Proton Competition and Free Ion Activities Drive Cadmium, Copper, and Nickel Accumulation in River Biofilms in a Nordic Ecosystem

Abstract

Biofilms can be used as a biomonitoring tool to determine metal bioavailability in streams affected by mining and other anthropogenic activities. Surface water and biofilm were sampled over two years from rivers located in the vicinity of a mine located in a Nordic ecosystem (Nunavik, Quebec). Biofilm metal content (Cd, Cu, and Ni) as well as a variety of physicochemical properties were determined to examine relationships between metal accumulation and water quality. Among the three metals of interest, copper and nickel had the highest levels of accumulation and cadmium had the lowest. When considering the exposure levels, nickel was the most abundant metal in our sampling sites. Both exposure and accumulation levels were consistent over time. Biofilm metal content was highly correlated to the ambient free metal ion concentration for sites of circumneutral pHs for all three metals. When the surface water pH was below 6, biofilm metal content was much lower than at other sites with similar aqueous metal concentrations of exposure. This apparent protective effect of decreasing pH can be explained by proton competition with dissolved metals for uptake binding sites at the surface of the organisms within the biofilm as described by the Biotic Ligand Model principles. The relationships obtained for Cd and Cu were overlapping those observed in previous publications, indicating strong similarities in metal accumulation processes in biofilms over very large geographical areas. Although more data are needed for Ni, our results show that biofilms represent a promising metal biomonitoring tool.