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Acid-sulphate hydrothermal alteration of andesitic tuffs and genesis of halloysite and alunite deposits in the Biga Peninsula, Turkey

Published online by Cambridge University Press:  09 July 2018

Ö. I. Ece ,
P. A. Schroeder ,
M. J. Smilley  and
J. M. Wampler
Ö. I. Ece*
Affiliation:
Istanbul Technical University, Faculty of Mines, Department of Geological Sciences, Mineralogy-Petrography Division, Maslak 34469 Istanbul, Turkey The University of Georgia, Department of Geology, Athens, GA 30602-2501, USA
P. A. Schroeder
Affiliation:
The University of Georgia, Department of Geology, Athens, GA 30602-2501, USA
M. J. Smilley
Affiliation:
The University of Georgia, Department of Geology, Athens, GA 30602-2501, USA
J. M. Wampler
Affiliation:
Georgia Institute of Technology, School of Earth and Atmospheric Sciences, Atlanta, GA 30332, USA
*
*E-mail: [email protected]
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Abstract

The Biga Peninsula of NW Turkey is host to six major halloysite deposits in the Go¨nen, Yenice and Balya districts. Mineralization took place in areas of Permian limestone blocks where the Triassic Karakaya Complex is in contact with early Miocene calc-alkaline volcanic rocks. Hypogene halloysite mineralization was controlled by the intersection of minor faults in the vicinity of clay deposits. During the Pleistocene, activity of the North Anatolian Fault (NAF) brought ascending geothermal solutions through the fault zones to the surface, which led to hydrothermal alteration and halloysite formation. N-MORB normalized element values for each halloysite deposit and the volcanic rocks suggest genetic links. Alunite and halloysite were formed in the Turplu area where upwelling hydrothermal waters contained major H2S and SO2 acids. Only halloysite mineralization occurred in outflow areas of the same fossil geothermal field.

Pyrite and alunite samples from the Turplu deposits have δ34S values of 0.6–1.8% and 4.8–7.9%, respectively, with values for gypsum of 3.1–3.5%. The δ34S values of pyrite suggest that local meteoric waters had partially mixed with the dominant fluid during the closure stage of fossil hydrothermal activities. The range of δD values of halloysite samples from Turplu is –58.4 to –68.6%. The δ18O values for halloysite are in the range 16.7–18.1%. All halloysite deposits in the study areas are either overlying or adjacent to limestone blocks, and these provide excellent drainage for the discharging geothermal waters. Subsurface drainage systems in the karstic environment and the SO2-bearing thermal waters indicate the importance of acidic waters and the continuous leaching of elements in forming relatively pure hydrated halloysite. A steam-heated dissolution-precipitation model is proposed for the occurrence of all halloysite and alunite deposits. Sulphur gases (H2S-SO2) of hypogene origin rose from deep in the fault zone to the surface where they encountered oxygenated groundwater at the water table. The occurrence of H2SO4 in this hydrothermal system enhanced the acidity of geothermal waters provoking advanced argillic alteration. Hypogene alunite deposits also have large P2O5 contents, suggesting a parent material with a magmatic origin deeper than the alkaline tuffs. Halloysite is a fast-forming metastable precursor to kaolinite.

