Characterization and Potential Environmental Implications of Select Cu-Based Fungicides and Bactericides Employed in US Markets

This exploratory study aimed to examine the extent and mineral speciation of nanosized Cu in two fungicide products (A and B) available in the U.S. markets. Electron microcopy results demonstrated the presence of spherical and polydisperse <100 nm Cu particles in product B. Other elements (e.g., Pb, Na, Ca, and S) were found in both products. Mineral speciation analysis indicated the dominance of spertiniite followed by cornetite and then malachite in product A. In product B, spertiniite and tenorite were the dominant Cu species followed by cornetite and malachite. Tenorite in product B (similar to 30%, <450 nm) has the potential for stronger toxicological impacts relative to those of other Cu minerals in the tested products. For both products, the particle hydrodynamic diameter was impacted by changes in environmental parameters (pH, ionic strength, and background electrolyte) in Milli-Q water and humic acid suspensions. However, a minimal impact was observed in polyvinylpyrrolidone suspensions. The findings are critically important for estimating the fate and transport of Cu particles in different environmental scenarios as well as allowing a more accurate assessment of their risk that is largely impacted by chemical speciation and size.