Thermodynamic modelling and purely empirical equations for H2O-NaCl-KCl solutions. Mineralogy and Petrology, 105, 1–29.10.1007/s00710-012-0192-zSearch in Google Scholar

Barton, P.B. Jr., and Skinner, B.J. (1979) Sulfide mineral stabilities. In H.L. Barnes, Ed., Geochemistry of the Hydrothermal Ore Deposits, 3rd ed., p. 236–333. Wiley, New York.Search in Google Scholar

Beaudoin, G., and Therrien, P. (2009) The updated web stable isotope fractionation calculator. In P.A. De Groot, Ed., Handbook of Stable Isotope Analytical Techniques, Volume II, Elsevier, 1120–1122.Search in Google Scholar

Bolhar, R., Ring, U., and Allen, C.M. (2010) An integrated zircon geochronological and geochemical investigation into the Miocene plutonic evolution of the Cyclades, Aegean Sea, Greece: Part 1: Geochronology. Contributions to Mineralogy and Petrology, 160, 719–742.10.1007/s00410-010-0504-4Search in Google Scholar

Brichau, S., Thomson, S.N., and Ring, U. (2010) Thermochronometric constraints on the tectonic evolution of the Serifos detachment, Aegean Sea, Greece. International Journal of Earth Sciences, 99, 379–393, 10.1007/s00531-008-0386-0.Search in Google Scholar

Bröcker, M., and Franz, L. (2005) P-T conditions and timing of metamorphism at the base of the Cycladic Blueschist unit, Greece: The Panormos window on Tinos re-visited. Neues Jahrbuch für Mineralogie Abhandlungen, 181, 91–93.Search in Google Scholar

Brown, P.E. (1989) FLINCOR: A microcomputer program for the reduction and investigation of fluid inclusion data. American Mineralogist, 74, 1390–1393.Search in Google Scholar

Chalkias, S., and Vavelidis, M. (1998) Interpretation of lead-isotope data from Greek Pb-Zn deposits, based on an empirical two-stage model. Bulletin of Geological Society of Greece, 23, 177–193.Search in Google Scholar

Cook, N.J., Ciobanu, C.L., Spry, P.G., Voudouris, P., and the participants of the IGCP-486 (2009) Understanding gold-(silver)-telluride-(selenide) mineral deposits. Episodes, 32, 249–263.10.18814/epiiugs/2009/v32i4/002Search in Google Scholar

Dhamelincourt, P., Beny, J.M., Dubessy, J., and Poty, B. (1979) Analyse d’ inclusions fluids à la microsonde mole à effet Raman. Bulletin Mineralogie, 102, 600–610.10.3406/bulmi.1979.7309Search in Google Scholar

Ducoux, M., Branquet, Y., Jolivet, L., Arbaret, L., Grasemann, B., Rabillard, A., Gumiaux, C., and Drufin, S. (2017) Synkinematic skarns and fluid drainage along detachments: The West Cycladic Detachment System on Serifos Island (Cyclades, Greece) and its related mineralization. Tectonophysics, 695, 1–26.10.1016/j.tecto.2016.12.008Search in Google Scholar

Etschmann, B.E., Liu, W., Pring, A., Grundler, P. V., Tooth, B., Borg, S., Testemale, D., Brewe, D., and Brugger, J. (2016) The role of Te(IV) and Bi(III) chloride complexes in hydrothermal mass transfer: an X-ray absorption spectroscopic study. Chemical Geology, 425, 37–51.10.1016/j.chemgeo.2016.01.015Search in Google Scholar

Fournier, R.O., and Truesdell, A.H. (1973) An empirical Na-K-Ca geothermometer for natural waters. Geochimica et Cosmochimica Acta, 37, 1255–1275.10.1016/0016-7037(73)90060-4Search in Google Scholar

Frezzotti, M.L., Tecce, F., and Casagli, A. (2012) Raman spectroscopy for fluid inclusion analysis. Journal of Geochemical Exploration, 112, 1–20.10.1016/j.gexplo.2011.09.009Search in Google Scholar

