| Abstract: | In the estuary of the river Scheldt, where an oxygen gradient exists in addition to the salinity gradient, redox processes will be of major importance for trace metal mobilisation. In this study, the influence of salinity and pH on the redox processes of dissolved Zn and Cd sulphides is investigated together with the effects on the ratio of the dissolved Zn and Cd concentrations. The speciation of these metals is calculated with the chemical equilibrium programme +. Zn sulphides are oxidised at lower oxygen concentrations than Cd sulphides, due to lower stability constants, causing a sudden increase or peak in the dissolved Zn/Cd ratio. The formation of dissolved Cd chloride complexes when oxidation occurs at high salinities (S=15) increases the mobility of Cd, causing a decrease in the Zn/Cd peak of the total dissolved concentrations. The peak is three to four times smaller at S=15 than when oxidation occurs at S=2. The simple model calculations compare very well with field data. The Scheldt estuary is suitable to illustrate these calculations. In the 1970s, the anoxic part of the estuary reached S=15–20, but since the early 1980s it has dropped to S=2–10. Historic data on metals in the estuary from 1978, 1987 and the 1990s were used to compare with the equilibrium calculations. The increase of the dissolved Zn/Cd peak at low salinity as a consequence, of the decreasing anoxic region is confirmed well by the data. The good agreement between model calculations and field data is a proof of the extreme importance of redox processes for the solubility of Zn and Cd sulphides in the estuary. |
