About Us | Help Videos | Contact Us | Subscriptions

Journal of Environmental Quality Abstract - Heavy Metals in the Environment

Experimental Oxidative Dissolution of Sphalerite in the Aznalcóllar Sludge and Other Pyritic Matrices


This article in JEQ

  1. Vol. 35 No. 4, p. 1032-1039
    Received: Sept 26, 2005

    * Corresponding author(s): torrent@uco.es
Request Permissions

  1. Raúl Hitaa,
  2. José Torrent *a and
  3. Jerry M. Bighamb
  1. a Departamento de Ciencias y Recursos Agrícolas y Forestales, Universidad de Córdoba, Edificio C4, Campus de Rabanales, 14071 Córdoba, Spain
    b School of Environment and Natural Resources, The Ohio State University, 2021 Coffey Road, 210 Kottman Hall, Columbus, OH 43210-1085


After the collapse on 25 Apr. 1998 of the Aznalcóllar mine tailings dike in southwestern Spain, 45 km2 of the Guadiamar valley were covered by a pyritic sludge containing up to 2% sphalerite (ZnS). Later, the sludge was mechanically removed and calcium carbonate was plowed into the soil to immobilize heavy metals. By June 2001 more than 60% of the sulfides in the residual sludge had oxidized and soil Zn contents reached locally phytotoxic levels. Therefore, the oxidative dissolution of sphalerite in the sludge and other pyritic samples was examined. Flow-through oxidation experiments showed that: (i) about 5 and 17% of the sludge Fe and Zn were in soluble form, respectively, because the sludge sample had been partly oxidized in the field; (ii) the oxidation rates of the residual pyrite and sphalerite were similar; (iii) the overall sulfide oxidation rate was relatively unaffected by the addition of calcite; and (iv) poorly crystalline Fe (hydr)oxides containing Zn in occluded form and Zn (hydroxi)carbonates were formed in the presence of calcite. The rate of oxidation of reference sphalerite greatly increased when it was incorporated in the sludge or in a reference pyrite matrix. This enhancement was due to galvanic interaction because pyrite oxidation was depressed in the presence of sphalerite. Oxidation by Fe3+ ions was less important because the oxidation rates of native sphalerite were not greater at low than at high pH. The fast oxidation rate of sphalerite in the Aznalcóllar sludge indicates a need for quick adoption of remediation measures in similar accidents elsewhere. The use of calcite amendments has little influence on the oxidation rate but does result in the accumulation of Zn in relatively insoluble forms.

  Please view the pdf by using the Full Text (PDF) link under 'View' to the left.

Copyright © 2006. American Society of Agronomy, Crop Science Society of America, Soil Science SocietyASA, CSSA, SSSA