Hostname: page-component-cd9895bd7-jkksz Total loading time: 0 Render date: 2024-12-24T02:09:11.193Z Has data issue: false hasContentIssue false
  • English
  • Français

Coprecipitates of Cd, Cu, Pb and Zn in Iron Oxides: Solid Phase Transformation and Metal Solubility after Aging and Thermal Treatment

Published online by Cambridge University Press:  28 February 2024

Carmen Enid Martínez  and
Murray B. McBride
Carmen Enid Martínez
Affiliation:
Department of Soil, Crop, and Atmospheric Sciences, Cornell University, Ithaca, New York 14853, USA
Murray B. McBride
Affiliation:
Department of Soil, Crop, and Atmospheric Sciences, Cornell University, Ithaca, New York 14853, USA
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Solid phase transformation and metal solubility were monitored after coprecipitation of Cd2+, Cu2+, Pb2+ and Zn2+ with Fe3+ to form ferrihydrite by titration to pH 6. The (co)precipitates were aged at room temperature for up to 200 d and subsequently heated for 60 d at 70 °C. The mode of (co)precipitate formation, rapid and slow titration, was also investigated. Metal solubility was measured by anodic stripping voltammetry. Surface area, Fourier transform infrared (FTIR) and X-ray diffraction (XRD) analysis were used to follow the transformation of ferrihydrite after initial (co)precipitation. Electron microprobe analysis (EMPA) was used to show the distribution of metals within ferrihydrite aggregates. Thermal treatment produced a reduction in soluble Cd2+ and Zn2+, whereas Pb2+ appeared to be expelled from the solid phase. The more stable coprecipitate (formed by slow titration) maintained a constant Cu2+ solubility after thermal treatment. Characterization of the solid phase by XRD indicated that the presence of low levels of metals did not affect the initial or final transformation products, although metals present during the slow titration seemed to stabilize a higher surface area material. The rapid titration resulted in a less ordered (1-line) ferrihydrite than the slow titration (9-line). Furthermore, FTIR analysis indicated that the presence of metals promoted the formation of mixed (microcrystalline) end-products. The initial coprecipitation products seem to determine the final thermal transformation products. These transformation products include ferrihydrite, hematite (Hm), and goethite (Gt)- and lepidocrocite-like microcrystalline structures. Although experimental conditions were favorable for the homogeneous distribution of metals throughout the coprecipitate, EMPA suggests that Cu and Zn segregation within aggregates of Fe oxides occurs.

Keywords

Aging StudyCoprecipitationElectron Microprobe AnalysisFerrihydrite TransformationMetal SolubilityRate of TitrationThermal Treatment
Type
Research Article
Information
Clays and Clay Minerals , Volume 46 , Issue 5 , October 1998 , pp. 537 - 545
Copyright
Copyright © 1998, The Clay Minerals Society

