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Experimental Study on the Formation of Clay Minerals from Obsidian by Interaction with Acid Solution at 150° and 200°C

Published online by Cambridge University Press:  28 February 2024

Motoharu Kawano  and
Katsutoshi Tomita
Motoharu Kawano
Affiliation:
Department of Environmental Sciences and Technology, Faculty of Agriculture, Kagoshima University, 1-21-24 Korimoto, Kagoshima 890, Japan
Katsutoshi Tomita
Affiliation:
Institute of Earth Sciences, Faculty of Science, Kagoshima University, 1-21-35 Korimoto, Kagoshima 890, Japan
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Abstract

Experimental alteration of obsidian with HCl solution was performed to elucidate dissolution mechanism and formation process of clay minerals in acid solution. Reactions were carried out using 0.1, 0.5, and 4.0 g of obsidian to 100 ml of 0.01 N HCl solution at 150° and 200°C for 1 to 60 days. The reaction products were examined by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy (TEM), and energy dispersive X-ray analysis. The surface composition of obsidian before and after alteration was investigated by X-ray photoelectron spectroscopy (XPS). TEM showed that boehmite precipitated at early stage and spherical kaolinite appeared subsequently by 200°C reactions. However, spherical halloysite occurred predominantly with small amounts of allophane, boehmite, and kaolinite by 150°C reaction in which formation process of the halloysite from allophane passing through an intermediate phase of small size rounded aggregate that consists of fine particles of allophane was observed. A boehmite exhibiting hexagonal platy habit with higher degree of crystallinity was formed by 200°C reaction as a stable phase in solution containing lower Si concentration at which the solution composition coincides with the stability field of boehmite on activity diagram for the system Na2O-Al2O3-SiO2-H2O. The fibrous boehmite having lower crystallinity appeared with increasing Si concentration, considered as a metastable phase in the stability field of kaolinite. XPS indicated that dissolution of obsidian in acid solution proceeded initially by cation exchange between Na ions and hydronium ions in solution and subsequently by preferential release of Al ions relative to Si from the Na depleted surface.

Keywords

Acid solutionAllophaneBoehmiteExperimental alterationHalloysiteObsidianSpherical kaolinite
Type
Research Article
Information
Clays and Clay Minerals , Volume 43 , Issue 2 , April 1995 , pp. 212 - 222
Copyright
Copyright © 1995, The Clay Minerals Society

