Metal partitioning in a sulfidic canal sediment: metal solubility as a function of pH combined with EDTA extraction in anoxic conditions

Abstract

The chemical forms of low concentrations of metals (Zn, Pb, Cu, Cd, Co and Mn) and main components (Fe and Ca) were determined under the original reducing conditions of a sulfide-rich sediment from the Gent-Terneuzen Canal (Belgium). Therefore, dissolution experiments as a function of pH were made in a salt solution mimicking the canal water. The centrifugates remaining after the dissolution vs. pH experiments were subsequently further extracted with 0.1 M EDTA/0.5 M NaAc (pH 4.65) to determine eventually readsorbed and/or reprecipitated metal ions. The experimental dissolution vs. pH edge of calcium, iron, manganese and cobalt had a lower slope than theoretically expected on the basis of the solubility of, respectively, calcium carbonate, iron sulfide/iron carbonate, manganese sulfide/manganese carbonate and cobalt sulfide and was explained by the combination of (a) the solubilities of the various minerals and (b) metal readsorption onto clay minerals and organic matter. Higher metal recoveries were measured in the 0.1 M EDTA/0.5 M NaAc mixture and proved that in addition coprecipitate formation with iron sulfide/iron carbonate minerals may occur. The solubility of zinc, lead, cadmium and copper was very low in the mimicking salt solution even at very low pH values (up to pH 1) in agreement with the theoretical solubility of their discrete metal sulfides. However, by using an additional 0.1 M EDTA/0.5 M NaAc extraction on the centrifugates remaining after the dissolution vs. pH experiments, it was qualitatively shown that zinc and lead were partly associated with iron sulfide/iron carbonate phases in the real sediment (in addition to their presence in discrete metal sulfides). Cadmium was present solely in discrete cadmium sulfide phases. It was not possible to verify whether copper was present in discrete copper sulfide phases and/or in mixed coprecipitates with iron sulfide/iron carbonate minerals.