Experimental and mathematical investigation of dynamic availability of metals in sediment

Contaminated sediments are periodically subjected to resuspension processes during either storm events or due to dredging. In sediments, metals are often contained in insoluble low bioavailability forms. Upon resuspension, however, biogeochemical processes associated with the exposure to more oxic conditions may lead to transformation and release of the metals, giving rise to exposure and risk in the water column. Batch experiments suggested that oxidation of reduced species and corresponding pH decrease were the most importance processes controlling metals release upon sediment resuspension. A mathematical model was implemented to better understand the complex underlying biogeochemical reactions that affect metals release. The model described the metals dynamics and other inter-related important biogeochemical factors well and was successful at predicting the metals release from different sediment reported in the literature. Tidal and other cyclic variations in oxygen, pH and other relevant parameters in the overlying water may also lead to cyclic transformations and release of metals from surficial sediments. In simulated estuarine microcosm experiments, cyclic variations in pH and salinity due to freshwater/saltwater exchange were shown to lead to cyclic variations in metal release. Both pH and salinity were important factors controlling interstitial dissolved metals concentrations, however, in terms of freely dissolved metals concentrations, which have been considered to be more related with toxicity and bioavailability, pH was the single most important parameter. The mathematical model was extended to the conditions of the cyclic behavior in an estuary and successfully described metals release under such conditions. It is believed that the model can be used to predict the metals behavior in other sediments and conditions by model calibration with a similar experimental approach to that used in this study.