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The speciation of metals in a contaminated, anoxic, sulfide-rich, freshwater sediment was determined experimentally, using a sequential extraction procedure based on the method of Tessier et al. Taking into account the advantages and disadvantages of sequential extractions, the applied methodology allowed the investigation of the influence of aeration and acidification on the distribution of various metals in the sediment. Aeration caused Zn and Cd to be released from sulfides. Carbonates were partly dissolved by the oxidation process, causing mobilisation of Ca. Fe became less mobile owing to a stronger binding to organic matter. The speciation of K, Al, Ni, Pb and Mn and to a lesser extent of Cu was not affected by aeration. As a result of acidification of the aerated sediment, Ca, Mn, Ni, Zn and Cd became more mobile owing to the dissolution of carbonates.

Abstract-The bioavailability of heavy metals in sediments may be strongly decreased by the presence of AVS (acid-volatile sulfide). In contaminated freshwater sediments, however, AVS levels may not be sufficiently high to scavenge all reactive heavy metals. In different seasons, the vertical distribution of AVS and SEM (simultaneously extracted metals) was studied in sediment cores of a recent sedimentation area of the river Meuse. In the suboxic layer of the sediments, the amount of AVS is always too low to bind all reactive metals as sulfides (SEM/AVS Ͼ 1). SEM/AVS decreases with depth in the sediments, going from ratios higher than one in the surface sediments to ratios on the order of one or even less than one at greater depths. This large vertical variation in AVS levels is attributed to diagenetic processes i.e., sulfide oxidation in the suboxic top layer and sulfate reduction in the underlying anoxic sediment layer. The depth of the boundary between the suboxic and the anoxic layer changes seasonally. An important implication of these findings is that SEM/AVS ratios in mixed homogenized sediment samples are generally not suited for the assessment of potential metal toxicity of sediments.

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