Keywords

calc-alkaline volcanismacid-sulphate thermal watershydrothermal alterationhalloysitealunitesulphur isotopesTurkey
Type
Research Article
Information
Clay Minerals , Volume 43 , Issue 2 , June 2008 , pp. 281 - 315
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2008

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References

Alpar, B. & Yaltırak, C. (2002) Characteristic features of the North Anatolian Fault in the Marmara region and its tectonic evolution. Marine Geology, 190, 329–350.CrossRefGoogle Scholar
Altunkaynak, Ş. & Yılmaz, Y. (1998) The Mount Kozak magmatic complex, Western Anatolia. Journal of Volcanology and Geothermal Research, 85, 211–231.CrossRefGoogle Scholar
Altunkaynak, Ş. & Yılmaz, Y. (1999) The Kozak Pluton and its emplacement. Geological Journal, 34, 257–274.3.0.CO;2-Q>CrossRefGoogle Scholar
Bailey, S.W. (1989) Halloysite — A critical assessment. Pp. 89–98 in: Proceedings of the 9th International Clay Conference; Strasbourg, France (Farmer, V.C. and Tardy, T., editors). Sciences Géologiques Mémoires (Strasbourg), 86.Google Scholar
Barka, A.A. (1992) The North Anatolian fault zone. Annales Tectonicae, 6, 164–195.Google Scholar
Brimhall, G.H. Jr. & Ghiorso, M.S. (1983) Origin and oreforming consequences of the advanced argillic alteration process in hypogene environments by magmatic gas contamination of meteoric fluids. Economic Geology, 78, 73–90.CrossRefGoogle Scholar
Browne, P.R.L. (1998) Hydrothermal Alteration. University of Auckland, Geothermal Institute, New Zealand, 70 pp.Google Scholar
Cornell, R.M. & Schwertmann, U. (1996) The Iron Oxides: Structure, Properties, Reactions, Occurrences, and Uses. Wiley-VCH, 573 pp.Google Scholar
Cunningham, C.G., Rasmussen, J.D., Steven, T.A., Rye, R.O., Rowley, P.D., Romberger, S.B. & Selverstone, J. (1998) Hydrothermal uranium deposits containing molybdenum and fluorite in the Marysvale volcanic field, west-central Utah. Mineralium Deposita, 33, 477–494.CrossRefGoogle Scholar
Dill, H.G. (2001) The geology of aluminium phosphates and sulphates of the alunite group minerals: a review. Earth Science Reviews, 53, 35–93.CrossRefGoogle Scholar
Dill, H.G., Bosse, H.R., Henning, K.H., Fricke, A. & Ahrendt, H. (1997) Mineralogical and chemical variations in hypogene and supergene kaolin deposits in a mobile fold belt the Central Andes of northwestern Peru. Mineralium Deposita, 32, 149–163.CrossRefGoogle Scholar
Ece, Ö.I. & Nakagawa, Z. (2003) Alteration of volcanic rocks and genesis of kaolin deposits in Sile region, northern Istanbul, Turkey. Part II. Differential mobility of elements. Clay Minerals, 38, 529–550.CrossRefGoogle Scholar
Ece, Ö.I. & Schroeder, P.A. (2007) Clay mineralogy and chemistry of the halloysite and alunite deposits in the Turplu area, Balıkesir, Turkey. Clays and Clay Minerals, 55, 18–36.CrossRefGoogle Scholar
Elliott, W.C., Edenfield, A.M., Wampler, J.M., Matisoff, G. & Long, P.E. (1999) The kinetics of the smectite to illite transformation in Cretaceous bentonites, Cerro Negro, New Mexico. Clays and Clay Minerals, 47, 286–296.CrossRefGoogle Scholar
Fournier, R.O. (1986) The behavior of silica in hydrothermal solutions. Pp. 45–61 in: Geology and Geochemistry of Epithermal Systems (Berger, B.R. & Bethke, P.M., editors). Reviews in Economic Geology, 2. Society of Economic Geologists, El Paso, Texas, USA.Google Scholar
Frakes, L. & Bolton, B. (1984) Origin of manganese giants: Sea-level change and anoxic-oxic history. Geology, 12, 83–86.2.0.CO;2>CrossRefGoogle Scholar
