Strong colloidal and dissolved organic ligands binding copper and zinc in rivers

The speciation or physicochemical form of copper and zinc in freshwater plays an important role in reactivity, bioavailability, and toxicity. Strong metal-binding ligands, which determine speciation, were detected by voltammetric methods, both anodic stripping voltammetry (ASV) and competitive ligand equilibration adsorptive stripping voltammetry (CLE-AdSV); the latter technique can detect nanomolar levels of extremely strong (log K' > 13) ligands. Through careful field site selection and the investigation of ultrafiltration permeate samples, natural organic ligands were measured with limited interferences of colloidal inorganic iron- and aluminum-based trace metal-binding phases. Furthermore, ultrafiltration allowed measurement of colloidal and dissolved ligands independently, and differences of ligand abundance and strength in different size classes are reported. For copper, ultrafilterable (<3 kDa) organic ligand site concentrations (expressed normalized to dissolved organic carbon) were on average 33% of the colloidal level, but ultrafilterable ligand log K' values were 0.5 log units stronger than those of the 0.4 microm filterable concentration. The ultrafilterable copper-binding ligand concentration showed a smaller variation across the rivers (25% rsd) than zinc-binding ligands (90% rsd). For all field sites and size fractions, strong ligand sites greatly exceeded metal concentrations; subsequently, equilibrium speciation modeling predict picomolar levels of free metal. Modeling also indicated that the very strong ligands (detected by CLE-AdSV) predominate, so modeling based solely on ASV data in freshwater may be inadequate. Competition experiments indicated that the very strong ligand sites are metal specific for copper and zinc.