Hostname: page-component-848d4c4894-nr4z6 Total loading time: 0 Render date: 2024-05-16T17:23:01.428Z Has data issue: false hasContentIssue false
  • English
  • Français

Retention of Cobalt by Pure and Foreign-Element Associated Goethites

Published online by Cambridge University Press:  28 February 2024

Allan Bibak ,
Joachim Gerth  and
Ole K. Borggaard
Allan Bibak
Affiliation:
Chemistry Department, Royal Veterinary and Agricultural University, 40 Thorvaldsensvej, DK-1871 Frederiksberg C, Denmark
Joachim Gerth
Affiliation:
Arbeitsbereich Umweltschutztechnik, Technische Universtät Hamburg-Harburg, Eissendorfer Str. 40, D-21073 Hamburg, Germany
Ole K. Borggaard
Affiliation:
Chemistry Department, Royal Veterinary and Agricultural University, 40 Thorvaldsensvej, DK-1871 Frederiksberg C, Denmark
Get access Rights & Permissions [Opens in a new window]

Abstract

Retention studies of the cobalt-goethite system were carried out using synthetic, star-shaped and lath-shaped pure, Al-, Cd-, Cu- and Si-associated goethites. Aluminium and Si are commonly occurring foreign elements in natural goethites. The goethites were prepared by coprecipitating Fe and the foreign element under controlled conditions and characterized by X-ray diffraction, transmission electron microscopy, specific surface area determination and 2 M HCl extraction. The foreign-element associated goethites contained ∼3, ∼5 and ∼9 mole % Al, ∼4 mole % Cd and ∼3 mole % Cu incorporated by isomorphous substitution but only ∼0.4 mole % of probably occluded Si. Crystal size and shape but also number of defects and domains, and hence specific surface area, unit-cell dimensions and reactivity towards 2 M HCl, exhibited great variability among the goethites. Accordingly the amounts of Co sorbed from initially 10−7 M Co in 0.1 M Ca(NO3)2 in relation to pH (3–8) and reaction time (2–504 h) were very different for the eight goethites. The affinity of Co is highest for Cd- and lowest for Cu-goethite. These samples also form the extremes regarding time-dependent sorption with Cu-goethite showing the smallest and Cd-goethite the largest increase in sorption with increasing reaction time. The Co uptake was not caused by precipitation Co(III) oxides due to Co(II) oxidation, since oxygen exclusion during sorption had no effect on the amount of Co sorbed. The amounts of sorbed Co extracted by 2 M HCl decreased with increasing sorption time but 40–87% of sorbed Co remained unextracted after 48 h, most in Cu-goethite and least in lath-shaped pure goethite. The strong retention suggests Co uptake by diffusion into micropores and fissures resulting from structural defects and intergrowths. The diffusion coefficients range from 3·10−19 to 6·10−17 cm2/s with the highest values for Al- and Si-associated goethites emphasizing the importance for Co immobilization, and hence availability, of foreign-element associations in goethite.

Keywords

Al-goethiteCd-goethiteCo-extractionCo-sorptionCu-goethiteMicropore diffusionSi-goethite
Type
Research Article
Information
Clays and Clay Minerals , Volume 43 , Issue 2 , April 1995 , pp. 141 - 149
Copyright
Copyright © 1995, 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