Fritz, P., Drimmie, R.J., and Norwick, K. (1974) Preparation of sulfur dioxide for mass spectrometer analysis by combustion of sulfide with copper oxide. Analytical Chemistry, 76, 164–166.10.1021/ac60337a044Search in Google Scholar

Grasemann, B., and Petrakakis, K. (2007) Evolution of the Serifos metamorphic complex. In G. Lister, M. Forster, and U. Ring, Eds., Inside the Aegean Metamorphic Core Complexes. Journal of the Virtual Explorer, 28, 1–18.Search in Google Scholar

Grasemann, B., Schneider, D.A., Stockli, D.F., and Iglseder, C. (2012) Miocene bivergent crustal extension in the Aegean: Evidence from the western Cyclades (Greece). Lithosphere, 4(1), 23–39, 10.1130/L164.1.Search in Google Scholar

Helgeson, H.C., Kirkham, D.H., and Flowers, G.C. (1981) Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures, Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600 °C and 5kb. American Journal of Science, 281, 1249–1516.10.2475/ajs.281.10.1249Search in Google Scholar

Henley, R.W., Mavrogenes, J.A., and Tanner, D. (2012) Sulfosalt melts and heavy metal (As-Sb-Bi-Sn-Pb-Tl) fractionation during volcanic gas expansion: the El Indio (Chile) paleo-fumarole. Geofluids, 10.1111/j.1468-8123.2011.00357.x.Search in Google Scholar

Johnson, J.W., Oelkers, E.H., and Helgeson, H.C. (1992) SUPCRT92, A software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species and reactions from 1 to 5000 bars and 0 to 1000 °C. Computer Geoscience, 18, 899–947.10.1016/0098-3004(92)90029-QSearch in Google Scholar

Kołodziejczyk, J., Pršek, J., Melfos, V., Voudouris, P., Maliqi, F., and Kozub-Budzyń G. (2015) Bismuth minerals from the Stan Terg deposit (Trepça, Kosovo). Mineralogical contribution to the evolution of the deposit. Neues Jahrbuch für Mineralogie, 192, 317–333.10.1127/njma/2015/0288Search in Google Scholar

Li, Y., and Liu, J. (2006) Calculation of sulfur isotope fractionation in sulfides. Geochimica et Cosmochimica Acta, 70, 1789–1795.10.1016/j.gca.2005.12.015Search in Google Scholar

Mavrogenes, J.A., Henley, R.W., Reyes, A.C., and Berger, B. (2010) Sulfosalt melts: evidence of high temperature vapor transport of metals in the formation of high sulfidation lode gold deposits. Economic Geology, 105, 257–262.10.2113/gsecongeo.105.2.257Search in Google Scholar

McCartney, R.A., and Lanyon, G.W. (1989) Calculations of steam fractions in vapor-dominated geothermal systems using an empirical method. In l4th Annual Workshop on Geothermal Reservoir Engineering, Stanford, 155–161.Search in Google Scholar

Nehring, N.L., and D’Amore, F. (1984) Gas chemistry and thermometry of the Cerro Prieto, Mexico, geothermal field. Geothermics, 13, 75–89.10.1016/0375-6505(84)90008-7Search in Google Scholar

Ohmoto, H., and Lasaga, A.C. (1982) Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems. Geochimica et Cosmochimica Acta, 46, 1727–1745.10.1016/0016-7037(82)90113-2Search in Google Scholar

Ohmoto, H., and Rye, R.O. (1979) Isotopes of sulfur and carbon. In H.L. Barnes, Ed., Geochemistry of the Hydrothermal Ore Deposits, 3rd ed., 509–567. Wiley, New York.Search in Google Scholar

Pearce, J.A., Czernichowski-Lauriol, I., Lombardi, S., Brune, S., Nador, A., Baker, J., Pauwels, H., Hatziyannis, G., Beaubien, S., and Faber, E. (2004) A review of natural CO2 accumulations in Europe as analogues for geological sequestration. Geological Society, London, Special Publication, 233, 29–41.10.1144/GSL.SP.2004.233.01.04Search in Google Scholar

