Fe-kaolinite in granite saprolite beneath sedimentary kaolin deposits: A mode of Fe substitution for Al in kaolinite
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Mayumi Jige
,
Yoshio Takahashi
Abstract
Fe-kaolinite has been detected in granite saprolite beneath sedimentary kaolin deposits in the Seto district of central Japan. Granite saprolite, which was found underneath sedimentary kaolin deposits formed in fluvial and lacustrine environments, had been subjected to kaolinization. The clay fractions of granite saprolite consist mostly of kaolinite with subordinate micaceous clay, quartz, and feldspars. Electron probe microanalysis (EPMA) showed that the kaolinite in clay fractions contained an average 3.30–3.72 wt% of Fe2O3, indicative of Fe-kaolinite. Fe+Si was inversely proportional to Al in Fe-kaolinite, indicating coupled substitution between Fe+Si and Al. The K2O contents of Fe-kaolinite increased with increasing Fe2O3 up to 0.77 wt%, whereas K did not correlate with other elements, suggesting that K was not contained with the structure of kaolinite but was present in its interlayers. X-ray absorption near-edge structure (XANES) spectroscopy showed that about 60 to 70% of Fe in the clay fractions is ferric iron, and extended X-ray absorption fine structure (EXAFS) spectroscopy indicated that Fe is situated in octahedral sites replacing Al. Fe-kaolinite was likely precipitated by the infiltration of acidic groundwater with higher Fe and alkali contents into granite saprolite, accompanied by the intense kaolinization of sedimentary kaolin deposits.
Acknowledgments
We deeply appreciate Sadahisa Sudo, Yoshiaki Kon, Daisuke Araoka, Buenaventurada C. Segwaben, Chizu Namatame, Kumiko Miyakoshi, Izumi Matsunaga, and Akiko Tokumoto for their technical assistance. We also thank Aichi prefectural association of porcelain industries, Aichi prefectural association of silica sand mining industries, Gifu ceramics material association, Marufuji Mine Ltd., and Chubu bureau of economy, trade, and industry for their financial and political assistance. This study was supported by Grants-in-Aid for scientific research from the Ministry of Education, Culture, Sports, Science and Technology of Japan (16H04073 and 16K12627). This work has been performed with the approval of KEK (Proposal Nos. 2015G664 and 2016G632) and SPring-8 (Proposal No. 2017A1798).
References cited
Amigó, J.M., Bastida, J., Garcia Agramunt, M.J., Sanz, A., and Galván, J. (1987) Crystallinity of Lower Cretaceous kaolinites of Teruel (Spain). Proceedings, 6th Meeting of the European Clay Groups, Euroclay, 87, 74–75.10.1016/0169-1317(94)90014-0Suche in Google Scholar
Balan, E., Allard, T., Boizot, B., Morin, G., and Muller, J.-P. (1999) Structural Fe3+ in natural kaolinites: new insights from electron paramagnetic resonance spectra fitting at X and Q-band frequencies. Clays and Clay Minerals, 47, 605–616.10.1346/CCMN.1999.0470507Suche in Google Scholar
Delineau, T., Allard, T., Muller, J.-P., Barres, O., Yvon, J., and Cases, J.-M. (1994) FTIR reflectance vs. EPR studies of structural iron in kaolinites. Clays and Clay Minerals, 42, 308–320.10.1346/CCMN.1994.0420309Suche in Google Scholar
González, J.A., and Ruiz, M. del C. (2006) Bleaching of kaolins and clays by chlorination of iron and titanium. Applied Clay Science, 33, 219–229.10.1016/j.clay.2006.05.001Suche in Google Scholar
Hart, R.D., St. Pierre, T.G., Gilkes, R.J., McKinley, A.J., Siradz, S., and Singh, B. (2002) Iron in soil kaolins from Indonesia and Western Australia. Clay Minerals, 37, 671–685.10.1180/0009855023740069Suche in Google Scholar
