Hostname: page-component-78c5997874-4rdpn Total loading time: 0 Render date: 2024-11-19T22:38:58.798Z Has data issue: false hasContentIssue false

Retrograde reactions involving galena and Ag-sulphosalts in a zoned ore deposit, Julcani, Peru

Published online by Cambridge University Press:  05 July 2018

R. O. Sack*
Affiliation:
Department of Earth & Space Sciences, Box 351310, University of Washington, Seattle, WA, 98195-1310, USA
P. C. Goodell
Affiliation:
Department of Geological Sciences, University of Texas, El Paso, TX 79968, USA
*

Abstract

The sulphide ores from the Julcani mining district (Peru) display many retrograde reactions that may be attributed to solid-state processes accompanying cooling. Fahlores [˜(Cu,Ag)10(Zn,Fe)2(Sb,As)4S13] from the Herminia mine exhibit pronounced downstream enrichments in molar Ag/(Ag+Cu) ratios that are strongly correlated with the abundance of PbS-AgSbS2-AgBiS2 phases. These correlations, discontinuous core to rim Sb/(Sb+As) enrichments in bournonites, and prominent reaction textures involving fahlores, bournonites and galenas provide strong evidence that the fahlores in these ores have been enriched in Ag by the Ag–Cu exchange reaction

which occurred during cooling following mineralization of a PbS-AgSbS2-AgBiS2 galena and has been documented elsewhere. Secondary PbS-AgSbS2-AgBiS2 minerals aramayoite, bismuthian diaphorite [Pb2Ag3(Bi,Sb)3S8], and diaphorite were produced from primary galenas with cooling of ores with high Pb/Cu and Bi/Sb; pyrargyrite formed from the breakdown of the Ag10Zn2Sb4S13 component in the most Ag-rich fahlores, as an exsolution product of galena, and from replacement of aramayoite and galena with the evolution of semimetal sulphides. Based on mineral compositions, phase equilibria, a thermochemical database for sulphides and sulphosalts, and the reintegrated composition for primary grains of Ag-rich PbS-AgSbS2-AgBiS2 phases, we estimate that the primary temperature of hydrothermal mineralization was >320±10°C, that these reactions ceased to affect fahlore Ag/(Ag+Cu) ratios and Bi/(Bi+Sb) ratios of aramayoite and miargyrite after cooling through 220±10°C. Galenas, however, appear to have continued to adjust their compositions to reflect even lower temperatures by continued exsolution of semimetals and production a diverse suite of sulphosalts that occur in fine intergrowths with galena.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2002

