Skip to main content
Log in

Reaction Scheme for the Oxidation of as(III) to as(V) by Birnessite

  • Published:
Clays and Clay Minerals

Abstract

The oxidation of As(III) to As(V) by K-birnessite was examined at different temperatures, pHs, and birnessite/As(III) ratios. Experiments ranged in duration from 5 to 64 hr, and solution and solid products were determined at several intervals. All experiments showed that the reaction produced large amounts of K+ to solution and very little Mn2+. As(V) was released to solution and incorporated into the K-birnessite. The oxidation was initially rapid and then slowed. The oxidation of As(III) was probably facilitated initially by autocatalytic Mn-As(V) reactions occurring mostly in the interlayer, in which large amounts of As(V) and K+ could be easily released to solution. The reaction also slowed when interlayer Mn was exhausted by forming Mn-As(V) complexes. Mn(IV) could only be acquired from the octahedral sheets of the birnessite. The two-stage reaction process proposed here depended on the layered structure of birnessite, the specific surface, and presence of exchangeable cations in K-birnessite.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Burns, R. G. and Bums, V. M. (1977) The mineralogy and crystal chemistry of deep-sea manganese nodules, a poly-metallic resource of the twenty-first century: Phil. Trans. R. Soc. Lond. A. 286, 283–301.

    Article  Google Scholar 

  • Catti, M. M. and Franchini-Angela, M. (1979) Krautite, Mn(H2O)(As03OH): Crystal structure, hydrogen bonding and relations with haidingerite and pharmacolite: Amer. Mineral. 64, 1248–1254.

    Google Scholar 

  • Coddington, K. (1986) A review of arsenals in biology: Tox. Environ. Chem. 11, 281–290.

    Article  Google Scholar 

  • Crowther, D. L., Dillard, J. G., and Murray, J. W. (1983) The mechanism of Co(II) oxidation on synthetic birnessite: Geochim. Cosmochim. Acta 47, 1399–1403.

    Article  Google Scholar 

  • Ferguson, J. F. and Gavis, J. (1972) A review of the arsenic cycle in natural waters: Water Research 6, 1259–1274.

    Article  Google Scholar 

  • Ficklin, W. H. (1983) Separation of arsenic(III) and arse-nic(V) in ground waters by ion-exchange: Talanta 5, 371–373.

    Article  Google Scholar 

  • Giovanoli, R., Stähl, E., and Feitknecht, W. (1970a) Über Oxidhydroxide des vierwertigen Mangans mit Schichtengitter, 2. Mitteilung: Mangan(III)-manganat(IV): Heb. Chitn. Acta 53, 453–464.

    Article  Google Scholar 

  • Giovanoli, R., Stähl, E., and Feitknecht, W. (1970b) Über Oxidhydroxide des vierwertigen Mangans mit Schichtengitter, 1. Mitteilung: Natriummangan(II, Hl)manganat(IV): Heb. Chim. Acta 53, 209–220.

    Article  Google Scholar 

  • Golden, D. C., Dixon, J. B., and Chen, C. C. (1986) Ion exchange, thermal transformations, and oxidizing properties of birnessite: Clays & Clay Minerals 34, 511–520.

    Article  Google Scholar 

  • Healy, T. W., Herring, A. P., and Fuerstenau, D. W. (1966) Effect of crystal structure on the surface properties of a series of manganese dioxides: J. Colloid Interface Sci. 21, 435–444.

    Article  Google Scholar 

  • Hem, J. D. (1979) Redox processes at surfaces of manganese oxide and their effects on aqueous metal ions: Chemical Geol. 21, 199–218.

    Article  Google Scholar 

  • Hem, J. D. (1980) Redox coprecipitation mechanisms of maganese oxides: in Particulates in Water, M. C. Kavanaugh and J. O. Leckie, eds., Adv. Chem. Ser. 189, American Chemical Society, Washington, D.C., 45–72.

    Article  Google Scholar 

  • Hem, J.D. (1981) Rates ofmanganese oxidation in aqueous systems: Geochim. Cosmochim. Acta 45, 1369–1374.

    Article  Google Scholar 

  • Jenne, E. A. (1968) Controls on Mn, Fe, Co, Ni, Cu, and Zn concentrations in soils and waters: American Chemical Society, Washington, D.C., Adv. Chem. Ser. 73, 337–387.

    Article  Google Scholar 

  • Jones, H. L. P. and Milne, A. A. (1956) Birnessite, a new manganese oxide mineral from Aberdeenshire, Scotland: Mineral. Mag. 31, 283–288.

    Google Scholar 

  • Krishnamurti, G. S. R. and Huang, P. M. (1987) The catalytic role of birnessite in the transformation of iron: Can. J. Soil Sci. 67, 533–543.

    Article  Google Scholar 

  • Lind, C. J. (1988) Hausmanite (Mn3O4) conversion to manganile (7-MnOOH) in dilute oxalate solution: Envir. Sci. Tech. 22, 62–70.

    Article  Google Scholar 

  • Martin, J. M. and Meybeck, M. (1979) Elemental mass balance of material carried by major world rivers: Mar. Chem. 7, 173–206.

    Article  Google Scholar 

  • McKenzie, R. M. (1971) The synthesis of birnessite, cryp-tomelene, and some other oxides and hydroxides of manganese: Mineral. Mag. 38, 493–502.

    Article  Google Scholar 

  • Murray, J. W. (1975) The interaction of cobalt with hydrous manganese dioxide: Geochim. Cosmochim. Acta 39, 635–647.

    Article  Google Scholar 

  • Oscarson, D. W., Huang, P. M., Defosse, C., and Herbillo, A. (1981a) Oxidative power of Mn(IV) and Fe(III) oxides with respect to As(III) in terrestrial and aquatic environments: Nature 291, 50–51.

    Article  Google Scholar 

  • Oscarson, D. W., Huang, P. M., and Liaw, W. K. (1980) The oxidation of arsenite by aquatic sediments: J. Envir. Qual. 9, 700–703.

    Article  Google Scholar 

  • Oscarson, D. W., Huang, P. M., and Liaw, W. K. (1981b) The role ofmanganese in the oxidation of arsenite by freshwater lake sediments: Clays & Clay Minerals 29, 219–225.

    Article  Google Scholar 

  • Oscarson, D. W., Huang, P. M., Liaw, W. K., and Hammer, U. T. (1983) Kinetics of oxidation of arsenite by various manganese dioxides: Soil Sci. Amer. J. 47, 644–648.

    Article  Google Scholar 

  • Pascal, P. (1966) Nouveau Traité de Chimie Minerale, Vol. 26: Masson, Paris, 453 pp.

    Google Scholar 

  • Stouff, P. and Boulegue, J. (1988) Synthetic 10Â and 7Â phyllomanganates: Their structures determined by EXAFS: Amer. Mineral. 73, 1162–1169.

    Google Scholar 

  • Turner, S. and Buseck, P. R. (1981) Todorokites: A new family of naturally occurring manganese oxides: Science 212, 1024–1027.

    Article  Google Scholar 

  • Wangersky, P. J. (1986) Biological control of trace metal residence time and speciation: A review and synthesis: Mar. Chem. 18, 269–297.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Moore, J.N., Walker, J.R. & Hayes, T.H. Reaction Scheme for the Oxidation of as(III) to as(V) by Birnessite. Clays Clay Miner. 38, 549–555 (1990). https://doi.org/10.1346/CCMN.1990.0380512

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1346/CCMN.1990.0380512

Key Words

Navigation