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Transformations of Synthetic Birnessite as Affected by pH and Manganese Concentration

Published online by Cambridge University Press:  28 February 2024

Shihua Tu ,
Geza J. Racz  and
Tee Boon Goh
Shihua Tu
Affiliation:
Department of Soil Science, University of Manitoba Winnipeg, Manitoba, Canada R3T 2N2
Geza J. Racz
Affiliation:
Department of Soil Science, University of Manitoba Winnipeg, Manitoba, Canada R3T 2N2
Tee Boon Goh
Affiliation:
Department of Soil Science, University of Manitoba Winnipeg, Manitoba, Canada R3T 2N2
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Abstract

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The amount of Mn2+ adsorbed or removed from solution by birnessite is several times greater than its reported cation exchange capacity. Extractability of the sorbed Mn2+ decreases with aging. It is uncertain whether the sorbed Mn2+ is oxidized on the surface or incorporated into the structure of birnessite. Using X-ray powder diffractometry and transmission electron microscopy, a study was conducted to examine the mineralogical alteration of birnessite after treatment with various concentrations of MnSO4 and solution pH.

The sorbed Mn2+ was not directly oxidized and remained on the birnessite surface. The sorption of Mn2+ was followed by alteration of birnessite with the formation of new Mn minerals. The specific Mn minerals formed were governed by the pH of the reaction, and the rate of the transformation was determined by Mn2+ concentration and pH. Nsutite and ramsdellite were identified at pH 2.4, crypto-melane at pH 4, groutite at pH 6, and manganite at pH 8. Other Mn minerals formed at these and other pH levels could not be identified. As the concentration of Mn in the solution decreased, the time required to form new minerals from the birnessite increased. The newly formed phases were the result of structural conversion since dissolution of birnessite and reprecipitation of new phases were not observed.

Keywords

BirnessiteManganese oxidesMn2+ concentrationpHStructural conversionTEMXRD
Type
Research Article
Information
Clays and Clay Minerals , Volume 42 , Issue 3 , June 1994 , pp. 321 - 330
Copyright
Copyright © 1994, Clay Minerals Society

