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Alteration of volcanic rocks and genesis of kaolin deposits in the Şile Region, northern İstanbul, Turkey. Part II: differential mobility of elements

Published online by Cambridge University Press:  09 July 2018

O. I. Ece*
Affiliation:
Istanbul Technical University, Faculty of Mines, Mineralogy-Petrography Division, Maslak80626, IstanbulTurkey Research Institute of Materialsand Resources, Faculty of Engineering and Resources Science, Akita University, Tegatagakuen-Cho, Akita 010-8502, Japan
Z.-E Nakagawa
Affiliation:
Research Institute of Materialsand Resources, Faculty of Engineering and Resources Science, Akita University, Tegatagakuen-Cho, Akita 010-8502, Japan
*

Abstract

In the area of S° ile, NW Turkey, Upper Cretaceous calc-alkaline volcanic rocks with compositions ranging from andesite to rhyolite have been recognized. The most widespread rocks of the suite are andesites, which can be grouped into altered and fresh. The oldest altered andesites are the parent rocks for the kaolin deposits of the study area. The Upper Cretaceous volcanic suite consists of spilite, basalt, andesite, trachyandesite, trachyandesitic and hyaloandesitic dacite, rhyolite lavas, tuffs and agglomerates. The highly altered andesites are composed of plagioclase, pyroxene, hornblende, biotite, augite and very fine opaque minerals. During the Turonian, an E –W trending extensional magmatic arc was developed in the Istanbul Tectonic Zone of the oceanic Western Black Sea basin and intermediate volcanic rocks were emplaced, mostly calc-alkaline andesites, suggesting multi-stage magmatism. The significant features of the andesites are: (1) enrichment of LILE (Rb, Ba, K) over HFSE (Zr, Nb, Hf, Ti, Th, U, Y) and LREE (La –Sm), resulting in high Ba/Nb, Th/Nb, Ba/La, K/Ti and Th/La ratios; (2) depletion of LREE over HFSE, MREE and HREE, generating high La/Nb, Ce/Ti, La/Sm and La/Y values; and (3) depletion of Nb, Sr and Ti; all of which are typical of island arc magmatism, with possible back arc signature. The Th-Hf-Ta diagram for tectonomagmatic classification shows that the S° ile calc-alkaline rocks are similar to volcanic rocks from the Mariana Arc, the Aeolian Arc of Salina, Italy, the Skaros island in the Aegean Sea and Sardinia's ignimbrites. Moreover, relatively low La/Th and Ce/Pb ratios suggest that the source region of volcanism was enriched in LILE with respect to REE, indicating crustal contamination during melting.

Highly weathered andesitic rocks, rich in smectite, were transported gradually and deposited in a lacustrine basin, a coal-forming dysaerobic environment, in which they were subject to post-depositional alteration, or in situkaolinization, to form a kaolin deposit in the presence of humic and fulvic acids. The mobility of major and trace elements and REEs during the progressive kaolinization of andesitic materials has been investigated to reveal the geochemical characteristics of Upper Cretaceous volcanic parent rocks and to explain mineralogical processes in a kaolin deposit as a daughter rock ‘end-product’ . Alteration is characterized by the loss of Si, Fe, Ca, Na and K, and by the gain of Al, Ti, Zr and LOI. Moreover, Ho, Er and Yb are immobile, and Hf, Zr and Nb are mobile. Th and U are slightly enriched in clay horizons with respect to the andesitic rocks. In addition, Cr, Ga, Nb and Ta enrichments indicate variable sources of terrigenous sediments and differential mobilities of elements in lake waters rich in organic acids. The anatase concentration increases in the <2 mm size fractions as subspherical particles and these precipitate at acidic conditions (pH ≈ 5) during early diagenesis.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2003

