S, Zn, Cr, Cu and Fe changes during fluvial sediments oxidation

Acidification of dredged sediments which have been disposed on land is highly dependent on redox shifts. The aim of the present work was to assess changes in sulphur, metal speciation (Zn, Fe, Cr y Cu) and acidity caused by a polluted sediment oxidation event. Sediments were dessicated under controlled conditions and sulphide compounds (acid volatile sulphides-AVS- and sulphate), pH and neutralization potential were measured through time during 36 days. Zinc, Cu, Cr and Fe speciation (BCR metal sequential extraction procedure) were measured at the beginning of the experiment and at day 22. An acid-base equilibrium method based on the BCR procedure was employed to assess the sediment acidification risk. Some of the re-suspension experiments were inoculated with an Acidithiobacillus ferrooxidans strain to assess biological catalysis on sulphide oxidation. Acid-base equilibrium results indicated the sediment sample had a significant acidification potential. Oxidation increased sulphate levels (56 to 2300 mg S kg-¹ in the desiccation experiment with a temporal evolution adjusted by a logistic model, and a 2100 to 3000 mg SO4 -² L-¹ increase for the resuspension experiments). Sulphide oxidation rates varied between 0 to 3.1.10-9 mg O2 kg-¹ s-¹ for the drying sediment. Zinc changes could be explained partially by ZnS conversion to ZnSO4 during oxidation. Iron reduction could be attributed to an increase in Fe oxides crystallinity. Acid-base equilibrium for the sample indicated it was a potentially acid-generating material. Zinc increased its bioavailability during drying and was the only metal that appeared in significant amounts in solution during re-suspension. Land-filling with dredged sediments could present increased metals bioavailability problems despite having an important and effective neutralization potential.