Petrakakis, K., Zamoyli, A., Iglseder, C., Rambousek, C., Grasemann, B., Dragamits, E., and Photiadis, A. (2007) Geological map of Serifos. 1:50.000. Geological map of Greece, Institute of Geological and Mineralogical Exploration, Athens, Greece.Search in Google Scholar

Rabillard, A., Arbaret, L., Jolivet, L., Le Breton, N., Gumiaux, C., Augier, R., and Grasemann, B. (2015) Interactions between plutonism and detachments during metamorphic core complex formation, Serifos Island (Cyclades, Greece). Tectonics, 34, 1080–1106, 10.1002/2014TC003650.Search in Google Scholar

Roedder, E. (1984) Fluid inclusions. Reviews in Mineralogy, 12, 550.10.1515/9781501508271Search in Google Scholar

Salemink, J. (1985) Skarn and ore formation at Serifos, Greece as a consequence of granodiorite intrusion, 232 p. Ph.D. thesis, Geology Ultraiectina.Search in Google Scholar

Seymour, K., Zouzias, D., Tombros, S.F., and Kolaiti, E. (2009) The geochemistry of the Serifos pluton and associated iron oxide and base metal sulphide ores: Skarn or metamorphosed exhalite deposits? Neues Jahrbuch für Mineralogie Abhandlungen, 186, 249–270, 10.1127/0077-7757/2009/0143.Search in Google Scholar

Shock, E.T., and Helgeson, H.C. (1998) Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures, Correlation algorithms for ionic species and equation of state prediction to 5 kb and 1000 °C. Geochimica et Cosmochimica Acta, 52, 2009–2036.10.1016/0016-7037(88)90181-0Search in Google Scholar

Simon, G., and Essene, E.J. (1996) Phase relations among selenides, sulfides, tellurides, and oxides: I. Thermodynamic properties and calculated equilibria. Economic Geology, 91, 1183–1208.10.2113/gsecongeo.91.7.1183Search in Google Scholar

Skirrow, R.G., and Walshem, J.L. (2002) Reduced and oxidized Au-Cu-Bi iron oxide deposits of the Tennant Creek Inlier, Australia: an integrated geologic model. Economic Geology, 97, 1167–1202.10.2113/gsecongeo.97.6.1167Search in Google Scholar

Staude, S., Werner, W., Mordhorst, T., Wemmer, K., Jacob, D.E., and 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. Mineralium Deposita, 47, 251–276, 10.1007/s00126-011-0365-4.Search in Google Scholar

Stos-Gale, A.Z. (1992) Application of lead isotope analysis to provenance studies in archaeology, 303 p. Ph.D. thesis, University of Oxford.Search in Google Scholar

Stouraiti, C., and Mitropoulos, P. (1999) Variation in amphibole composition from the Serifos intrusive complex (Greece), under magmatic and hydrothermal alteration conditions. An application of hornblende geobarometry. Bulletin of Geological Society of Greece, 33, 39–50.Search in Google Scholar

Tooth, B., Brugger, J., Ciobanu, C., and Liu, W. (2008) Modeling of gold scavenging by bismuth melts coexisting with hydrothermal fluids. Geology, 36, 815–818.10.1130/G25093A.1Search in Google Scholar

Tooth, B., Ciobanu, C.L., Green, L., O’Neill, B., and Brugger, J. (2011) Bi-melt formation and gold scavenging from hydrothermal fluids: an experimental study. Geochimica et Cosmochimica Acta, 75, 5423–5443.10.1016/j.gca.2011.07.020Search in Google Scholar

Voudouris, P., Spry, P.G., Melfos, V., and Alfieris, D. (2007) Tellurides and bismuth sulfosalts in gold occurrences of Greece: mineralogy and genetic considerations. Geological Survey of Finland Guide, 53, 85–94.Search in Google Scholar

