Evidence for Strong Copper(I) Complexation by Organic Ligands in Seawater

Abstract

Thiols like glutathione and cysteine form such stable complexes with copper(I) that they preclude the presence of copper(II). Conventionally seawater is titrated with copper(II) whilst monitoring the labile or reactive copper concentration by voltammetry or with other techniques, to determine the concentration of copper(II) binding complexing ligands in seawater. Titrations of seawater to which copper(I) binding ligands have been added reveal that the copper(I) binding ligands are detected when seawater is titrated with copper(II). The copper(II) in seawater is reduced to copper(I) within 2 to 40 minutes depending on the nature of the copper(I) binding ligand. The titrations of seawater with copper(II) thus give a response to the presence of copper(I) binding ligands indiscernible from that for copper(II) binding ligands. The stoichiometry of the detected apparent ligand concentrations for given concentrations of glutathione and cysteine suggest that 2 : 1 (thiol : Cu) complexes are formed. This was confirmed using voltammetry of free glutathione. Values of 21.2 and 22.2 were found for log β″CuL for glutathione and cysteine respectively (for the reaction of Cu′ + 2L′ ↔ CuL2). The complex stability is similar to that of natural organic species in the oceanic water column. The high stability of the copper(I) complexes was apparent from values of 32.1 and 32.6 for log β″Cu(I)L2 (for the reaction Cu+ + 2L″ ↔ CuL2) for the copper(I) complexes with glutathione and cysteine in seawater. Glutathione and other thiols are common in the marine system including the water column. It is therefore possible that at least some of the ligands detected in seawater, and previously assumed to be copper(II) binding ligands, are in fact strongly complexed as copper(I). The copper(I) oxidation state may thus be stabilised in seawater.