Novel speciation analysis of copper in river water: observation of soluble anionic copper–ligand complexes

Abstract

In natural water, copper is believed to be complexed with organic materials such as humic and fulvic acids, as well as anthropogenic substances such as ethylenediaminetetraacetic acid (EDTA). The nature of the complexes is known to be a main factor in determining copper toxicity to aquatic biota, as well as its geochemical transport. In this study, organically chelated copper species in river water were revealed to be classified into hydrophobic and anionic components using column cartridge separation techniques based on C18 and anion exchange. The amounts of anionic ligated copper species in the tested water samples ranged from 0 to 46 nM, and the average contribution of the anionic ligated copper to the total dissolved copper concentration was around 30 %. Several water samples contained discharged sewage effluents with high contents of EDTA, which may be the main chelating agent responsible for copper retention on the anionic ion exchange cartridge column. However, most of the river water samples were not contaminated with EDTA, and therefore, fulvic substances are expected to be responsible for retention. As this is the first observation of anionic copper species in the natural aquatic environment, further geochemical and biological studies of these substances should be undertaken.