Frakes, L. & Bolton, B. (1992) Effects of ocean chemistry, sea level, and climate on the formation of primary sedimentary manganese ore deposits. Economic Geology, 87, 1207–1217.CrossRefGoogle Scholar
Fytikas, M., Giuliani, O., Innocenti, F., Marinelli, G. & Mazzuoli, R. (1976) Geochronological data on recent magmatism of Aegean Sea. Tectonophysics, 31, 29–34.CrossRefGoogle Scholar
Fytikas, M., Innocenti, F., Manetti, P., Mazzuoli, R., Peccerillo, A. & Villari, L. (1984) Tertiary to Quaternary evolution of volcanism in the Aegean Region. Pp. 687–699 in: The Geological Evolution of the Aegean Mediterranean (Dixon, J.E. & Robertson, A.H.F., editors). Special Publication 17, The Geological Society, London.Google Scholar
Genç, C.Ş. (1998) Evolution of the Bayramiç magmatic complex, northwestern Anatolia. Journal of Volcanology and Geothermal Research, 85, 233–249.CrossRefGoogle Scholar
Gözler, Z. (1984) Çannakkle Bogazı dogusu —Marmara Denizi guneyi —Bandırma-Balıkesir-Edremit ve Ege Denizi arasındaki alanın jeolojisi ve kompilasyonu. MTA (Mineral Reseach and Exploration Institute) Open File Report 7430.Google Scholar
Harris, C., Compton, J.S. & Bevington, S.A. (1999) Oxygen and hydrogen isotope composition of kaolinite deposits, Cape Peninsula, South Africa; low-temperature, meteoric origin. Economic Geology, 94, 1353–1366.CrossRefGoogle Scholar
Harris, N.B.W., Pearce, J.A. & Tindle, A.G. (1986) Geochemical characteristics of collision-zone magmatism. Pp. 67–81 in: Collision Tectonics (Coward, M.P. & Ries, A.C., editors). Special Publication 19. The Geological Society, London.Google Scholar
Harris, N.B.W., Kelley, S. & Okay, A.I. (1994) Post-collision magmatism and tectonics in northwest Anatolia. Contributions to Mineralogy and Petrology, 117, 241–252.CrossRefGoogle Scholar
Harvey, C.C. & Murray, H.H. (1993) The geology, mineralogy and exploitation of halloysite clays of Northland, New Zealand. Pp. 233–248 in: Kaolin Genesis and Utilization (Murray, H., Bundy, W. & Harvey, C., editors) CMS Special Publication, 1.Google Scholar
Hayba, D.O., Bethke, P.M., Heald, P. & Faley, N.K. (1985) Geologic, mineralogic and geochemical characteristics of volcanic-hosted epithermal precious-metal deposits. Reviews in Economic Geology, 2, 129-167.Google Scholar
Heald, P., Foley, N.K. & Hayba, D.O. (1987) Comparative anatomy of volcanic-hosted epithermal deposits: acid-sulphate and adularia-sericite types. Economic Geology, 82, 1–26.CrossRefGoogle Scholar
Henley, R.D. & Ellis, A.J. (1983) Geothermal systems ancient and modern: a geochemical review. Earth Science Reviews, 19, 1–50.CrossRefGoogle Scholar
Herece, E. (1990) 1953 Yenice-Gönen earthquake fracture and the extension of North Anatolian Fault zone in Biga peninsula. Mineral Research and Exploration Bulletin, 11, 47–59.Google Scholar
Hill, C.A. (1986) Fiume Vento cave, Italy — ‘a baby’ Carlsbad Cavern. Cave Research Foundation Annual Report, 28, 18–20.Google Scholar
Hill, C.A. (1987) Geology of Carlsbad Cavern and other caves in the Guadalupe Mountains, New Mexico and Texas. New Mexico Bureau of Mines and Mineral Resources Bulletin, 117, 150.Google Scholar
Hill, C.A. (1990) Sulfuric acid speleogenesis of Carlsbad cavern and its relationship to hydrocarbons, Delawarer basin, New Mexico and Texas. American Association of Petroleum Geologists Bulletin, 74, 1685–1694.Google Scholar
Holland, H.D. (1965) Some applications of thermochemical data to problems of ore deposits, II. Mineral fluids. Economic Geology, 60, 1101–1166.CrossRefGoogle Scholar