Herbillon, A.J., Mestdash, M.M., Vielvoye, L., and Derouane, E.G. (1976) Iron in kaolinite with special reference to kaolinite from tropical soils. Clay Minerals, 11, 201–220.10.1180/claymin.1976.011.3.03Suche in Google Scholar
Hinckley, D.N. (1963) Variability in crystallinity values among the kaolin deposits of the coastal plain of Georgia and South Carolina. Clays and Clay Minerals, 11, 229–235.10.1346/CCMN.1962.0110122Suche in Google Scholar
Imai, N., Terashima, S., Itoh, S., and Ando, A. (1995) 994 compilation values for GSJ reference samples, “Igneous rock series”. Geochemical Journal, 29, 91–95.10.2343/geochemj.29.91Suche in Google Scholar
Iriarte, I., Petit, S., Huertas, F.J., Fiore, S., Grauby, O., Decarreau, A., and Linares, J. (2005) Synthesis of kaolinite with a high level of Fe3+ for Al substitution. Clays and Clay Minerals, 53, 1–10.10.1346/CCMN.2005.0530101Suche in Google Scholar
Ishihara, S., and Murakami, H. (2006) Fractionated ilmenite-series granites in southwest Japan: Source magma for REE-Sn-W mineralizations. Resource Geology, 56, 245–256.10.1111/j.1751-3928.2006.tb00282.xSuche in Google Scholar
Kesler, T.L. (1956) Environment and origin of the Cretaceous kaolin deposits of Georgia and South Carolina. Economic Geology, 51, 541–554.10.2113/gsecongeo.51.6.541Suche in Google Scholar
Kogel, J.E., Pickering, S.M. Jr., Shelobolina, E., Chowns, T., Yuan, J., and Avant, D.M. Jr. (2002) Origin of the Georgia-South Carolina commercial-grade kaolins. In The Georgia Kaolins, Geology and Utilization, p. 45–50 Society for Mining, Metallurgy, and Exploration, Inc. (SME), Colorado.Suche in Google Scholar
Makimoto, H., Yamada, N., Mizuno, K., Takada, A., Komazawa, M., and Sudo, S. (2004) Geological Map of Japan 1:200,000 Toyohashi and Irago Misaki. Geological Survey of Japan, AIST.Suche in Google Scholar
Maynard, R.N., Millman, N., and Iannicelli, J. (1968) A method for removing titanium dioxide impurities in kaolin. Clays and Clay Minerals, 17, 59–62.10.1346/CCMN.1969.0170203Suche in Google Scholar
Mendelovici, E., Yariv, S.H., and Villalba, R. (1979) Iron-bearing kaolinite in Venezuelan laterites: I. Infrared spectroscopy and chemical dissolution evidence. Clay Minerals, 14, 323–331.10.1180/claymin.1979.014.4.08Suche in Google Scholar
Morita, S., Takagi, T., Kon, Y., and Araoka, D. (2012) The accuracy and determination limits of rock chemical analysis by X-ray fluorescence spectrometry at Mineral Resources Research Group, Geological Survey of Japan. GSJ Open-file report, No. 624, 36 p.Suche in Google Scholar
Murray, H.H., and Lyons, S.C. (1959) Further correlations of kaolinite crystallinity with chemical and physical properties. Clays and Clay Minerals, Proceedings of 8th National Conference, 11–22.10.1016/B978-0-08-009351-2.50008-8Suche in Google Scholar
Nagasawa, K. (1978) Kaolin minerals. In T. Sudo and S. Shimoda, Eds., Clays and Clay Minerals of Japan, p. 189–219. Developments in Sedimentology 26, Kodansha-Elsevier.10.1016/S0070-4571(08)70686-1Suche in Google Scholar
Nakayama, K. (1991) Depositional processes of the Neogene Seto porcelain clay formation in the northern part of Seto city, central Japan. The Journal of Geological Society of Japan, 97, 945–958 (in Japanese with English abstract).10.5575/geosoc.97.945Suche in Google Scholar
Nogami, K. (1996) Spectrophotometric determination of FeO content in igneous rock by using 1,10 phenanthroline. Kazan, 41, 275–278 (in Japanese).Suche in Google Scholar
