A new method to measure effective soil solution concentration predicts copper availability to plants

Risk assessments of metal contaminated soils need to address metal bioavailability. To predict the bioavailability of metals to plants, it is necessary to understand both solution and solid phase supply processes in soils. In striving to find surrogate chemical measurements, scientists have focused either on soil solution chemistry, including free ion activities, or operationally defined fractions of metals. Here we introduce the new concept of effective concentration, C-E, which includes both the soil solution concentration and an additional term, expressed as a concentration, that represents metal supplied from the solid phase. C-E was measured using the technique of diffusive gradients in thin films (DGT) which, like a plant, locally lowers soil solution concentrations, inducing metal supply from the solid phase, as shown by a dynamic model of the DGT-soil system. Measurements of Cu as C-E, soil solution concentration, by EDTA extraction and as free Cu2+ activity in soil solution were made on 29 different soils covering a large range of copper concentrations. They were compared to Cu concentrations in the plant material of Lepidium heterophyllum grown on the same soils. Plant concentrations were linearly related and highly correlated with C-E but were more scattered and nonlinear with respect to free Cu2+ activity, EDTA extraction, or soil solution concentrations. These results demonstrate that the dominant supply processes in these soils are diffusion and labile metal release, which the DGT-soil system mimics. The quantify CE is shown to have promise as a quantitative measure of the bioavailable metal in soils.