Voudouris, P., Melfos, V., Spry, P.G., Bonsall, T., Tarkian, M., and Economou-Eliopoulos, M. (2008a) Mineralogy and fluid inclusion constraints on the evolution of the Plaka intrusion-related ore system, Lavrion, Greece. Mineralogy and Petrology, 93, 79–110.10.1007/s00710-007-0218-0Search in Google Scholar

Voudouris, P., Melfos, V., Spry, P.G., Bonsall, T., Tarkian, M., and Solomos, C. (2008b) Carbonate-replacement Pb-Zn-Ag±Au mineralization in the Kamariza area, Lavrion, Greece: Mineralogy and thermochemical conditions of formation. Mineralogy and Petrology, 94, 85–106.10.1007/s00710-008-0007-4Search in Google Scholar

Xypolias, P., Iliopoulos, I., Chatzaras, V., and Kokkalas, S. (2012) Subduction and exhumation related structures in the Cycladic Blueschists: insights from Evia Island (Aegean region, Greece). Tectonics, 31, TC2001, 10.1029/2011TC002946.Search in Google Scholar

Yardley, B.W.D., Banks, D.A., and Bottrell, S.H. (1993) Post-metamorphic gold-quartz veins from N.W. Italy: the composition and origin of the ore fluid. Mineralogical Magazine, 57, 407–422.10.1180/minmag.1993.057.388.05Search in Google Scholar

Yuan, H., Chen, K., Zhian, B., Zong, C., Dai, M., Fan, C., and Yin, C. (2013) Determination of lead isotope compositions of geological samples using femtosecond laser ablation MC-ICPMS. Chinese Science Bulletin, 58, 3914–3921.10.1007/s11434-013-5804-4Search in Google Scholar

Zartman, R.E., and Doe, B.R. (1981) Plumbotectonics. The Model. Tectonophysics, 75, 135–162.10.1016/0040-1951(81)90213-4Search in Google Scholar

Zhou, H., Sun, X., Fu, Y., Lin, H., and Jiang, L. (2016) Mineralogy and mineral chemistry of Bi-minerals: Constraints on ore genesis of the Beiya giant porphyryskarn gold deposit, southwestern China. Ore Geology Reviews, 79, 408–424.10.1016/j.oregeorev.2016.06.008Search in Google Scholar

Received: 2017-3-1
Accepted: 2017-4-28
Published Online: 2017-7-31
Published in Print: 2017-8-28

© 2017 by Walter de Gruyter Berlin/Boston

Articles in the same Issue

  2. How many boron minerals occur in Earth’s upper crust?
  3. Outlooks in Earth and Planetary Materials
  4. Network analysis of mineralogical systems
  5. Special collection: From magmas to ore deposits
  6. Geochemistry of the Cretaceous Kaskanak Batholith and genesis of the Pebble porphyry Cu-Au-Mo deposit, Southwest Alaska
  7. Special collection: From magmas to ore deposits
  8. Physicochemical controls on bismuth mineralization: An example from Moutoulas, Serifos Island, Cyclades, Greece
  9. Special collection: Earth analogs for martian geological materials and processes
  10. Geochemistry and mineralogy of a saprolite developed on Columbia River Basalt: Secondary clay formation, element leaching, and mass balance during weathering
  11. Special collection: Apatite: A common mineral, uncommonly versatile
  12. An ab-initio study of the energetics and geometry of sulfide, sulfite, and sulfate incorporation into apatite: The thermodynamic basis for using this system as an oxybarometer
  13. Special collection: Dynamics of magmatic processes
  14. The role of modifier cations in network cation coordination increases with pressure in aluminosilicate glasses and melts from 1 to 3 GPa
  16. Nitrides and carbonitrides from the lowermost mantle and their importance in the search for Earth’s “lost” nitrogen
  18. Accounting for the species-dependence of the 3500 cm−1 H2Ot infrared molar absorptivity coefficient: Implications for hydrated volcanic glasses
  20. A finite strain approach to thermal expansivity’s pressure dependence
  22. Ilmenite breakdown and rutile-titanite stability in metagranitoids: Natural observations and experimental results
  24. Single-crystal equations of state of magnesiowüstite at high pressures
  26. Analysis of erionites from volcaniclastic sedimentary rocks and possible implications for toxicological research
  28. Reconstructive phase transitions induced by temperature in gmelinite-Na zeolite
  30. Smoking gun for thallium geochemistry in volcanic arcs: Nataliyamalikite, TlI, a new thallium mineral from an active fumarole at Avacha Volcano, Kamchatka Peninsula, Russia
  32. How to facet gem-quality chrysoberyl: Clues from the relationship between color and pleochroism, with spectroscopic analysis and colorimetric parameters
  33. Letter
  34. Mn-Fe systematics in major planetary body reservoirs in the solar system and the positioning of the Angrite Parent Body: A crystal-chemical perspective
  35. Letter
  36. Dolomite-IV: Candidate structure for a carbonate in the Earth’s lower mantle
  37. Book Review
  38. Book Review
https://doi.org/10.2138/am-2017-6125
Keywords for this article
Native bismuth; retrograde skarn; supergene alteration; Moutoulas; Serifos