Schroeder, P.A., and Pruett, R.J. (1996) Fe ordering in kaolinite: Insights from 29Si and 27Al MAS NMR spectroscopy. American Mineralogist, 81, 26–31.10.2138/am-1996-1-204Suche in Google Scholar
Smrčok, L., Tunega, D., Ramirez-Cuesta, A.J., and Scholtzová, E. (2010) The combined inelastic neutron scattering and solid state DFT study of hydrogen atoms dynamics in a highly ordered kaolinite. Physics and Chemistry of Minerals, 37, 571–579.10.1007/s00269-010-0358-3Suche in Google Scholar
Tardy, Y., and Nahon, D. (1985) Geochemistry of laterites, stability of Al-goethite, Al-hematite, and Fe3+-kaolinite in bauxite and ferricretes: an approach to the mechanism of concretion formation. American Journal of Science, 285, 865–903.10.2475/ajs.285.10.865Suche in Google Scholar
Tessier, A., Campbell, P.G.C., and Bisson, M. (1979) Sequential extraction procedure for the speciation of particulate trace metals. Analytical Chemistry, 51, 845–851.10.1021/ac50043a017Suche in Google Scholar
Tomura, S., Kitamura, M., Shibasaki, Y., and Maeda, T. (1981) Iron in gairome clay-analytical electron microscope study. Yogyo-Kyokai-Shi, 98, 362–366. (in Japanese with English abstract)10.2109/jcersj1950.90.1043_362Suche in Google Scholar
Wilke, M., Farges, F., Petit, P.E., Brown, G.E. Jr., and Martin, F. (2001) Oxidation state and coordination of Fe in minerals: An Fe K-XANES spectroscopic study. American Mineralogist, 86, 714–730.10.2138/am-2001-5-612Suche in Google Scholar
Zabinsky, S.I., Rehr, J.J., Ankudinov, A., Albers, R.C., and Eller, M.J. (1995) Multiple-scattering calculations of X-ray-absorption spectra. Physical Review B, 52, 2995–3009.10.1103/PhysRevB.52.2995Suche in Google Scholar
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Artikel in diesem Heft
- Highlights and Breakthroughs
- Biosilica: Structure, function, science, technology, and inspiration
- Gypsum, bassanite, and anhydrite at Gale crater, Mars
- Redox-induced nucleation and growth of goethite on synthetic hematite nanoparticles
- Effect of alkalinity on sulfur concentration at sulfide saturation in hydrous basaltic andesite to shoshonite melts at 1270 °C and 1 GPa
- Is fibrous ferrierite a potential health hazard? Characterization and comparison with fibrous erionite
- Experimental investigation of basalt and peridotite oxybarometers: Implications for spinel thermodynamic models and Fe3+ compatibility during generation of upper mantle melts
- Pressure, sulfur, and metal-silicate partitioning: The effect of sulfur species on the parameterization of experimental results
- Analysis and visualization of vanadium mineral diversity and distribution
- On the relative timing of listwaenite formation and chromian spinel equilibration in serpentinites
- The dynamics of Fe oxidation in riebeckite: A model for amphiboles
- AMFORM, a new mass-based model for the calculation of the unit formula of amphiboles from electron microprobe analyses
- Fe-kaolinite in granite saprolite beneath sedimentary kaolin deposits: A mode of Fe substitution for Al in kaolinite
- Kalistrontite, its occurrence, structure, genesis, and significance for the evolution of potash deposits in North Yorkshire, U.K.
- The uppermost mantle section below a remnant proto-Philippine Sea island arc: Insights from the peridotite fragments from the Daito Ridge
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- Heat capacity measurements of CaAlSiO4F from 5 to 850 K and its standard entropy
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