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References

Allen, B. L., and Hajek, B. F. . Mineral occurrence in soil environments. In Minerals in Soil Environments. Dixon, J. B., and Weed, S. B., 1989 eds. Wisconsin: Soil Science Society, 199–278.Google Scholar
Brindley, G. W., and Radoslovich, W. W. 1956. X-ray studies of the alteration of soda feldspar. In Proc. Fourth Nat. Conf. Clays Clay Minerals, Vol. 4. Ada Swineford, ed. National Academy of Science: Washington, D.C.Google Scholar
Brown, G., 1980. Associated minerals. In Crystal Structure of Clay Minerals and Their X-ray Identification. Brindley, G. W., and Brown, G., eds. London: Mineralogical Society, 361–410.CrossRefGoogle Scholar
Busenberg, E., 1978. The products of the interaction of feldspars with aqueous solutions at 25°C. Geochim. Cosmochim. Acta 42: 1679–1686.CrossRefGoogle Scholar
Calvet, É., Boivinet, P., Noël, M., Thibon, H., Maillard, A., and Tertian, R. 1953 . Contribution à l'étude des gels d'alumine. Bull. Soc. Chim. Fr. 20: 99–108.Google Scholar
Chou, L., and Wollast, R. 1984 . Study of the weathering of albite at room temperature and pressure with a fluidized bed reactor. Geochim. Cosmochim. Acta 48: 2205–2218.CrossRefGoogle Scholar
Christoph, G. G., Corbató, C. E., Hofmann, D. A., and Tettenhorst, R. T. 1979 . The crystal structure of boehmite. Clays & Clay Miner. 27: 81–86.CrossRefGoogle Scholar
Dixon, J. B., 1989. Kaolin and serpentine group minerals. In Minerals in Soil Environments. Dixon, J. B., and Weed, S. B., eds. Wisconsin: Soil Science Society of America, 467–525.CrossRefGoogle Scholar
Farmer, V. C., Fraser, A. R., and Tait, J. M. 1979 . Characterization of the chemical structure of natural and synthetic aluminosilicate gels and sols by infrared spectroscopy. Geochim. Cosmochim. Acta 43: 1417–1420.CrossRefGoogle Scholar
Gruner, J. W., 1944. The hydrothermal alteration on feldspars in acid solutions between 300° and 400°C. Econ. Geol. 39: 578–589.CrossRefGoogle Scholar
Hall, P. L., Churchman, G. J., and Theng, B. K. G. 1985 . Size distribution of allophane unit particles in aqueous suspensions. Clays & Clay Miner. 33: 345–349.CrossRefGoogle Scholar
Helgeson, H. C., Garrels, R. M., and Mackenzie, T. 1969 . Evaluation of irreversible reactions in geochemical processes involving minerals and aqueous solutions—II. Applications. Geochim. Cosmochim. Acta 33: 455–481.CrossRefGoogle Scholar
Helgeson, H. C., 1971. Kinetics of mass transfer among silicates and aqueous solutions. Geochim. Cosmochim. Acta 35: 421–469.CrossRefGoogle Scholar
Hinckley, D. N., 1963. Variability in “crystallinity” values among the kaolin deposits of the coastal plain of Georgia and South Carolina. Clays & Clay Miner. 11: 229–235.CrossRefGoogle Scholar
Holdren, G. H. Jr., and Berner, R. A. 1979 . Mechanism of feldspar weathering—I. Experimental studies. Geochim. Cosmochim. Acta 43: 1161–1171.CrossRefGoogle Scholar
Huang, W. H., and Keller, W. D. 1973 . New stability diagrams of some phyllosilicates in the SiO2-Al2O3-K2O-H2O system. Clays & Clay Miner. 21: 331–336.CrossRefGoogle Scholar
Kawano, M., and Tomita, K. 1992 . Formation of allophane and beidellite during hydrothermal alteration of volcanic glass below 200°C. Clays & Clay Miner. 40: 666–674.CrossRefGoogle Scholar
Kawano, M., and Tomita, K. 1993 . Formation of clay minerals during low temperature hydrothermal alteration of obsidian (Part 1). Effect of addition of Al ions. Nendo Kagaku (J. Clay Sci. Soc. Japan) 33: 59–71 (in Japanese).Google Scholar
Kawano, M., Tomita, K., and Kamino, Y. 1993 . Formation of clay minerals during low temperature experimental alteration of obsidian. Clays & Clay Miner. 41: 431–441.CrossRefGoogle Scholar
Kittrick, J. A., 1970. Precipitation of kaolinite at 25°C and 1 atm. Clays & Clay Miner. 18: 216–267.CrossRefGoogle Scholar
La Iglesia, A., and Galan, E. 1975 . Halloysite-kaolinite transformation at room temperature. Clays & Clay Miner. 23: 109–113.CrossRefGoogle Scholar
La Iglesia, A., Martin-Vivaldi, J. L. Jr., and Aguayo, F. Lopez. 1976 . Kaolinite crystallization at room temperature by homogeneous precipitation—II: Hydrolysis of feldspars. Clays & Clay Miner. 24: 36–42.CrossRefGoogle Scholar
La Iglesia, A., and Van Oosterwyck-Gastuche, M. C. 1978 . Kaolinite synthesis. I. Crystallization conditions at low temperatures and calculation of thermodynamic equilibria. Application to laboratory and field observations. Clays & Clay Miner. 26: 397–408.CrossRefGoogle Scholar
Minato, H., and Utada, M. . Mode of occurrence and mineralogy of halloysite. In Proc. Inter. Clay Conf., Tokyo, 1969, Vol. 1. Heller, L., 1969 ed. Jerusalem: Israel University Press, 393–402.Google Scholar
Morey, G. W., and Chen, W. T. 1955 . The action of hot water on some feldspars. Amer. Mineral. 40: 996–1000.Google Scholar
Morey, G. W., and Fournier, R. O. 1961 . The decomposition of microcline, albite and nepheline in hot water. Amer. Mineral. 46: 688–699.Google Scholar
