Determination of metal speciation by reverse titrations

A new method is proposed to determine metal speciation by varying the concentration of a competing ligand at a constant metal concentration, with detection by cathodic stripping voltammetry. The free metal ion concentration is gradually lowered from its natural level while the method probes progressively deeper into the already complexed metal fraction: it is therefore a reverse titration rather than the forward titration which is used for conventional complexing ligand titrations. The sensitivity is greatest at the lowest free metal ion concentration, where it matters most, and the method can be carried out in a single sample aliquot in the voltammetric cell. The method is applied here to copper speciation, but in principle, it can also be used for other metals. Modeling shows that this method has good sensitivity at ligand concentrations near the metal concentration (lower as well as greater). Comparative measurements of copper speciation using reverse and forward titrations of representative water samples of oceanic and coastal origin show good agreement. The data showed that these samples did not contain low levels of strong ligands in addition to the ligands detected by the forward titrations.