Interfacial Metal Flux in ligand Mixtures. 3. Unexpected Flux Enhancement Due to Kinetic Interplay at the Consuming Surface, Computed for Aquatic Systems

摘要

Understanding the processes controlling metal biouptake in a mixture of ligands is a requirement for making predictions on dynamic risk assessment in ecotoxicology. In ligand mixtures, the metal uptake flux, due to the dissociation of non labile complexes, can be significantly enhanced by the presence of ligands forming labile complexes, even when the proportions of the latter are very small in the bulk solution. The flux enhancement results from a peculiar kinetic interplay, at the interface, between the labile and non labile species, which influences the lifetime of free metal ion and the reaction layer thickness. An extension of the concept of reaction layer, to multiligand systems, is used here, to explain the physicochemical basis of this flux enhancement and to compute the flux of trace metals in a simple way. This phenomenon is exemplified with four environmentally relevant systems including: (ⅰ) simple ligands (Pb-NTA-diglycolate; Cu-OH~--CO_3~(2-), (ⅱ) fulvic substances (Cu-fulvics-citrate), and (ⅲ) aggregate complexants (Pb-aggregate-CO_3~(2-)). These examples are typical cases in laboratory experiments, in natural freshwaters and in soil-waters. They show that the flux enhancement effect may occur with all major inorganic and organic environmental complexants. It may be ubiquitous in natural waters or in biological systems and might play an important role in biouptake of toxic or vital metals.