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References

Anand, R.R. & Gilkes, R.J. (1984) Weathering of ilmenite in a lateritic pallid zone. Clays and Clay Minerals, 32, 363 374.Google Scholar
Bau, M. (1991) Rare-earth element mobility, hydrothermal and metamorphic fluid-rock interaction, and the significance of the oxidation state of europium. Chemical Geology, 93, 219230.Google Scholar
Berner, R.A. (1970) Sedimentary pyrite formation. American Journal of Science, 268, 123.Google Scholar
Bohor, B.F. & Triplehorn, D.M. (1993) Tonsteins: Altered volcanic ash layers in coal-bearing sequences. GSA Special Paper, 285, 44 pp.Google Scholar
Boynton, W.V. (1984) Geochemistry of the rare earth elements: meteorite studies. Pp. 63114 in. Rare Earth Element Geochemistry (Henderson, P., editor). Developments in Geochemistry, 2. Elsevier, Amsterdam.Google Scholar
Brimhall, G.H. & Dietrich, W.E. (1987) Constitutive mass balance relations between chemical composotion, volume, density, porosity and strain in metasomatic hydrochemical systems: Results on weathering and pedogenesis. Geochimica et Cosmochimica Acta, 51, 567587.Google Scholar
Bristow, C.M. (1993) The genesis of the china clays of Southwest England – A multistage story. Pp. 171 203.in. Kaolin Genesis and Utilization (Murray., H.H. Bundy, W. and Harvey, C., editors). Special Publica tion 1. The Clay Mineral s Society, Bloomington, Indiana, USA.Google Scholar
Brookins, D.G. (1989) Aqueous geochemistry of rare earth elements. Pp. 201225 in. Geochemistry and Mineralogy of Rare Earth Elements (Lipin, B.P. and McKay, G.A., editors). Reviews in Mineralogy, 21. Mineralogical Society of America, Washington, D.C.Google Scholar
Chadwick, O.A., Brimhall, G.H. & Hendricks, D.M. (1990) From a black to a gray box – a mass balance interpretation of pedogenesis. Geomorphology, 3, 369390.Google Scholar
Christidis, G.E. (1998) Comparative study of the mobility of major and trace elements during alteration of an andesite and a rhyolite to bentonite, in the islands of Milos and Kimolos, Aegean, Greece. Clays and Clay Minerals, 46, 379399.Google Scholar
Christidis, G. & Dunham, A.C. (1993) Compositional variations in smectites: Part I. Alteration of intermediate volcanic rocks. A case study from Milos Island, Greece. Clay Minerals, 28, 255 273.CrossRefGoogle Scholar
Christidis, G. & Dunham, A.C. (1997) Compositional variations in smectites: Part II. Alteration of acidic precursors. A case study from Milos Island, Greece. Clay Minerals, 32, 253270.Google Scholar
Çoban, F., Ece, Ö.I., Yavuz, O. & Özdamar, S. (2002) Petrogenesis of volcanic rocks and clay mineralogy and genesis of underclays, Şile Region, Istanbul, Turkey. Neues Jahrbuch für Mineralogie Abhandlungen, 178, 125.Google Scholar
Ece, Ö.I., Nakagawa, Z. & Schroeder, P.A. (2003) Alteration of volcanic rocks and genesis of kaolin deposits in Şile region, Northern Istanbul, Turkey. Part I. Clay Mineralogy. Clays and Clay Minerals, 51, 675688.Google Scholar
Garrels, R.M. & Christ, C.L. (1965) Solutions Minerals and Equilibria. Harper & Row, New York, 450 pp.Google Scholar
Gertisser, R. & Keller, J. (2000) From basalt to dacite: origin and evolution of the calc-alkaline series of Salina, Aeolian Arc, Italy. Contribu tions to Mineralogy and Petrology, 139, 607626.Google Scholar
Gresens, R.L. (1967) Composition-volume relationship of metasomatism. Chemical Geology, 2, 4765.Google Scholar
Grill, J.B. (1981) Orogenic Andesites and Plate Tectonics. Springer-Verlag, Berlin, 385 pp.Google Scholar
