Creating metal-spiked bed sediments: a case study from Orewa estuary, New Zealand

Spiking sediments to achieve target concentrations of heavy metal pollutants is a key step in sediment toxicity tests. It is difficult, however, to ensure that metals in an artificially spiked sediment will behave naturally. A method has been developed in the present study to create Cu-, Pb-, and Zn-spiked sediments in which naturally occurring adsorption onto sediment surfaces is the dominant process binding the metals and in which precipitation of readily redissolved minerals and other metal-bearing phases (artifacts of the spiking procedure) are avoided. Uncontaminated bed sediment from an intertidal mudflat in the Orewa estuary, New Zealand, was characterized in terms of existing metal content, optimal adsorption pH, and adsorption capacity. Competitive adsorption between Cu and Pb as well as complexation by seawater anions only slightly affected metal adsorption from seawater. Surface complexation modeling indicated that iron oxide surfaces in the sediment likely were dominating metal adsorption processes. Spiking experiments were designed using these established adsorption characteristics but with significantly higher (>100-fold) concentrations of sediments and dissolved metals and a liquid to solid (L:S) ratio of approximately 5.5. An equilibration time of at least 36 h was required to achieve a reproducible target metal concentration, which could be reliably predicted from the L:S ratio and the initial metal concentration in the spiking solution. Adsorption equilibrium remained the process governing metal binding to the sediment, and no indication was observed that the adsorption capacity of the sediment had been exceeded or that additional metal-bearing phases had been formed.