Holland, H.D. (1967) Gangue minerals in hydrothermal deposits. Pp. 382–436 in: Geochemistry of Hydrothermal Ore Deposits (Barnes, H.L., editor) New York, Holt, Rinehart and Winston.Google Scholar
Huang, W.H. & Keller, W.D. (1971) Dissolution of clay minerals in dilute organic acids at room temperature. American Mineralogist, 56, 1082–1095.Google Scholar
Inoue, A. & Utada, M. (1991a) Hydrothermal alteration related to Kuroko mineralization in the Kamikita area, Northern Honshu, Japan, with special reference to the acid-sulfate alteration. Geological Survey of Japan Report, 277, 39–48.Google Scholar
Inoue, A. & Utada, M. (1991b) Hydrothermal alteration in Kamikita Kuroko mineralization area, Northern Honshu, Japan. Mining Geology, 41, 203–218.Google Scholar
Ishihara, S., Jin, M.S. & Sasaki, A. (2000) Source diversity of ore sulfur from Mesozoic-Cenozoic mineral deposits in the Korean Peninsula region. Resource Geology, 50, 203–212.CrossRefGoogle Scholar
Jeong, G.Y. (1998) Formation of vermicular kaolinite from halloysite aggregates in the weathering of plagioclase. Clays and Clay Minerals, 46, 270–279.CrossRefGoogle Scholar
Joussein, E., Petit, S., Churchman, J., Theng, B., Righi, D. & Delvaux, B. (2005) Halloysite clay minerals —A review. Clay Minerals, 40, 383–426.CrossRefGoogle Scholar
Kadir, S. & Karakaş, Z. (2004) Mineralogy, chemistry and origin of halloysite, kaolinite and smectite from Miocene ignimbrites, Konya, Turkey. Neues Jahrbuch für Mineralogie-Abhandlungen, 177, 113–132.CrossRefGoogle Scholar
Karacık, Z. & Yılmaz, Y. (1998) Geology of the ignimbrites and the associated volcano-plutonic complex of the Ezine area, northwestern Anatolia. Journal of Volcanology and Geothermal Research, 85, 251–264.CrossRefGoogle Scholar
Keller, W.D. (1963) Hydrothermal kaolinitization (endellization) of volcanic glassy rock. Clays and Clay Minerals, 10th International Conference, pp. 333–343.CrossRefGoogle Scholar
Keller, W.D. & Hanson, R.F. (1968) Hydrothermal alteration of a rhyolitic flow breccia near San Luis Potosi, Mexico, to refractory kaolin. Clays and Clay Minerals, 16, 223–230.CrossRefGoogle Scholar
Keller, W.D. & Hanson, R.F. (1969) Hydrothermal argillation of volcanic pipes in limestone in Mexico. Clays and Clay Minerals, 17, 9–12.CrossRefGoogle Scholar
Keller, W.D., McGrain, P., Reesman, A.L. & Saum, N.M. (1966) Observations on the origin of endellite in Kentucky and their extension to ‘indianaite’. Clays and Clay Minerals, 3, 97–120.Google Scholar
Keller, W.D., Hanson, R.F., Huang, W.H. & Cervantes, A. (1971) Sequential active alteration of rhyolitic volcanic rock to endellite and a precursor phase of it at a spring in Michoacan, Mexico. Clays and Clay Minerals, 19, 121–127.CrossRefGoogle Scholar
Kttrick, J.A. (1969) Soil minerals in the Al2O3-SiO2- H2O system and a theory of their formation. Clays and Clay Minerals, 17, 157–167.CrossRefGoogle Scholar
Le Maitre, R.W. (1989) A Classification of Igneous Rocks and Glossary of Terms. Blackwell Science, Oxford, 193 pp.Google Scholar
Love, D.A., Clark, A.H., Jay Hodson, C., Mortensen, I.K., Archibald, D.A. & Farrar, E. (1998) The timing of adularia-sericite-type mineralization and alunitekaolinite-type alteration, Mount Skukum epithermal gold deposit, Yukon Territory, Canada: 40Ar/39Ar and U-Pb geochronology. Economic Geology, 93, 437–462.CrossRefGoogle Scholar