Murray, H. H., 1988. Kaolin minerals: Their genesis of occurrences. In Hydrous Phyllosilicates (Exclusive of Micas). Bailey, S. W., ed. Reviews in Mineralogy, Vol. 19. New York: Mineralogical Society of America, 67–89.CrossRefGoogle Scholar
Nagasawa, K., 1978a. Weathering of volcanic ash and other pyroclastic materials. In Clays & Clay Minerals of Japan. Sudo, T., and Shimoda, S., eds. Developments in Sedimentology, 26. Amsterdam: Elsevier, 105–125.CrossRefGoogle Scholar
Nagasawa, K., 1978b. Kaolin minerals. In Clays & Clay Minerals of Japan. Sudo, T., and Shimoda, S., eds. Developments in Sedimentology, 26. Amsterdam: Elsevier, 189–219.CrossRefGoogle Scholar
Papée, D., Tertian, R., and Biais, R. 1958 . Recherches sur la constitution des gels et des hydrates cristallisés d'alumine. Bull. Soc. Chim. Fr., Mem. Ser. 5: 1301–1310.Google Scholar
Parfitt, R. L., and Kimble, J. M. 1989 . Conditions for formation of allophane in soils. Soil Sci. Soc. Am. J. 53: 971–977.CrossRefGoogle Scholar
Parham, W. E., 1969. Formation of halloysite from feldspar: Low temperature artificial weathering versus natural weathering. Clays & Clay Miner. 17: 13–22.CrossRefGoogle Scholar
Robbie, R. A., and Waldbaum, D. R. 1968 . Thermodynamic properties of minerals and related substances at 298.15°K (25.0°C) and one atmosphere (1.013 bars) pressure and at higher temperatures. U.S. Geol. Surv. Bull. 1259: 256 pp.Google Scholar
Roy, R., and Osborn, E. F. 1954 . The system Al2O3-SiO2-H2O. Amer. Mineral. 39: 853–885.Google Scholar
Siefferann, G., and Millot, G. . Equatorial and tropical weathering of Recent basalts from Cameron: Allophane, halloysite, metahalloysite, kaolinite and gibbsite. In Proc. Inter. Clay Conf., Tokyo, 1969, Vol. 1. Heller, L., 1969 ed. Jerusalem: Israel University Press, 417–430.Google Scholar
Sudo, T., and Takahashi, H. 1956 . Shapes of halloysite particles in Japanese clays. Clays & Clay Miner. 4: 67–79.CrossRefGoogle Scholar
Sudo, T., and Takahashi, H. . The chlorites and interstratified minerals. In The Electron-optical Investigation of Clays. Gard, J. A., 1971 ed. London: Mineralogical Society, 277–300.CrossRefGoogle Scholar
Tamura, T., and Jackson, M. L. 1953 . Structural and energy relationships in the formation of iron and aluminium oxides, hydroxides and silicates. Science 117: 381–383.CrossRefGoogle ScholarPubMed
Tazaki, K., 1978. Micromorphology of plagioclase surface at incipient stage of weathering. Earth Science (Chikyu Kagaku) 32: 58–62 (in Japanese).Google Scholar
Tazaki, K., 1982. Analytical electron microscopic studies of halloysite formation processes—Morphology and composition of halloysite. In Inter. Clay Conf., 1981. Olphen, H. van and Veniale, F., eds. Developments in Sedimentology, 35. Amsterdam: Elsevier, 573–584.Google Scholar
Tchoubar, C., 1965. Formation de la kaolinite à partir d'albite altérée par l'eau à 200°C. Étude en microscopie et diffraction électroniques. Bull. Soc. Franc. Minér. Crist. 88: 483–518.Google Scholar
Tettenhorst, R., and Hofmann, D. A. 1980 . Crystal chemistry of boehmite. Clays & Clay Miner. 28: 373–380.CrossRefGoogle Scholar
Thomas, F. B., 1971. The kaolin minerals. In The Electronoptical Investigation of Clays. Gard, J. A., ed. London: Mineralogical Society, 109–157.Google Scholar
Tomura, S., Shibasaki, Y., Mizuta, H., and Kitamura, M. 1983 . Spherical kaolinite: Synthesis and mineralogical properties. Clays & Clay Miner. 31: 413–421.CrossRefGoogle Scholar
Tomura, S., Shibasaki, Y., Mizuta, H., and Kitamura, M. 1985 . Growth conditions and genesis of spherical and platy kaolinite. Clays & Clay Miner. 33: 200–206.CrossRefGoogle Scholar
Tsuzuki, Y., and Suzuki, K. 1980 . Experimental study of the alteration process of labradorite in acid hydrothermal solutions. Geochim. Cosmochim. Acta 44: 673–683.CrossRefGoogle Scholar
Tsuzuki, Y., and Kawabe, I. 1983 . Polymorphic transformations of kaolin minerals in aqueous solutions. Geochim. Cosmochim. Acta 47: 59–66.CrossRefGoogle Scholar
van Olphen, H., 1971. Amorphous clay materials. Science 171: 90–91.CrossRefGoogle Scholar
Velde, B., 1985. Clay Minerals, A physico-Chemical Explanation of their Occurrence, Developments in Sedimentology, 40: Amsterdam: Elsevier, 427 pp.Google Scholar
Wada, K., 1989. Allophane and imogolite. In Minerals in Soil Environments. Dixon, J. B., and Weed, S. B., eds. Wisconsin: Soil Science Society of America, 1051–1087.Google Scholar
Wada, S.-I., Eto, A., and Wada, K. 1979 . Synthetic allophane and imogolite. J. Soil Sci. 30: 347–355.CrossRefGoogle Scholar
Wada, S.-I., and Wada, K. 1981 . Formation between aluminate ions and orthosilicic acid in dilute alkaline to neutral solutions. Soil Sci. 132: 267–273.CrossRefGoogle Scholar
Watanabe, T., and Sudo, T. . Study on small-angle scattering of some clay minerals. In Proc. Int. Clay Conf., Tokyo, 1969, Vol. 1. Heller, L., 1969 ed. Jerusalem: Israel University Press, 173–181.Google Scholar
Wells, N., Childs, C. W., and Downes, C. J. 1977 . Silica spring, Tongariro National Park, New Zealand—Analysis of the spring water and characterization of the aluminosilicate deposit. Geochim. Cosmochim. Acta 41: 1498–1506.CrossRefGoogle Scholar