Limitations of Applying Diffusive Gradients in Thin Films to Predict Bioavailability of Metal Mixtures in Aquatic Systems with Unstable Water Chemistries.

The present study accessed the use of diffusive gradients in thin film (DGT) as a surrogate for estimating the bioavailability and bioaccumulation of copper (Cu) and zinc (Zn) in a freshwater mussel. We coupled DGTs with mussels and deployed them in a constructed wetland. Water quality parameters were measured for a 4-d period on 3 continuous occasions during 12-d trials in the summer and winter; metal speciation was modeled for each occasion. Higher cumulative rainfall and water turbidity during the summer trial resulted in higher particulate metal concentrations compared to the winter trial. Mussel accumulated metals did not correlate with DGT-measured metals but positively correlated with particulate metals in the summer because filtering particulate food mainly contributed to the bioaccumulation. In contrast, the winter trial suggested a positive correlation between metal bioaccumulation and DGT-measured metals because uptake of dissolved organic matter (DOM) from water mainly contributed to the bioaccumulation, and the labile metal species complexed with DOM generally overlapped with DGT-targeted metals. Though Cu has a higher affinity for organic ligands than Zn, the interactions between Cu and Zn in the mixture did not impede their uptake and bioaccumulation. The deployment duration when DGTs and mussels are coupled to compare metal bioavailability should be no less than 12 d so that mussels have enough time to accumulate contaminants from the environmental media. In summary, DGT is a convenient surrogate for biomonitoring, but it may not fit the real environment such as the aquatic system with unstable water chemistries. Geochemical modeling is good at calculating metal speciation but inferior to DGT in predicting bioavailability and mimicking bioaccumulation. Environ Toxicol Chem 2020;39:2485-2495. © 2020 SETAC.