Murray, H.H. & Keller, W.D. (1993) Kaolins, kaolins, and kaolins. Pp. 1–25 in: Kaolin Genesis and Utilization (Murray, H., Bundy, W. & Harvey, C., editors). Special Publication, 1. The Clay Minerals Society, Boulder, Colorado, USA.CrossRefGoogle Scholar
Nicholson, K. (1993) Geothermal Fluids; Chemistry and Exploration Techniques. Springer-Verlag, Berlin, 262 pp.CrossRefGoogle Scholar
Ohmoto, H. (1972) Systematics of sulfur and carbon isotopes in hydrothermal ore deposits. Economic Geology, 67, 551–579.CrossRefGoogle Scholar
Ohmoto, H. & Goldhaber, M.B. (1997) Sulfur and carbon isotopes. Pp. 517–612 in: Geochemistry of Hydrothermal Ore Deposits 3rd edition (Barnes, H.L., editor). Wiley, New York.Google Scholar
Ohmoto, H. & Lasaga, A.C. (1982) Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems. Geochimica et Cosmochimica Acta, 46, 1727–1748.CrossRefGoogle Scholar
Ohmoto, H. & Rye, R.O. (1979) Isotopes of sulfur and carbon. Pp. 509–567 in: Geochemistry of Hydrothermal Ore Deposits (Barnes, H.L., editor). New York, Holt, Rinehart and Winston.Google Scholar
Okay, A.I., Siyako, M. & Burkan, K.A. (1991) Geology and tectonic evolution of the Biga Peninsula, northwest Turkey. Bulletin of Istanbul Technical University, 44, 191–256.Google Scholar
Okay, A.I., Demirbağ, E., Kurt H, Okay, N. & Kuşçu, I. (1999) An active, deep marine strike-slip basin along the North Anatolian Fault in Turkey. Tectonics, 18, 129–147.CrossRefGoogle Scholar
Okay, A.I., Kaslılar-Özcan, A., Imren, C., Boztepe-Güney, A., Demirbağ, E. & Kuşçu, I. (2000) Active faults and evolving strike-slip basins in the Marmara Sea, northwest Turkey: a multichannel seismic reflection study. Tectonophysics, 321, 189–218.CrossRefGoogle Scholar
Öngen, S. (1978) Genetische aussagen uber das Çavuslu— Karaköy granotoid massiv. Istanbul Üniversity, Fen Fakultesi Mecmuasi, B43, 141–150.Google Scholar
Örgün, Y., Gültekin, A.H. & Onal, A. (2005) Geology, mineralogy and fluid inclusion data from the Arapucan Pb-Zn-Cu-Ag deposit, Çanakkale, Turkey. Journal of Asian Earth Sciences, 25, 629–642.CrossRefGoogle Scholar
Öztürk, H., Hein, J.R. & Hanılçı, N. (2002) Genesis of the Doğankuzu and Mortas. bauxite deposits, Taurides, Turkey: Seperation of Al, Fe, and Mn and implications for passive margin metallogeny. Economic Geology, 97, 1063–1077.CrossRefGoogle Scholar
Pearce, J.A., Bender, J.F., De Long, S.E., Kidd, W.S.F., Low, P.J., Güner, Y., Saroglu, F., Yılmaz, Y., Moorbath, S. & Mitchell, J.J. (1990) Genesis of collision volcanism in eastern Anatolia, Turkey. Journal of Volcanology and Geothermal Research, 44, 189–229.CrossRefGoogle Scholar
Perruchot, A., Dupuis, C., Brouard, E., Nicaise, D. & Ertus, R. (1997) L’halloysite karstique: comparaison des gisements types de Wallonie (Belgique) et du Perigord (France). Clay Minerals, 32, 271–287.CrossRefGoogle Scholar
Polyak, V.J. & Güven, N. (1996) Alunite, natroalunite and hydrated halloysite in Carlsbad Cavern and Lechuguilla cave, New Mexico. Clays and Clay Minerals, 44, 843–850.CrossRefGoogle Scholar
Poulson, S.R., Kubilius, W.P. & Ohmoto, H. (1991) Geochemical behavior of sulfur in granitoids during intrusion of the South Mountain Batholith, Nova Scotia, Canada. Geochimica et Cosmochimica Acta, 55, 3809–3830.CrossRefGoogle Scholar
Railsback, L.B. (2003) An earth scientist's periodic table of the elements and their ions. Geology, 31, 737–740.CrossRefGoogle Scholar
Rye, R.O., Bethke, P.M. & Wasserman, W.D. (1992) The stable isotope geochemistry of acid sulfate alteration. Economic Geology, 87, 225–262.CrossRefGoogle Scholar
