Abstract

The spiking of metals into sediments lowers pH, raises the oxidative state, and exacerbates the partitioning of Fe, Mn, and spiked metal to the porewater. This study reports the geochemical response of three sediments of varying metal-binding capacity to Cu-/Zn-additions and the influence of pH-adjustment on the major metal-partitioning processes. The increase in redox potential and porewater metal concentrations observed in metal-spiked sediment was minimized by sediment neutralization to pH 7 irrespective of sediment type. In the presence of minimal sulfide concentrations, porewater metal concentrations suggested a greater affinity of copper for organic carbon than zinc, which was thought more dependent on iron oxyhydroxide phases. The amount of iron in the porewater of metal-spiked pH adjusted sediment was, in turn, affected by the type and concentration of spiked metal in the porewater. Increasing porewater concentrations of copper and zinc corresponded to decreasing and increasing porewater iron concentrations, respectively. Porewater copper appeared to act as a toxicant of Fe(III) reducing bacteria, while porewater zinc is thought to have had a stimulatory effect. The present study provides further insight on geochemical changes occurring to metal-spiked sediments and their implications for the interpretation of toxicity tests.

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