Hostname: page-component-76fb5796d-25wd4 Total loading time: 0 Render date: 2024-04-28T22:31:38.567Z Has data issue: false hasContentIssue false

The effect of CO2 and oxidation rate on the formation of goethite versus lepidocrocite from an Fe(II) system at pH 6 and 7

Published online by Cambridge University Press:  09 July 2018

L. Carlson
Affiliation:
Lehrstuhl für Bodenkunde, Technische Universität München, D-8050 Freising-Weihenstephan, Federal Republic of Germany
U. Schwertmann
Affiliation:
Lehrstuhl für Bodenkunde, Technische Universität München, D-8050 Freising-Weihenstephan, Federal Republic of Germany

Abstract

To investigate the influence of carbonate on the formation of goethite and lepidocrocite, ∼200 samples were synthesized by oxidizing FeCl2 solutions with air/CO2 gas mixtures at ambient temperature and pH 6 and 7. The proportion of lepidocrocite in the lepidocrocite/goethite mixtures (Lp/(Lp + Gt)) decreased from 100 to 0% with increasing in solution and with decreasing average oxidation rate (AOR). These two parameters explained 81% of the variation of Lp/(Lp + Gt)). At a given , more goethite was formed at pH 6 than at pH 7. The Lp + Gt mixtures contained 0–8 mg g−1 carbon (Ct) which could not be removed by washing. Ct reached apparent saturation at a equilibrium concentration of ∼6–8 and 60–80 mmol l−1 at pH 6 and pH 7, respectively. In a plot of Ct vs. Lp/(Lp + Gt) all data fell on the same line irrespective of oxidation parameters (pH, AOR). IR spectra showed two broad bands at ∼1300 and 1500 cm−1 which can be assigned to distorted carbonate adsorbed at the goethite surface. Identical bands were also found in a young, poorly crystalline goethite formed from coal mine drainage in Ohio. It is suggested that carbonate anions direct the polymerization of the double bands of FeO3(OH)3 octahedra common to both minerals toward a corner sharing arrangement, and thereby to goethite, whereas chloride permits edge-sharing as in lepidocrocite.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1990

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Carter, D., Heilman, M.D. & Gonzales, C.L. (1965) Ethylene glycol monoethyl ether for determining surface areas of silicate minerals. Soil Sci., 100, 356–360.Google Scholar
Fey, M.V. & Dixon, J.B. (1981) Synthesis and properties of poorly crystalline hydrated aluminous goethites. Clays Clay Miner., 29, 91–100.Google Scholar
Goodman, B.A. & Lewis, D.G. (1981) Mossbauer spectra of aluminous goethites (α-FeOOH). J. Soil Sci., 32, 351–363.Google Scholar
Harrison, J.B. & Berkheishr, V.E. (1982) Anion interaction with freshly precipitated hydrous iron oxides. Clays Clay Miner., 30, 97–102.Google Scholar
Rochester, C.H. & Topham, S. A. (1979) Infrared studies of the adsorption of probe molecules onto the surface of goethite. J. Chem. Soc., Faraday Trans. I 75, 872882.Google Scholar
Russell, J.D., Paterson, E., Fraser, A.R. & Farmer, V.C. (1975) Adsorption of carbon dioxide on goethite (α-FeOOH) surfaces, and its implications for anion adsorption. J. Chem. Soc., Faraday Trans. I 71, 16231630.Google Scholar
Schwertmann, U. (1959) Uber die Synthese definierter Eisenoxyde unter verschiedenen Bedingungen. Z. anorg. allg. Chemie, 298, 337–348.Google Scholar
Schwertmann, U. & Fitzpatrick, R.W. (1977) Occurrence of lepidocrocite and its association with goethite in Natal soils. Soil Sci. Soc. Am. J., 41, 1013–1018.Google Scholar
Taylor, R.M. & McKenzie, R.M. (1980) The influence of aluminum on iron oxides. VI. The formation of Fe(II)-Al(III) hydroxychlorides, -sulfates, and -carbonates as new members of the pyroaurite group and their significance in soils. Clays Clay Miner., 28, 179–187.Google Scholar
Yapp, C.J. (1987) A possible goethite-iron(III)carbonate solid solution and the determination of CO2 partial pressures in low-temperature geological systems. Chem. Geol., 64, 259–268.Google Scholar