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In Situ Infrared Speciation of Adsorbed Carbonate on Aluminum and Iron Oxides

Published online by Cambridge University Press:  28 February 2024

Chunming Su  and
Donald L. Suarez
Chunming Su*
Affiliation:
USDA-ARS, U.S. Salinity Laboratory, 450 West Big Springs Road, Riverside, California 92507-4617
Donald L. Suarez
Affiliation:
USDA-ARS, U.S. Salinity Laboratory, 450 West Big Springs Road, Riverside, California 92507-4617
*
†Present address: U.S. Environmental Protection Agency, National Risk Management Research Laboratory, 919 Kerr Research Drive, Ada, Oklahoma 74820.
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Abstract

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Surface adsorption mechanisms of dissolved inorganic carbon species on soil minerals are not well understood. Traditional infrared (IR) study of adsorbed species of inorganic carbon using air-dried samples may not reveal true species in the solid/water interface in suspension. The purpose of this study was to obtain information on interfacial carbonate speciation between solid and aqueous phases. The interaction of bicarbonate and carbonate ions with X-ray amorphous (am) Al and Fe oxides, gibbsite (γ−Al(OH)3) and goethite (α-FeOOH) was examined by electrophoresis and in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The presence of carbonate lowered the electrophoretic mobility and decreased the point of zero charge (PZC) of all minerals, implying specific adsorption. Inner-sphere complexation of bicarbonate and carbonate was supported by a lowering in the anion symmetry due to the interaction with Al and Fe oxide surfaces. Only complexed monodentate carbonate was identified in am-Al(OH)3/aqueous solution at pH 4.1-7.8 when the solid was reacted with either NaHC03 or Na2CO3 solutions. Am-Al(OH)3 was transformed to a crystalline sodium aluminum hydroxy carbonate, dawsonite [NaAl(CO3)(OH)2], and bayerite (α-Al(OH)3) after reacting with 1.0 M Na2CO3 for 24 h. Gibbsite adsorbed much less carbonate than am-Al(OH)3 such that adsorbed carbonate on gibbsite gave weak IR absorption. It is probable that monodentate carbonate is also the complexed species on gibbsite. Evidence suggesting the presence of both surface complexed bicarbonate and carbonate species in the interfacial region of am-Fe(OH)3 in suspension and the dependence of their relative distribution on solution pH is shown. Only monodentate carbonate was found in the interfacial region of goethite in 1.0 M NaHCO3. A ligand exchange reaction was proposed to describe the interaction of bicarbonate and carbonate with the surface functional groups of Al and Fe oxides.

Keywords

Attenuated Total Reflectance-Fourier Transform InfraredCarbonate AdsorptionElectro-phoretic MobilityInfraredPoint of Zero ChargePoint of Zero Net Proton ChargeX-ray Diffraction
Type
Research Article
Information
Clays and Clay Minerals , Volume 45 , Issue 6 , December 1997 , pp. 814 - 825
Copyright
Copyright © 1997, The Clay Minerals Society