Articles in the same Issue

  2. How many boron minerals occur in Earth’s upper crust?
  3. Outlooks in Earth and Planetary Materials
  4. Network analysis of mineralogical systems
  5. Special collection: From magmas to ore deposits
  6. Geochemistry of the Cretaceous Kaskanak Batholith and genesis of the Pebble porphyry Cu-Au-Mo deposit, Southwest Alaska
  7. Special collection: From magmas to ore deposits
  8. Physicochemical controls on bismuth mineralization: An example from Moutoulas, Serifos Island, Cyclades, Greece
  9. Special collection: Earth analogs for martian geological materials and processes
  10. Geochemistry and mineralogy of a saprolite developed on Columbia River Basalt: Secondary clay formation, element leaching, and mass balance during weathering
  11. Special collection: Apatite: A common mineral, uncommonly versatile
  12. An ab-initio study of the energetics and geometry of sulfide, sulfite, and sulfate incorporation into apatite: The thermodynamic basis for using this system as an oxybarometer
  13. Special collection: Dynamics of magmatic processes
  14. The role of modifier cations in network cation coordination increases with pressure in aluminosilicate glasses and melts from 1 to 3 GPa
  16. Nitrides and carbonitrides from the lowermost mantle and their importance in the search for Earth’s “lost” nitrogen
  18. Accounting for the species-dependence of the 3500 cm−1 H2Ot infrared molar absorptivity coefficient: Implications for hydrated volcanic glasses
  20. A finite strain approach to thermal expansivity’s pressure dependence
  22. Ilmenite breakdown and rutile-titanite stability in metagranitoids: Natural observations and experimental results
  24. Single-crystal equations of state of magnesiowüstite at high pressures
  26. Analysis of erionites from volcaniclastic sedimentary rocks and possible implications for toxicological research
  28. Reconstructive phase transitions induced by temperature in gmelinite-Na zeolite
  30. Smoking gun for thallium geochemistry in volcanic arcs: Nataliyamalikite, TlI, a new thallium mineral from an active fumarole at Avacha Volcano, Kamchatka Peninsula, Russia
  32. How to facet gem-quality chrysoberyl: Clues from the relationship between color and pleochroism, with spectroscopic analysis and colorimetric parameters
  33. Letter
  34. Mn-Fe systematics in major planetary body reservoirs in the solar system and the positioning of the Angrite Parent Body: A crystal-chemical perspective
  35. Letter
  36. Dolomite-IV: Candidate structure for a carbonate in the Earth’s lower mantle
  37. Book Review
  38. Book Review
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2025 De Gruyter Brill
Downloaded on 14.12.2025 from https://www.degruyterbrill.com/document/doi/10.2138/am-2017-6125/html
Scroll to top button