Multivariate Curve Resolution by Alternating LeastSquares (MCR-ALS) is applied to voltammetric dataobtained in the study of competitive complexation of Zn(II)and Cd(II) by
- and
-domains of metallothionein (MT).The application of MCR-ALS allows the estimation of boththe voltammograms and the concentration profilesassociated with each electrochemical process. Thecomplexity of the voltammograms obtained in titrations ofthe
- or
-domains of MT with Cd(II) and later Zn(II)(or vice versa) prevents their direct interpretation usingtraditional electrochemical methods. But when MCR-ALSis applied, voltammograms can be interpreted rathersatisfactorily in both qualitative and quantitative terms. MCR-ALS showed the formation of Cd
2Zn
dom and Cd
3Zn
domcomplexes when both metals were competitively added.A method based on the combined use of voltammetry andsome chemometric techniques is proposed. It can beuseful for the metal speciation of environmentally relevantnatural ligands.