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Amcoff, O. (1976) The solubility of silver and antimony in galena. Neues Jahrbuch für Mineralogie Monatshefte, 247261.Google Scholar
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (1990) Handbook of Mineralogy: Volume I. Elements, Sulfides, Sulfosalts. Mineral Data Publishing, Tuscon, AZ, USA.Google Scholar
Arribas, A. Jr., (1995) Characteristics of high-sulfidation epithermal deposits, and their relation to magmatic fluid. Pp. 419454 in: Magmas, Fluids, and Ore Deposits (Thompson, J.F.H., editor). Short Course Volume 23, Mineralogical Association of Canada.Google Scholar
Balabin, A.I. and Sack, R.O. (2000) Thermodynamics of (Zn,Fe)S sphalerite: a CVM approach with large basis clusters. Mineral ogical Magazine 64, 923943.CrossRefGoogle Scholar
Borodayev, Y.S., Nenasheva, S.N., Gamyanin, G.N. and Mozgova, N.N. (1986) First find of aramayoite–galena–matildite exsolution textures. Doklady Akademii Nauk SSSR, 290, 192195.Google Scholar
Chang, L.L.Y., Knowles, C.R. and Chen, T.T. (1977) Phase relations in the systems Ag2S–Sb2S3–Bi2S3, Ag2S–As2S3–Sb2S3 and Ag2S–As2S3–Bi2S3 . Memoirs of the Geological Society of China, 2, 229237.Google Scholar
Chang, L.L.Y., Wu, D. and Knowles, C.R. (1988) Phase relations in the system Ag2S–Cu2S–PbS–Bi2S3 . Economic Geology, 83, 405418.CrossRefGoogle Scholar
Charlat, M. and Levy, C. (1974) Substitutions multiples dans la série tennantite–tetrahedrite. Bulletin Societé francais Minéralogie et Cristallographie, 97, 241250.CrossRefGoogle Scholar
Charnock, J.M., Garner, C.D., Pattrick, R.A.D. and Vaughan, D.J. (1989) EXAFS and Mössbauer spectroscopic study of Fe-bearing tetrahedrites. Mineralogical Magazine, 53, 193199.CrossRefGoogle Scholar
Ciobanu, C.L., Cook, N.J., Topa, D.K., Bogdanov, K. and Merkle, R.K.W. (2002) Compositional variance in the cuprobismutite series and related (Pb-bearing) paderaite; insights from new occurrences. IMA 18th General Meeting, Edinburgh, UK, Programme with Abstracts, p. 264.Google Scholar
Deen, J.A. (1990) Hydrothermal ore deposition related to high-level igneous activity: A stable isotopic study of the Julcani mining district, Peru. PhD thesis, University of Colorado, Boulder, CO, USA.Google Scholar
Deen, J.A., Rye, R.O., Munoz, J.L. and Drexler, J.W. (1994) The magmatic hydrothermal system at Julcani, Peru: evidence from fluid inclusions and hydrogen and oxygen isotopes. Economic Geology, 89, 19241938.CrossRefGoogle Scholar
Ebel, D.S. (1993) Thermochemistry of fahlore (tetrahedrite) and biotite mineral solutions. PhD thesis, Purdue University, Indiana, USA.Google Scholar
Ebel, D.S. and Sack, R.O. (1991) As-Ag incompatibility in fahlore. Mineralogical Magazine, 55, 521528.CrossRefGoogle Scholar
Effenberger, H., Paar, W.H., Topa, D., Criddle, A.J. and Fleck, M. (2002) The new mineral baumstarkite and a structural reinvestigation of aramayoite and miargyrite. American Mineralogist, 87, 753764.CrossRefGoogle Scholar
Feiss, G.P. (1970) Arsenic and antimony partitioning between the tetrahedrite-tennantite and enargitefamatinite series. PhD thesis, Harvard University, Cambridge, MA, USA.Google Scholar
Foord, E.E., Shawe, D.R. and Conklin, N.N. (1988) Coexisting galena, PbS and sulfosalts: Evidence for multiple episodes of mineralization in the Round Mountain and Manhattan gold districts, Nevada. The Canadian Mineralogist, 26, 355376.Google Scholar
Gaines, R.V., Skinner, H.K., Foord, E.E., Mason, B., Rosenzweig, A., King, V.T. and Dowty, E. (1997) Dana's New Mineralogy. John Wiley & Sons, Inc., New York, USA.Google Scholar
Gemmell, J.B. (1987) Geochemistry of metallic trace elements in fumarolic condensates from Nicaraguan and Costa Rican volcanoes. Journal of Volcanological and Geothermal Research, 33, 161181.CrossRefGoogle Scholar
Ghosal, S. and Sack, R.O. (1995) As-Sb energetics in argentian sulfosalts. Geochimica et Cosmochimica Acta, 59, 35733579.CrossRefGoogle Scholar
Ghosal, S. and Sack, R.O. (1999) Bi-Sb energetics in sulfosalts and sulfides. Mineralogical Magazine, 63, 723733.CrossRefGoogle Scholar
Goodell, P.C. (1970) Zoning and paragenesis in the Julcani district, Peru. PhD thesis, Harvard University, Cambridge, MA, USA.Google Scholar
Goodell, P.C. (1974) A typical sulfosalt environment: The mineralogy of the Julcani district, Peru. Mineralogical Record, 5, 215221.Google Scholar
Goodell, P.C. (1975) Binary and ternary sulphosalt assemblages in the Cu2S-Ag2S-PbS-As2S3-Sb2S3- Bi2S3 system. The Canadian Mineralogist, 13, 2742.Google Scholar
Goodell, P.C. and Petersen, U. (1974) Julcani mining district, Peru: a study of metal ratios. Economic Geology, 69, 347361.CrossRefGoogle Scholar
Graham, A.R. (1951) Matildite, aramayoite, miargyrite. American Mineralogist, 36, 436449.Google Scholar
Hackbarth, C.J. and Petersen, U. (1984) Systematic compositional variations in argentian tetrahedrite. Economic Geology, 79, 448460.CrossRefGoogle Scholar
Hall, W.E. and Czamanske, G.K. (1972) Mineralogy and trace-element content of the Wood River lead-silver deposit, Blaine County, Idaho. Economic Geology, 67, 350361.CrossRefGoogle Scholar