Sakai, H. & Matsubaya, O. (1977) Stable isotope studies of Japanese geothermal systems. Geothermics, 5, 97–124.CrossRefGoogle Scholar
Sengör, A.M.C., Tüysüz, O., Imren, C., Sakinc, M., Eyidogan, H., Görür, N., Le Pichon, X. & Rangin, C. (2005) The North Anatolian Fault: A new look. Annual Review of Earth and Planetary Sciences, 33, 37–112.CrossRefGoogle Scholar
Sheppard, S.M.F. & Gilg, H.A. (1996) Stable isotope geochemistry of clay minerals. Clay Minerals, 31, 1–24.CrossRefGoogle Scholar
Siyako, M., Bürkan, K.A. & Okay, A.I. (1989) Tertiary geology and hydrocarbon potential of the Biga and Gelibolu Peninsulas. Turkish Association of Petroleum Geologists Bulletin, 1, 183–199.Google Scholar
Stoffregen, R. (1987) Genesis of acid-sulfate alteration and Au-Cu-Ag mineralization at Summitville, Colorado. Economic Geology, 82, 1575–1591.CrossRefGoogle Scholar
Stumm, W. & Morgan, J.J. (1970) Aqueous Chemistry. Wiley, New York, 583 pp.Google Scholar
Su, C. & Harsh, J.B. (1994) Gibbs free energies of formation at 298 K for imogolite and gibbsite from solubility measurements. Geochimica et Cosmochimica Acta, 58, 1667–1677.CrossRefGoogle Scholar
Sun, S.S. & McDonough, W.F. (1989) Chemical and isotopic systematics of oceanic basalts: implications for mantle composition and processes. Pp. 313–345 in: Magmatism in the Ocean Basins (Saunders, A.D. & Norry, M.J., editors). Special Publication, 42. The Geological Society, London.Google Scholar
Tazaki, K. (2005) Microbial formation of a halloysitelike mineral. Clays and Clay Minerals, 53, 224–233.CrossRefGoogle Scholar
Thorpe, R.S., Francis, P.W. & O’Callaghan, L. (1984) Relative roles of source composition, fractional crystallization and crustal contamination in the petrogenesis of Andean volcanic rocks. Philosophical Transactions of the Royal Society London, A310, 675–692.Google Scholar
Uygun, A. (1999) KB Anadolu’da karbonat kayaçların içine yerlegmis. bazı halloysit yataklarının jeolojisi ve olugumu. (Occurrence and geology of some halloysite deposits embedded in carbonate rocks in NW Anatolia). MTA Dergisig, 121, 141–151.Google Scholar
Whitney, J.A. (1984) Fugacities of sulfurous gases in pyrrhotite-bearing silicic magmas. American Mineralogist, 69, 69–78.Google Scholar
Winchester, J.A. & Floyd, P.A. (1977) Geochemical discrimination of different magma series and their differentiation products using immobile elements. Chemical Geology, 20, 325–343.CrossRefGoogle Scholar
Yalçın, T.H. (1997) Hydrogeological investigation of Gönen and Eksidere (Balıkesir) thermal waters (NW Turkey). Pp. 275–300 in: Active Tectonics of Northwestern Anatolia - The Marmara Poly- Project (Schindler, C. & Pfister, M., editors), Hochschulverlag AG an der ETH Zurich.Google Scholar
Yalçın, T.H. & Sarp, S. (2008) Investigation of thermal waters in Biga Peninsula. Mineral Research and Exploration (MTA) open-file report (in prep).Google Scholar
Yau, Y.C., Peacor, D.R. & Essene, E.J. (1987) Hydrothermal treatment of smectite, illite and basalt to 460°C —comparison of natural with hydrothermally formed clay minerals. Clays and Clay Minerals, 35, 241–250.CrossRefGoogle Scholar
Yılmaz, Y., Genç, Ş.C., Karacık, Z. & Altunkaynak, Ş. (2001) Two contrasting magmatic associations of NW Anatolia and their tectonic significance. Journal of Geodynamics, 31, 243–271.CrossRefGoogle Scholar
Ziegler, K., Hsieh, J.C.C., Chadwick, O.A., Kelly, E.F., Hendricks, D.M. & Savin, S.M. (2003) Halloysite as a kinetically controlled end product of arid-zone basalt weathering. Chemical Geology, 202, 461–478.CrossRefGoogle Scholar