Hostname: page-component-76fb5796d-45l2p Total loading time: 0 Render date: 2024-04-27T21:24:50.976Z Has data issue: false hasContentIssue false

Effects of Oxyanions on the Edta-Promoted Dissolution of Goethite

Published online by Cambridge University Press:  01 January 2024

Jillian L. Campbell
Affiliation:
Department of Crop and Soil Environmental Sciences, 236 Smyth Hall, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, USA
Matthew J. Eick*
Affiliation:
Department of Crop and Soil Environmental Sciences, 236 Smyth Hall, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, USA
*
*E-mail address of corresponding author: eick@vt.edu

Abstract

Organic ligands, such as EDTA, accelerate the dissolution of silicate and oxide minerals. In natural systems, oxyanions can compete with organic ligands for mineral surface sites thereby affecting ligand-promoted dissolution rates, either enhancing or inhibiting dissolution, depending upon pH. The influence of selenite, molybdate and phosphate on the EDTA-promoted dissolution of goethite has been examined and a mechanism proposed for the observed differences in dissolution rates over a pH range of 4–8. We propose that the surface complex formed by EDTA is the controlling factor for the observed dissolution rate, with mononuclear complexes accelerating dissolution compared to bi- or multinuclear complexes. Dissolution results from our experiments suggest that EDTA forms multinuclear complexes at pH values ⩾6 and mononuclear complexes at pH values <6. Dissolution results show that when the oxyanion and the EDTA are present in the system at concentrations nearly equalling the surface sites available for adsorption, the oxyanion reduces the adsorption of EDTA and inhibits dissolution. However, if the oxyanion is present at lower concentrations at pH values ⩾6, EDTA is adsorbed but the number of carboxylic groups that can bind to the surface is reduced causing the formation of mononuclear complexes. This shift to a weaker surface complex enhances the EDTA-promoted dissolution of goethite in the presence of the oxyanions compared to EDTA-promoted dissolution in their absence.

Type
Research Article
Copyright
Copyright © 2002, The Clay Minerals Society

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

Bibak, A. and Borggaard, O.K., (1994) Molybdenum adsorption by aluminum and iron oxides and humic acid Soil Science 158 323328 10.1097/00010694-199411000-00003.CrossRefGoogle Scholar
Bondietti, G. Sinniger, J. and Stumm, W., (1993) The reactivity of Fe(III) (hydr)oxides: Effects of ligands in inhibiting the dissolution Colloids and Surfaces A: Physiochemical and Engineering Aspects 79 157167 10.1016/0927-7757(93)80171-A.CrossRefGoogle Scholar
Borggaard, O.K., (1991) Effects of phosphate on iron oxide dissolution in ethylenediamine-N,N,N′,N′-tetraacetic acid and oxalate Clays and Clay Minerals 39 324328 10.1346/CCMN.1991.0390313.CrossRefGoogle Scholar
Chang, H.C. and Matijevic, E., (1983) Interactions of metal hydrous oxides with chelating agents Journal of Colloid and Interface Science 92 479488 10.1016/0021-9797(83)90169-8.CrossRefGoogle Scholar
Eick, M.J. Peak, J.D. and Brady, W.D., (1999) The effect of ox yanions on the oxalate-promoted dissolution of goethite Soil Science Society of America Journal 63 11331141 10.2136/sssaj1999.6351133x.CrossRefGoogle Scholar
Goldberg, S. and Forster, H.S., (1998) Factors affecting molybdenum adsorption by soils and minerals Soil Science 163 109114 10.1097/00010694-199802000-00004.CrossRefGoogle Scholar
Hiemstra, T. and Van Riemsdijk, W.H., (1996) A surface structural approach to ion adsorption: The charge distribution (CD) model Journal of Colloid and Interface Science 179 488508 10.1006/jcis.1996.0242.CrossRefGoogle Scholar
Hingston, F.J. Posner, A.M. and Quirk, J.P., (1972) Anion adsorption by goethite and gibbsite: I. The role of the proton in determining adsorption envelopes Journal of Soil Science 23 177192 10.1111/j.1365-2389.1972.tb01652.x.CrossRefGoogle Scholar
Litter, M.I. and Blesa, M.A., (1987) Photodissolution of iron oxides Journal of Colloid and Interface Science 125 679687 10.1016/0021-9797(88)90035-5.CrossRefGoogle Scholar
Manceau, A. and Charlet, L., (1994) The mechanism of selenate adsorption on goethite and hydrous ferric oxide Journal of Colloid and Interface Science 168 8793 10.1006/jcis.1994.1396.CrossRefGoogle Scholar
McBride, M.B., (1994) Environmental Chemistry of Soils New York Oxford University Press 406 pp.Google Scholar
McKenzie, R.M., (1983) The adsorption of molybdenum on oxide surfaces Australian Journal of Soil Research 21 505513 10.1071/SR9830505.CrossRefGoogle Scholar
Means, J.L. Kucak, T. and Crear, D.A., (1980) Relative degradation rates of NTA, EDTA, and DTPA, and environmental implications Environmental Pollution 1 45 60.Google Scholar
Nowack, B. and Sigg, L., (1996) Adsorption of EDTA and metal-EDTA complexes onto goethite Journal of Colloid and Interface Science 177 106121 10.1006/jcis.1996.0011.CrossRefGoogle ScholarPubMed
Nowack, B. and Sigg, L., (1997) Dissolution of Fe(III) (hyr)oxides by metal-EDTA complexes Geochimica et Cosmochimica Acta 61 951963 10.1016/S0016-7037(96)00391-2.CrossRefGoogle Scholar
Parfitt, R.L., (1978) Anion adsorption by soils and soil materials Advances in Agronomy 30 1 50.Google Scholar
Rueda, E.H. Grass, R.L. and Blesa, M.A., (1985) Adsorption and dissolution in the system goethite/aqueous EDTA Journal of Colloid and Interface Science 106 243246 10.1016/0021-9797(85)90401-1.CrossRefGoogle Scholar
Schwertmann, U. and Cornell, R.M., (1991) Iron Oxides in the Laboratory New York VCH Publishers, Inc. 137 pp.Google Scholar
Schwertmann, U. Cambier, P. and Murad, E., (1985) Properties of goethites varying in crystallinity Clays and Clay Minerals 33 369378 10.1346/CCMN.1985.0330501.CrossRefGoogle Scholar
Stumm, W., (1992) Chemistry of the Solid-Water Interface New York John Wiley & Sons, Inc. 428 pp.Google Scholar
Stumm, W., (1997) Reactivity at the mineral-water interface: dissolution and inhibition Colloids and Surfaces A: Physiochemical and Engineering Aspects 120 143166 10.1016/S0927-7757(96)03866-6.CrossRefGoogle Scholar
Tejedor-Tejedor, I.M. and Anderson, M.A., (1986) ‘In situ’ attenuated total reflection Fourier transform infrared studies of the goethite (α-FeOOH)-aqueous solution interface Langmuir 2 203210 10.1021/la00068a016.CrossRefGoogle Scholar
Weast, R.C., (1986) CRC Handbook of Chemistry and Physics Boca Raton, Florida CRC Press D159 D163.Google Scholar
Zhang, P.C. and Sparks, D.L., (1989) Kinetics and mechanisms of molybdate adsorption/desorption at the goethite/water interface using pressure-jump relaxation Soil Science Society of America Journal 53 10281034 10.2136/sssaj1989.03615995005300040007x.CrossRefGoogle Scholar