Huang, W.H. & Keller, W.D. (1971) Dissolution of clay minerals in dilute organic acids at room temperature. American Mineralogist, 56, 10821095.Google Scholar
Huang, W.H. & Keller, W.D. (1972) Geochemical mechanics for the dissolution, transport, and deposition of aluminium in the zone of weathering. Clays and Clay Minerals, 20, 6974.Google Scholar
Huang, W.H. & Keller, W.D. (1973) New stability diagrams of some phyllosili cates in the SiO2 –Al2O3–K2O –H2O system. Clays and Clay Minerals, 21, 331336.Google Scholar
Hurst, V.J. & Pickering, S.M. (1997) Origin and classification of coastal-plain kaolins, southeastern U.A. and the role of groundwater and microbial action. Clays and Clay Minerals, 45, 274285.Google Scholar
Kittrick, J.A. (1970) Precipitation of kaolinite at 25ºC and 1 atm. Clays and Clay Minerals, 18, 261267.Google Scholar
Krower, H. (1980) Clays and clay minerals in the Federal Republic of Germany. Geologisches Jahrbuch, D39, 2545.Google Scholar
Kurtz, A.C., Derry, L.A., Chadwick, O.A. & Jo Alfano, M. (2000) Refractory element mobility in volcanic soils. Geology, 28, 683686.Google Scholar
Langmuir, D. & Herman, J.S. (1980) The mobility of thorium in natural waters at low temperatures. Geochimica et Cosmochimica Acta, 44, 17531766.Google Scholar
Le Maitre, R.W. (1989) A Classification of Igneous Rocks and Glossary of Terms. Blackwell Science Publications, Oxford, UK, 193 pp.Google Scholar
Linares, J. & Huertas, F. (1971) Kaolinite: Synthesis at Room Temperature. Science, 171, 896897.Google Scholar
Loughman, F.C. (1978) Flint clays, tonsteins and the kaolinite clay rock facies. Clay Minerals, 13, 387400.Google Scholar
MacLean, W.H. (1988) Rare earth element mobility at constant inter-REE ratios in the alteration zone at the Phelps Dodge massive sulphide deposit, Matagami, Quebec. Mineralium Deposita, 23, 231238.Google Scholar
McCulloch, M.T. & Gamble, J.A. (1991) Geochemical and geodynamical constraints on subduction zone magmatism. Earth and Planetary Science Letters, 102, 358374.Google Scholar
McDonough, W.F. (1991) Partial melting of subducted oceanic crust and isolation of its residual eclogitic lithology. Philosophical Transactions of the Royal Society, London, 335A, 407418.Google Scholar
Miller, D.M., Goldstein, S.L. & Langmuir, C.H. (1994) Cerium/lead and lead isotopes in arc magmas and enrichment of lead in the continents. Nature, 368, 514519.Google Scholar
Millero, F.J. (1992) Stability constants for the formation of rare earth inorganic complexes as a function of ionic strength. Geochimica et Cosmochimica Acta, 56, 31233132.Google Scholar
Moretti, A. & Pieruccini, U. (1968) Italian kaolin deposits. 23rd International Geological Congress, Prague, 15, 201209.Google Scholar
Okay, A.., Şengör, A.M.C. & Görür, N. (1994) Kinematic history of the Black Sea and its effect on the surrounding regions. Geology, 22, 267 270.Google Scholar
Pearce, J.A. (1983) Role of subcontinental lithosphere in magma genesis at active continental margins. Pp. 230 253.in. Continental Basalts and Mantle Xenoliths (Hawkesworth, C.J. and Norry, M.J., editors). Springer-Verlag, Berlin.Google Scholar
Pearce, J.A. & Peate, D.W. (1995) Tectonic implications of the composition of volcanic arc magmas. Annual Review of Earth and Planetary Science, 23, 251285.Google Scholar
Satoh, H., Ishiyama, D., Mizuta, T. & Ishikawa, Y. (1999) Rare earth element analysis of rock and thermal water samples by inductively coupled plasma mass spectrometry (ICP – MS). Scientific and Technical Reports of Akita University, 20, 18.Google Scholar
