THE CATALYTIC ROLE OF BIRNESSITE IN THE TRANSFORMATION OF IRON

The influence of birnessite (δ-MnO2) on the precipitation products of iron was studied, in the FeCl2-NH4OH system at different Mn/Fe molar ratios (0, 0.01, 0.1 and 1.0) and in the acidic pH (4.0, 5.0 and 6.0) range, by X-ray, TEM, IR and chemical analyses. The precipitation products formed at pH 5.0 and 6.0 were found to be lepidocrocite (γ-FeOOH) in the absence of birnessite. Birnessite promoted increased precipitation of Fe oxide; the oxidation of Fe(II) by MnO2 was thermodynamically feasible and was confirmed by the presence of Mn(II) in the solution by ESR data. Birnessite also influenced the crystallization processes of hydrolytic products of Fe which range from lepidocrocite through goethite (α-FeOOH), akaganeite (β-FeOOH), to X-ray noncrystalline Fe oxides. The noncrystalline Fe oxides formed at a Mn/Fe molar ratio of 1.0 were characterized by infrared absorption maxima at 1400 and 750 cm−1. Key words: Birnessite, Fe(II) oxidation, ESR, lepidocrocite, akaganeite, noncrystalline oxide

[1]  P. Huang,et al.  Significance of Mn(IV) oxide in abiotic formation of organic nitrogen complexes in natural environments , 1984, Nature.

[2]  P. Huang,et al.  Kinetics of Oxidation of Arsenite by Various Manganese Dioxides1 , 1983 .

[3]  P. Huang,et al.  Role of Mn(IV) oxide in abiotic formation of humic substances in the environment , 1982 .

[4]  P. Huang,et al.  Oxidative power of Mn(IV) and Fe(III) oxides with respect to As(III) in terrestrial and aquatic environments , 1981, Nature.

[5]  P. Huang,et al.  The Nature of Selected Prairie Lake and Stream Sediments , 1981 .

[6]  U. Schwertmann,et al.  Natural and synthetic poorly crystallized lepidocrocite , 1979, Clay Minerals.

[7]  H. W. Van der Marel,et al.  Atlas of Infrared Spectroscopy of Clay Minerals and Their Admixtures , 1976 .

[8]  J. A. Gadsden Infrared Spectra of Minerals and Related Inorganic Compounds , 1975 .

[9]  J. Murray The surface chemistry of hydrous manganese dioxide , 1974 .

[10]  R. Mckenzie,et al.  The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese , 1971, Mineralogical Magazine.

[11]  M. Jackson Soil Chemical Analysis - Advanced Course. , 1969 .

[12]  E. Jenne Controls on Mn, Fe, Co, Ni, Cu, and Zn Concentrations in Soils and Water: the Significant Role of Hydrous Mn and Fe Oxides , 1968 .

[13]  J. Gebicki,et al.  Atlas of Electron Spin Resonance Spectra , 1967 .

[14]  U. Schwertmann Inhibitory Effect of Soil Organic Matter on the Crystallization of Amorphous Ferric Hydroxide , 1966, Nature.

[15]  D. Fuerstenau,et al.  The effect of crystal structure on the surface properties of a series of manganese dioxides , 1966 .

[16]  U. Schwertmann Zur Goethit- und Hämatitbildung aus amorphem Eisen(III)-hydroxid. 2. Mitteilung , 1965 .

[17]  A. Krause,et al.  Der Einfluß von PO43−-Ionen auf die Oxydation des Fe(OH)2 mit Luftsauerstoff und die Verhinderung der Magnetitbildung sowie die Struktur der Oxydationsprodukte , 1963 .

[18]  Konrad B. Krauskopf,et al.  Separation of manganese from iron in sedimentary processes , 1957 .

[19]  L. Jones Birnessite, a New Manganese Oxide Mineral from Aberdeenshire, Scotland , 1956 .