Alloway, B. J., 1990. Heavy Metals in Soils. Glasgow: Blackie, 339 pp.Google Scholar
Benjamin, M. M., and Leckie, J. O. 1981 . Multiple-site adsorption of Cd, Cu, Zn, and Pb on amorphous iron oxyhydroxide. J. Colloid Interf. Sci. 79: 209–221.CrossRefGoogle Scholar
Borggaard, O. K., 1990. Dissolution and Adsorption Properties of Soil Iron Oxides. Copenhagen: DSR-Forlag, 122 pp.Google Scholar
Bruemmer, G. W., Gerth, J., and Tiller, K. G. 1988 . Reaction kinetics of the adsorption and desorption of nickel, zinc and cadmium by goethite. I. Adsorption and diffusion of metals. J. Soil Sci. 39: 37–52.CrossRefGoogle Scholar
Cornell, R. M., and Giovanoli, R. 1986 . Factors that govern the formation of multi-domainic goethites. Clays & Clay Miner. 34: 557–564.CrossRefGoogle Scholar
Cornell, R. M., Giovanoli, R., and Schindler, P. W. 1987 . Effect of silicate species on the transformation of ferrihydrite into goethite and hematite in alkaline media. Clays & Clay Miner. 35: 21–28.CrossRefGoogle Scholar
Crank, J., 1975. The Mathematics of Diffusion, 2. Ed. Oxford: Clarendon Press, 11–27.Google Scholar
Fordham, A., and Norrish, K. 1983 . The nature of soil particles particularly those reacting with arsenate in a series of chemically treated samples. Aus. J. Soil Res. 31: 455–477.CrossRefGoogle Scholar
Gerth, J., 1990. Unit-cell dimensions of pure and trace metal-associated goethites. Geochim. Cosmochim. Acta 54: 363–371.CrossRefGoogle Scholar
Gerth, J., Brümmer, G. W., and Tiller, K. G. 1993 . Retention of Ni, Zn and Cd by Si-associated goethite. Z. Pflanzenernähr. Bodenk. 156: 123–129.CrossRefGoogle Scholar
Gillman, G. P., 1984. Using variable charge characteristics to understand the exchangeable cation status of oxic soils. Aust. J. Soil Res. 22: 71–80.CrossRefGoogle Scholar
Kosmas, C. S., Franzmeier, D. P., and Schulze, D. G. 1986 . Relationship among derivative spectroscopy, color, crystallite dimensions, and Al substitution of synthetic goethites and hematites. Clays & Clay Miner. 34: 625–634.CrossRefGoogle Scholar
Kumar, R., Ray, R. K., and Biswas, A. K. 1990 . Physicochemical nature and leaching behaviour of goethites containing Ni, Co and Cu in the sorption and coprecipitation mode. Hydrometallurgy 25: 61–83.CrossRefGoogle Scholar
Mann, S., Cornell, R. M., and Schwertmann, U. 1985 . The influence of aluminium on iron oxides: XII. High-resolution transmission electron microscopic (HRTEM) study of aluminous goethites. Clay Miner. 20: 255–262.CrossRefGoogle Scholar
Norrish, K., and Taylor, R. M. 1961 . The isomorphous replacement of iron by aluminium in soil goethite. J. Soil Sci. 12: 294–306.CrossRefGoogle Scholar
Padmanabham, M., 1983. Competitive study of the adsorption-desorption behaviour of Cu(II), Zn(II), Co(II) and Pb(II) at the goethite-solution interface. Aust. J. Soil Res. 21: 515–525.CrossRefGoogle Scholar
Quin, T. G., Long, G. J., Benson, C. G., Mann, S., and Williams, R. J. P. 1988 . Influence of silicon and phosphorus on structural and magnetic properties of synthetic goethite and related oxides. Clays & Clay Miner. 36: 165–175.CrossRefGoogle Scholar
Schenck, C. V., Dillard, J. G., and Murray, J. W. 1983 . Surface analysis and sorption of Co(II) on goethite. J. Colloid Interf. Sci. 95: 398–409.CrossRefGoogle Scholar
Schulze, D. G., 1984. The influence of aluminium on iron oxides. VIII. Unit-cell dimensions of Al-substituted goethites and estimation of Al from them. Clays & Clay Miner. 32: 36–44.CrossRefGoogle Scholar
Schulze, D. G., and Schwertmann, U. 1984 . The influence of Al on iron oxides. X. Properties of Al-substituted goethites. Clay Miner. 19: 521–539.CrossRefGoogle Scholar
Schulze, D. G., and Schwertmann, U. 1987 . The influence of aluminium on iron oxides: XIII. Properties of goethites synthesised in 0.3 M KOH at 25°C. Clay Miner. 22: 83–92.CrossRefGoogle Scholar
Schwertmann, U., 1964. Differenzierung der Eisenoxide des Bodens durch Extraktion mit Ammoniumoxalat-Lösung. Z. Pflanzenernähr. Düng. Bodenk. 105: 194–202.CrossRefGoogle Scholar
Schwertmann, U., 1984. The influence of Al on iron oxides. IX. Dissolution of Al-Goethites in 6 M HCl. Clay Miner. 19: 9–19.CrossRefGoogle Scholar
Smith, K. L., and Eggleton, R. A. 1983 . Botryoidal goethite: A transmission electron microscope study. Clays & Clay Miner. 31: 392–396.CrossRefGoogle Scholar
White, A. F., and Yee, A. . Near-surface alkali diffusion into glassy and crystalline silicates at 25°C to 100°C. In Geochemical Processes at Mineral Surfaces. Davis, J. A., and Hayes, K. F., 1986 eds. Washington: American Chemical Society Symposium Series 323, 586–598.Google Scholar