Two experimental methods to determine the speciation of cadmium in sediment from the River Neckar

The binding forms of Cd to an anaerobic sediment of low sulfide content from Lauffen reservoir (River Neckar, Germany) were studied using two different approaches, i.e. sequential extraction (modified from published protocols) and titrimetric study of the pH-dependent Cd release. Thermodynamic equilibrium calculations were applied to calculate both the release pattern of Cd during the titrations and the speciation of Cd within the single fractions of the extraction protocol. The calculations were based on measured sediment parameters such as hydrous ferric oxide (HFO), acid volatile sulfide, carbonate content and total Cd content, and the extractants (oxalate, acid etc.) used. The results of the two independent approaches coincided well in that they both assigned more than two thirds of the total Cd content to be adsorbed to organic matter. Cd bound as US is of little importance. Sequential extraction after a 3-month oxidation period at pH 7 revealed a shift of Cd from being mainly bound in stronger surface complexes with organic matter to being mainly bound in weaker surface complexes with organic matter and HFO, and thus becoming more bioavailable. This study suggests that the use of sequential extraction although being frequently criticized due to its operational character can be used to determine binding forms of metal ions if they are accompanied by 1) careful supporting experiments, 2) analysis of important sediment parameters, and 3) the use of thermodynamic equlibrium models which can help to understand Cd speciation within the extraction fractions.