Information about the speciation of Pb and Cu in different types of Port wines (white, single-year and blended aged red, and young red wines) was gathered to estimate their respective bioavailabilities to man. For this purpose, wines were subjected to in vitro simulated gastrointestinal digestion, and the following properties were studied in the wines and its gastric and intestinal digests: (1) average conditional stability constant (K(av)) of the Cu complexes (by potentiometry), of the strongest Pb complexes (those inert to cathodic voltammetry, K'(av)), and of the respective ligand concentrations (CC or CC(inert)); (2) the distribution of the metal among the different groups of compounds of different molecular weights and/or polarities in the different bands separated by reverse phase high-performance liquid chromatography; (3) the total metal concentration present in the wines and the respective fractions present in the soluble and in the dialyzable fractions of the digest (an estimation of the assimilable fraction). The study showed that the complexing affinity for Pb (expressed by either CC(inert) or K'(av)) of white and very aged red Port wines was lower than for the remainder of the wines. For Cu, the strength of the ligands in the white wines was lower (<log K(av) values) than in the other wines, but their concentrations (CC) were higher. For Pb, CC(inert) was much higher after the digestion than for the untreated wines, whereas the log K'(av) values were approximately 1 order of magnitude lower. These parameters could not be determined for Cu in the gastrointestinal digests. For all of the studied wines the dialyzable fraction of Pb during the intestinal digestion was low (10-22% of the total Pb) and the dialyzable fractions of Cu were close to 50% of the total Cu.