Harlov, D.E. and Sack, R.O. (1994) Thermochemistry of polybasite–pearceite solutions. Geochimica et Cosmochimica Acta, 58, 43634375.CrossRefGoogle Scholar
Harris, D.C. and Chen, T.T. (1976) Crystal chemistry and re-examination of nomenclature of sulfosalts in the aikinite–bismuthinite series. The Canadian Mineralogist, 14, 194205.Google Scholar
Hoda, S.N. and Chang, L.L.Y. (1975) Phase relations in the system PbS–Ag2S–Sb2S3 and PbS–Ag2S–Bi2S3 . American Mineralogist, 60, 621633.Google Scholar
Korzhinskii, D.S. (1970) Theory of Metasomatic Zoning (translated by Agrell, J.). Oxford University Press, Oxford, UK.Google Scholar
Lueth, V.W. (1988) Studies of the geochemistry of the semimetal elements: arsenic, antimony, and bismuth. PhD thesis, University of Texas, El Paso, TX, USA.Google Scholar
Lueth, V.W., Goodell, P.C. and Pingitore, N.E. (1990) Encoding the evolution of an ore system in bismuthinite–stibnite compositions. Economic Geology, 85, 14621472.CrossRefGoogle Scholar
Lueth, V.W., Megaw, P.K.M., Pingatore, N.E. and Goodell, P.C. (2000) Systematic variation in galena solid solution at Santa Eulalia, Chihuahua, Mexico. Economic Geology, 95, 16731687.Google Scholar
Makovicky, E. (1989) Modular Classification of sulphosalts – current status, definition and application of homologous series. Neues Jahrbuch für Mineralogie Abhandlungen, 160, 269297.Google Scholar
Makovicky, E. and Karup-Møller, S. (1994) Exploratory studies on substitution of minor elements in synthetic tetrahedrite Part I. Substitution by Fe, Zn, Co, Ni, Mn, Cr, V, and Pb. Unit-cell parameter changes on substitution and the structural role of “Cu2+. Neues Jahrbuch für Mineralogie Abhandlungen, 167, 247261.Google Scholar
Makovicky, E. and Skinner, B.J. (1978) Studies of the sulfosalts of copper. VI. Low temperature exsolution in synthetic tetrahedrite solid solution, Cu12+xSb4+yS13 . The Canadian Mineralogist, 16, 611623.Google Scholar
Makovicky, E. and Skinner, B.J. (1979) Studies of the sulfosalts of copper. VII. Crystal structures of the exsolution products Cu12.3Sb4S13 and Cu13.3Sb4S13 of unsubstituted synthetic tetrahedrite. The Canadian Mineralogist, 17, 619634.Google Scholar
Makovicky, E., Forcher, K., Lottermoser, W. and Amthauer, G. (1990) The role of Fe2+ and Fe3+ in synthetic Fe–substituted tetrahedrite. Mineralogy and Petrology, 43, 7381.CrossRefGoogle Scholar
Noble, D.C. and McKee, E.H. (1999) The Miocene metallogenic belt of central and northern Peru. Pp. 155193 in: Geology and Ore Deposits of the Central Andes (Skinner, B.J., editor). Special Publication 7. Society of Economic Geologists, USA.Google Scholar
Petersen, U., Noble, D.C., Arenas, M.J. and Goodell, P.C. (1977) Geology of the Julcani mining district, Peru. Economic Geology, 72, 931949.CrossRefGoogle Scholar
Sack, R.O. (1992) Thermochemistry of tetrahedrite–tennantite fahlores. Pp. 243266 in: The Stability of Minerals (Ross, N.L. and Price, G.D., editors). Chapman & Hall, London.Google Scholar
Sack, R.O. (2000) Internally consistent database for sulfides and sulfosalts in the system Ag2S-Cu2S-ZnS- Sb2S3-As2S3 . Geochimica et Cosmochimica Acta, 64, 38033812.CrossRefGoogle Scholar
Sack, R.O. and Ebel, D.S. (1993) As–Sb exchange energies in tetrahedrite-tennant ite fahlores and bournonite-seligmannite solid solutions. Mineralogical Magazine, 57, 633640.CrossRefGoogle Scholar
Sack, R.O. and Loucks, R.R. (1985) Thermodynamic properties of tetrahedrite-tennantites: Constraints on the interdependence of the Ag⇋Cu, Fe⇋Zn, Cu⇋Fe, and As⇋Sb exchange reactions. American Mineralogist, 70, 12701289.Google Scholar
Sack, R.O., Kuehner, S.M. and Hardy, L.S. (2002) Retrograde Ag-enrichment in fahlores from the Coeur d'Alene mining district, Idaho, USA. Mineralogical Magazine, 66, 215229.CrossRefGoogle Scholar
Sewell, D.A., Love, G. and Scott, V.D. (1985) Universal correction procedure for electron-probe microanalysis: II. The absorption correction. Journal of Physics D: Applied Physics, 18, 12451268.CrossRefGoogle Scholar
Sharp, T.G. and Buseck, P.R. (1993) The distribution of Ag and Sb in galena: Inclusions versus solid solution. American Mineralogist, 78, 8595.Google Scholar
Spycher, N.F. and Reed, M.H. (1989 a) Evolution of a Broadlands-type epithermal ore fluid along alternative P-T paths: Implications for the transport and deposition of base, precious, and volatile metals. Economic Geology, 84, 328359.CrossRefGoogle Scholar
Spycher, N.F. and Reed, M.H. (1989 b) As (III) and Sb (III) sulfide complexes: An evaluation of stoichiometry and stability from existing experimental data. Geochimica et Cosmochimica Acta, 53, 21852194.CrossRefGoogle Scholar
Van Hook, H.J. (1960) The ternary system Ag2S-Bi2S3-PbS. Economic Geology, 55, 759788.CrossRefGoogle Scholar
Wood, S.A., Crerar, D.A. and Borcsik, M.A. (1987) Solubility of the assemblage pyrite-pyrrhotite-magnetite-sphalerite-galena-gold-stibnite-bismuthiniteargentite-molybdenite in H2O-NaCl-CO2 solutions from 200–350°C. Economic Geology, 82, 18641887.CrossRefGoogle Scholar
Wu, I. and Petersen, U. (1977) Geochemistry of tetrahedrite–tennantite at Casapalca, Peru. Economic Geology, 72, 9931016.CrossRefGoogle Scholar