Schroeder, P.A. & Shiflet, J. (2000) Ti-bearing phases in the Huber Formation, an east Georgia kaolin deposit. Clays and Clay Minerals, 48, 151158.Google Scholar
Senkayi, A.L., Dixon, J.B., Hossner, L.R., Abder-Ruhman, M. & Fanning, D.S. (1984) Mineralogy and genetic relationships of tonstein, bentonite and lignitic strata in the Eocene Yegua Formation of East-Central Texas. Clays and Clay Minerals, 32, 259271.Google Scholar
Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, A32, 751767.Google Scholar
Spears, D.A. & Kanaris-Sotiriou, R. (1979) A geochemical and mineralogical investigation of some British and other European tonstein. Sedimentology, 26, 407425.Google Scholar
Sun, S.S. (1980) Lead isotopic study of young volcanic rocks from mid-ocean ridges, ocean islands and island arcs. Philosophical Transactions of the Royal Society, A297, 409445.Google Scholar
Sun, S.S. & McDonough, W.F. (1989) Chemical and isotopic systematics of oceanic basaltic: implications for mantle composition and processes. Pp. 313345 in. Magmatism in the Ocean Basins (Saunders, A.D. and Norry, M.J., editors). GSA Special Publication, 42. Geological Society of America.Google Scholar
Sunal, G. & Tüysüz, O. (2002) Palaeostress analysis of Tertiary post-collisional structures in the Western Pontides, northern Turkey. Geological Magazine, 139, 343 359.Google Scholar
Thirwall, R.S., Francis, P.W., Hammill, M. & Baker, M.C.W. (1982) The Andes. Pp. 187205 in. Andesites: Orogenic Andesites and Related Rocks (Thorpe., R.S. editor). John Wiley & Sons, London, New York. Google Scholar
Tüysüz, O. (1999) Geology of the Cretaceous sedimentary basins of the Western Pontides. Geological Journal, 34, 7593.Google Scholar
Weaver, C.E. (1976) The nature of T.O. in kaolinite. Clays and Clay Minerals, 24, 215218.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, 325343.Google Scholar
Wintsch, R.P. & Kvale, C.M. (1994) Differential mobility of elements in burial diagenesis of siliciclastic rocks. Journal of Sedimentary Resources, A64, 349 361.Google Scholar
Wood, D.A. (1980) The application of a Th-Hf-Ta diagram to problems of tectonomagnetic classification and to establishing the nature of crustal contamination of basaltic lavas of the British Tertiary volcanic province. Earth and Planetary Science Letters, 50, 11 30.Google Scholar
Wood, S.A. (1990) The aqueous geochemistry of the rare earth elements and yttrium (1) Review of available low-temperature data for inorganic complexes and the inorganic REE speciation of natural waters. Chemical Geology, 82, 159186.Google Scholar
Vallance, T.G. (1975) Spilitic degradation of a tholetitic basalt. Journal of Petrology, 15, 7996.Google Scholar
Yeniyol, M. & Ercan, T. (1989) Geology of the Northern Istanbul, petrochemical characteristics of Upper Cretaceous volcanism and its regional distribution in Pontides. I.U. Yerbilimleri Dergisi, 7, 125147.Google Scholar
Yiíitbas°, E., Elmas, A. & Yõlmaz, Y. (1999) Pre-Cenozoic tectono-stratigraphic components of the Western Pontides and their geological evolution. Geological Journal, 34, 5574.Google Scholar
Zhou, Y., Ren, Y. & Bohor, B.F. (1982) Origin and distribution of tonsteins in lake Permien coal seams of southwestern China. International Journal of Coal Geology, 2, 49 77.Google Scholar
Zielinski, R.A. (1982) The mobility of U and other elements during alteration of rhyolite ash to montmorillonite: A case study in the Troublesome formation, Colorado, USA. Chemical Geology, 35, 185 204.Google Scholar
Zielinski, R.A. (1985) Element mobility during alteration of silicic ash to kaolinite – A study of tonstein. Sedimentology, 32, 567579.Google Scholar