Risk assessment of trace-metal contamination in soils requires predictive models that can accurately describe the complex uptake processes at the soil-plant interface, which are usually characterized by the coexistence of and interaction between multiple components. Competing cations such as Ca and H can affect metal availability to plants and subsequent rhizotoxicity. The biotic ligand model (BLM) has been proposed as a promising approach to model these interactive processes. Under the BLM assumption, we designed experiments to investigate how the solution chemistry is correlated with metal uptake and rhizotoxicity. Our first goal is to acquire a set of BLM parameters that can accurately represent the experimental data over varied solution conditions and parameters that are easy to integrate with general speciation models. The second objective is to get insight into the physical nature of the interactions. Our titration experiments revealed three types of biotic ligands in the pea roots with defined site densities and stability constants with H. Our ion sorption experiments estimated the surface-adsorption stability constants of Ca, Mg, Cd, Cu, Ni, and Zn with excised fresh pea roots. Our 48-h root growth tests have established the formation constants (KMe's) of living pea roots with Ca, Cd, Cu, Ni, and Zn. In these studies, we hypothesized and confirmed that the concentration of the metal-root complexes correlated with observed rhizotoxicity and that Ca, H, and trace metals competed for root absorption where lower solution pH decreased both Ca and metal uptake. Root elongation was found to be highly sensitive to root Ca content rather than merely to the direct toxic effects of the trace metals. It is shown that the physiological complexity arising from a living root affected our modeling so that adjustable KMe values, as a function of solution and root chemistry, are required for good model fits. The established model parameters were tested in hydroponic mixture solutions for their ability to predict the uptake of multiple metals simultaneously. The joint effects of Cd, Cu, and Ni in mixtures on root growth were studied and the potential interactions between these ions were also investigated.

Soil quality guidelines are currently based on total trace metal loads. There is a need to define indices of bioavailability to allow reasonable predictions for plant metal uptake and toxicity in soils. Trace metal toxicities to plants often correlate best with free metal ion activities. The first objective was to develop a plant bioassay that is sensitive to trace metals at concentrations realistic for soils. The root elongation of lettuce Lactuca sativa 'Buttercrunch' was used as toxicological endpoint. This endpoint was sensitive and reproducible to environmentally relevant concentrations of Cd, Cu, Ni, Pb and Zn. The second objective was to test whether free metal ion activities are constant predictors of metal toxicities in synthetic solutions and in soil extracts that differ in their concentrations of cations and ligands. The root elongation assay was used to test this hypothesis. In synthetic solutions, the rhizotoxicity of Cd, Cu, Ni, Pb and Zn decreased with increasing Ca and H concentrations. This could not be explained with the effect of higher cationic concentrations on root growth or on solution speciation. It was concluded that Ca and H inhibited the rhizotoxicity of all metals tested. The rhizotoxicity of Cu and Cd was further examined in soil extracts. Both metals became less rhizotoxic at higher H and dissolved organic matter concentrations. The rhizotoxicity endpoints from the experiments in synthetic solution were used to develop parameters for a Biotic Ligand Model (BLM) for Cd, Cu, Ni, Pb and Zn. The BLM accounts for solution speciation and interprets cationic inhibition of rhizotoxicity as competition of metals with Ca and H for potential sites of rhizotoxicity. The BLM predicted metal rhizotoxicity better than the free metal ion activity in synthetic solutions and in soil extracts. Different models were tested against literature rhizotoxicity data for metals at different Ca and H concentrations. Predictions for metal rhizotoxicity given by BLM, Gouy-Chapman-Stern model and Freundlich equation model were compared with predictions based on free metal ion activities in solution. The BLM predicted rhizotoxicity most accurately. The BLM seems promising for predictions of metal toxicity and metal bioavailability in soils to support site-specific environmental risk assessments.

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