References

Ainsworth, C.C. Pilon, J.L. Gassman, P.L. and Van Der Sluys, W.G., 1994 Cobalt, cadmium, and lead sorption to hydrous iron oxide: Residence time effects Soil Sci Soc Am J 58 1615–1623 10.2136/sssaj1994.03615995005800060005x.CrossRefGoogle Scholar
Anderson, P.R. and Benjamin, M.M., 1985 Effects of silicon on the crystallization and adsorption properties of ferric oxides Environ Sci Technol 19 1048–1053 10.1021/es00141a004.CrossRefGoogle ScholarPubMed
Cornell, R.M., 1988 The influence of some divalent cations on the transformation of ferrihydrite to more crystalline products Clay Miner 23 329–332 10.1180/claymin.1988.023.3.10.CrossRefGoogle Scholar
Cornell, R.M. and Giovanoli, R., 1987 Effect of manganese on the transformation of ferrihydrite into goethite and jacobsite in alkaline media Clays Clay Miner 35 11–20 10.1346/CCMN.1987.0350102.CrossRefGoogle Scholar
Cornell, R.M. and Giovanoli, R., 1988 The influence of copper on the transformation of ferrihydrite (5Fe2O3-9H2O) into crystalline products in alkaline media Polyhedron 7 385–391 10.1016/S0277-5387(00)80487-8.CrossRefGoogle Scholar
Cornell, R.M. and Giovanoli, R., 1989 Effect of cobalt on the formation of crystalline iron oxides from ferrihydrite in alkaline media Clays Clay Miner 37 65–70 10.1346/CCMN.1989.0370108.CrossRefGoogle Scholar
Cornell, R.M. Schneider, W. and Giovanoli, R., 1989 The transformation of ferrihydrite into lepidocrocite Clay Miner 24 549–553 10.1180/claymin.1989.024.3.08.CrossRefGoogle Scholar
Crawford, R.J. Harding, I.H. and Mainwaring, D.E., 1993 Adsorption and coprecipitation of single heavy metal ions onto the hydrated oxides of iron and chromium Langmuir 9 3050–3056 10.1021/la00035a051.CrossRefGoogle Scholar
Ford, R.G. Bertsch, P.M. and Farley, K.J., 1997 Changes in transition and heavy metal partitioning during hydrous iron oxide aging Environ Sci Technol 31 2028–2033 10.1021/es960824+.CrossRefGoogle Scholar
Kinniburgh, D.G. Jackson, M.L. and Syers, J.K., 1976 Adsorption of alkaline earth, transition, and heavy metal cations by hydrous oxide gels of iron and aluminum Soil Sci Soc Am J 40 796–799 10.2136/sssaj1976.03615995004000050047x.CrossRefGoogle Scholar
Kolthoff, I.M. and Moskovitz, B., 1937 Studies on coprecipitation and aging. XI. Adsorption of ammonio copper ion on and coprecipitation with hydrous ferric oxides. Aging of the precipitate J Phys Chem 41 629–644 10.1021/j150382a013.CrossRefGoogle Scholar
Manceau, A. Charlet, L. Boisset, M.C. Didier, B. and Spadini, L., 1993 Sorption and spéciation of heavy metals on hydrous Fe and Mn oxides: From microscopic to macroscopic Appl Clay Sci 7 201–223 10.1016/0169-1317(92)90040-T.CrossRefGoogle Scholar
Martínez, C.E. and McBride, M.B., 1998 Solubility of Cd2+, Cu2+, Pb2+, and Zn2+ in aged coprecipitates with amorphous iron hydroxides Environ Sci Technol 32 743–748 10.1021/es970262+.CrossRefGoogle Scholar
McBride, M.B., 1978 Retention of Cu2+, Ca2+, Mg2+, and Mn2+ by amorphous alumina Soil Sci Soc Am J 42 27–31 10.2136/sssaj1978.03615995004200010007x.CrossRefGoogle Scholar
Nalovic, L.J. Pedro, G. Janot, C. and Bailey, S.W., 1975 Demonstration by Mössbauer spectroscopy of the role played by transitional trace elements in the crystallogenesis of iron hydroxides (III) Proc Int Clay Conf Wilmette, IL Applied Publishing 601–610.Google Scholar
Sauve, S. McBride, M.B. and Hendershot, W.H., 1995 Ion-selective electrode measurements of copper (II) activity in contaminated soils Arch Environ Contam Toxicol 29 373–379 10.1007/BF00212503.CrossRefGoogle Scholar
Schwertmann, U. and Murad, E., 1983 Effect of pH on the formation of goethite and hematite from ferrihydrite Clays Clay Miner 31 277–284 10.1346/CCMN.1983.0310405.CrossRefGoogle Scholar
Schwertmann, U. Taylor, R.M., Dixon, J.B. and Weed, S.B., 1989 Iron oxides Minerals in soil environments Madison, WI Soil Sci Soc Am. 379–438.Google Scholar
Spadini, L. Manceau, A. Schindler, P.W. and Charlet, L., 1994 Structure and stability of Cd2+ surface complexes on ferric oxides 1. Results from EXAFS spectroscopy J Colloid Interface Sci 168 73–86 10.1006/jcis.1994.1395.CrossRefGoogle Scholar
Willett, I.R. Chartres, C.J. and Nguyen, T.T., 1988 Migration of phosphate into aggregated particles of ferrihydrite J Soil Sci 39 275–282 10.1111/j.1365-2389.1988.tb01214.x.CrossRefGoogle Scholar