References

Bruno, J. Stumm, W. and Wersin, P B F, 1992 On the influence of carbonate in mineral dissolution: I. The thermodynamics and kinetics of hematite dissolution in bicarbonate solutions at T= 25 °C Geochim Cosmochim Acta 56 1139–1147 10.1016/0016-7037(92)90051-J.CrossRefGoogle Scholar
Compton, S C DAC and Coleman, P.B., 1993 Optimization of data recorded by internal reflectance spectroscopy Practical sampling techniques for infrared analysis Boca Raton, FL CRC Pr 55–92.Google Scholar
Evans, T.D. Leal, J.R. and Arnold, P.W., 1979 The interfacial electrochemistry of goethite (α-FeOOH) especially the effect of CO2 contamination J Electroanal Chem 105 161–167 10.1016/S0022-0728(79)80347-2.CrossRefGoogle Scholar
Feldkamp, J.R. Shah, D.N. Meyer, S.L. White, J.L. and Hem, S.L., 1981 Effect of adsorbed carbonate on surface charge characteristics and physical properties of aluminum hydroxide gel J Pharm Sci 70 638–640 10.1002/jps.2600700616.CrossRefGoogle ScholarPubMed
Frueh, A.J. and Golightly, J.P., 1967 The crystal structure of daw-sonite NaAl(CO3)(OH)2 Can Mineral 9 51–56.Google Scholar
Hage, W. Hallbrucker, A. and Mayer, E., 1993 Carbonic acid: Synthesis by protonation of bicarbonate and FTIR spectroscopic characterization via a new cryogenic technique J Am Chem Soc 115 8427–8431 10.1021/ja00071a061.CrossRefGoogle Scholar
Harrison, J.B. and Berkheiser, V.E., 1982 Anion interactions with freshly prepared hydrous iron oxides Clays Clay Miner 30 97–102 10.1346/CCMN.1982.0300203.CrossRefGoogle Scholar
Hsu, P.H., 1967 Effect of salts on the formation of bayerite versus pseudo-boehmite Soil Sci 103 101–110 10.1097/00010694-196702000-00003.CrossRefGoogle Scholar
Hsu, P.H. and Bates, T.F., 1964 Formation of x-ray amorphous and crystalline aluminum hydroxides Mineral Mag 33 749–768.Google Scholar
Hunter, R.J., 1981 Zeta potential in colloid science London Academic Pr..Google Scholar
Hunter, D.B. and Bertsch, P.M., 1994 In situ measurements of te-traphenylboron degradation kinetics on clay mineral surfaces by IR Environ Sci Technol 28 686–691 10.1021/es00053a024.CrossRefGoogle ScholarPubMed
Kittrick, J.A., 1966 The free energy of formation of gibbsite and Al(OH)4 − by solubility measurements Soil Sci Soc Am Proc 30 595–598 10.2136/sssaj1966.03615995003000050018x.CrossRefGoogle Scholar
Kodama, H., 1985 Infrared spectra of minerals: Reference guide to identification and characterization of minerals for the study of soils Ottawa Agriculture Canada..Google Scholar
Lumsdon, D.G. and Evans, L.J., 1994 Surface complexation model parameters for goethite (α-FeOOH) J Colloid Interface Sci 164 119–125 10.1006/jcis.1994.1150.CrossRefGoogle Scholar
Nakamoto, K., 1986 Infrared and Raman spectra of inorganic and coordination compounds. 4th ed New York Wiley..Google Scholar
Nelson, R.E. et al. , Page, A.L. 1982 et al. , Carbonate and gypsum Methods of soil analysis. Part 2 Madison, WI Agron Monograph 181–197.Google Scholar
Ross, D., 1972 Inorganic infrared and Raman spectra London McGraw Hill..Google Scholar
Russell, J.D. Paterson, E. Fraser, A.R. and Farmer, V.C., 1975 Adsorption of carbon dioxide on goethite (α-FeOOH) surfaces, and its implications for anion adsorption J Chem Soc, Faraday Trans. 71 1623–1630 10.1039/f19757101623.CrossRefGoogle Scholar
Scholtz, E.C. Feldkamp, J.R. White, J.L. and Hem, S.L., 1984 Properties of carbonate-containing aluminum hydroxide produced by precipitation at constant pH J Pharm Sci 73 967–973 10.1002/jps.2600730727.CrossRefGoogle ScholarPubMed
Scholtz, E.C. Feldkamp, J.R. White, J.L. and Hem, S.L., 1985 Point of zero charge of amorphous aluminum hydroxide as a function of adsorbed carbonate J Pharm Sci 74 478–481 10.1002/jps.2600740423.CrossRefGoogle ScholarPubMed
Schulthess, C. M. J., 1990 Competitive adsorption of aqueous carbonic and acetic acids by an aluminum oxide Soil Sci Soc Am J 54 688–694 10.2136/sssaj1990.03615995005400030009x.CrossRefGoogle Scholar
Schwertmann, U. and Cornell, R.M., 1991 Iron oxides in the laboratory: Preparation and characterization New York VCH..Google Scholar
Serna, C.J. White, J.L. and Hem, S.L., 1977 Anion-aluminum hydroxide gel interactions Soil Sci Soc Am J 41 1009–1013 10.2136/sssaj1977.03615995004100050041x.CrossRefGoogle Scholar
Sposito, G., 1984 The surface chemistry of soils New York Oxford University Pr..Google Scholar
Stumm, W., 1986 Coordinative interactions between soil solids and water—An aquatic chemist’s point of view Geoderma 38 19–30 10.1016/0016-7061(86)90004-2.CrossRefGoogle Scholar
Su, C. and Suarez, D.L., 1995 Coordination of adsorbed boron: A FTIR spectroscopic study Environ Sci Technol 29 302–311 10.1021/es00002a005.CrossRefGoogle Scholar
Tejedor-Tejedor, M. and Anderson, M.A., 1986 “In situ” attenuated total reflection Fourier transform infrared studies of the goethite (α-FeOOH)-aqueous solution interface Langmuir 2 203–210 10.1021/la00068a016.CrossRefGoogle Scholar
Tejedor-Tejedor, M. and Anderson, M.A., 1990 Protonation of phosphate on the surface of goethite as studied by CIR-FTIR and electrophoretic mobility Langmuir 6 602–613 10.1021/la00093a015.CrossRefGoogle Scholar
Van Geen, A. Robertson, A.P. and Leckie, J.O., 1994 Complexation of carbonate species at the goethite surface: Implications for adsorption of metal ions in natural waters Geochim Cosmochim Acta 58 2073–2086 10.1016/0016-7037(94)90286-0.CrossRefGoogle Scholar
Weast, R.T., 1976 Handbook of chemistry and physics. 57th ed. Cleveland, OH CRC Pr..Google Scholar
White, J.L. and Hem, S.L., 1975 Role of carbonate in aluminum hydroxide gel established by Raman and IR Analyses J Pharm Sci 64 468–469 10.1002/jps.2600640330.CrossRefGoogle ScholarPubMed
Yapp, C.J. and Poths, H., 1990 Infrared spectral evidence for a minor Fe (III) carbonate-bearing component in natural goethite Clays Clay Miner 4 442–444 10.1346/CCMN.1990.0380414.CrossRefGoogle Scholar
Zachara, J.M. Girvin, D.C. Schmidt, R.L. and Resch, C.T., 1987 Chromate adsorption on amorphous iron oxyhydroxide in the presence of major groundwater ions Environ Sci Technol 21 589–594 10.1021/es00160a010.CrossRefGoogle ScholarPubMed
Zeltner, W.A. and Anderson, M.A., 1988 Surface charge development at the goefhite/aqueous solution interface: Effects of CO2 adsorption Langmuir 4 469–474 10.1021/la00080a039.CrossRefGoogle Scholar