References

Brown, F. H., Pabst, A., and Sawyer, D. L., (1971) Birnessite on colemanite at Boron, California: Amer. Mineral. 56, 1057–1064.Google Scholar
Buser, W. P., and Feitknecht, W., (1954) Beitrag zur Kenntnis der Mangan(II)-manganite und des δ-MnO2: Helv. Chim. Acta 37, 2322–2333.CrossRefGoogle Scholar
Davis, J. A., and Kent, D. B.. () Surface complexation modelling in aqueous geochemistry: in Mineral-water Interface Geochemistry: Reviews in Mineralogy, 23, Hochella, M. F. Jr. and White, A. F., 1990 eds., 177–260.CrossRefGoogle Scholar
Feitknecht, W., Oswald, H. R., and Feitknecht-Steimann, V., (1960) Uber die topochemische einphasige reduktion von γ-MnO2. Helv. Chim. Acta. 48, 1947–1950.CrossRefGoogle Scholar
Fendorf, S. E., Sparks, D. L., Franz, J. A., and Camaioni, D. M., (1993) Electron paramagnetic resonance stopped-flow kinetic study of manganese(II) sorption-desorption on birnessite: Soil Sci. Soc. Am. J. 57, 57–62.CrossRefGoogle Scholar
Frondel, O., Mervin, O. B., and Ito, J., (1960) New data on birnessite and hollandite: Amer. Mineral. 45, 871–875.Google Scholar
Gattow, G., and Glemser, O., (1961) Darstellung und Eigenschaften von Braunstein. Part II: Die γ-and $eT-Gruppe der Brausteine: Z. Anorg. Allg. Chem. 309, 20–36.CrossRefGoogle Scholar
Glemser, O., Gattow, G., and Heisiek, H., (1961) Darstellung und Eigenschaften von Braunstein. Part I: Die δ-Gruppe der Brausteine: Z. Anorg. Allg. Chem. 309, 1–19.CrossRefGoogle Scholar
Golden, D. C., Dixon, J. B., and Cheng, C. C., (1986) Ion exchange, thermal transformations, and oxidizing properties of birnessite: Clays & Clay Minerals 34, 511–520.CrossRefGoogle Scholar
Healy, T. W., Herring, A. P., and Fuerstenau, D. W., (1966) The effect of crystal structure on the surface properties of a series of manganese dioxides: J. Colloid Interface Sci. 21, 435–444.CrossRefGoogle Scholar
Hem, J. D., (1963) Chemical equilibria and rates of manganese of oxidation: US. Geol. Surv. Water Supply Paper 1667–A.Google Scholar
JCPDS—International Centre for Diffraction Data. (1992) Feint-Marquart's μPDSM micropowder diffraction search/match. Release 4.30. Pennsylvania, USA.Google Scholar
Jones, L. H. P., and Milne, A. A., (1956) Birnessite, a new manganese oxide mineral from Aberdeenshire, Scotland: Mineral Mag. 31, 283–288.Google Scholar
Koljonen, T., Lahermo, P., and Garlson, L., (1976) Origin, mineralogy and geochemistry of manganese rocks and ferruginous precipitates found in sand graveldeposits in Finland: Bull. Geol. Soc. Finland 48, 111–135.CrossRefGoogle Scholar
Krauskopf, K. B., (1972) Geochemistry of micronutrients: in Micronutrients in Agriculture, Mortvedt, J. J., Cox, F. R., Shuman, L. M., and Walsh, R. M., eds., Soil Science Society of America, Madison, Wisconsin, 7–36.Google Scholar
McKenzie, R. M., (1971) The synthesis of birnessite, cryptomelane and some other oxides and hydroxides of manganese: Mineral Mag. 38, 493–502.CrossRefGoogle Scholar
McKenzie, R. M., (1980a). The adsorption of lead and other heavy metals on oxides of manganese and iron. Aust. J. Soil Res. 18, 61–73.CrossRefGoogle Scholar
McKenzie, R. M., (1980b) The manganese oxides in soils: in Geology and Geochemistry of Manganese, Vol. I, I. M. Varentsov and Gy Grasselly, eds., Hungarian Academy of Science, Budapest, 259–269.Google Scholar
McKenzie, R. M., (1981) The surface charge on manganese dioxide: Aust. J. Soil. Sci. Res. 19, 41–50.CrossRefGoogle Scholar
McKenzie, R. M., (1989) The manganese oxides and hydroxides: in Minerals in Soil Environments, Dixon, J. B., and Weed, S. B., eds., Soil Science Society of America, Madison, Wisconsin, 439–465.Google Scholar
Morgan, J. J., and Stumm, W., (1964) The role of multivalent metal oxides in limnological transformations as exemplified by iron and manganese: Adv. Water Pollut. Res., Proc. Int. Conf. 2nd. (Tokyo), Pergamon Press, Oxford. 103–118.Google Scholar
Murray, J. W., and Dillard, J. G., (1979) The oxidation of cobalt(II) adsorbed on manganese oxide: Geochim. Cosmochim. Acta. 43, 781–787.CrossRefGoogle Scholar
Pankow, J. F., and Morgan, J. J., (1981) Kinetics for the aquatic environment: Environmental Sci. and Tech, 15, 1306–1313.CrossRefGoogle ScholarPubMed
Sung, W., and Morgan, J. J., (1981) Oxidative removal of Mn(II) from solution catalysed by the γ-FeOOH (lepidocrocite) surface: Geochim. Cosmochim. Acta 45, 2377–2383.CrossRefGoogle Scholar
Tu, S., (1993) Effects of KCl on solubility and bioavailability of Mn in soil and some reactions of birnessite in the presence of some Mn compounds. Ph.D. Dissertation, University of Manitoba, 112 pp.Google Scholar