The available experimental information on the occurrence of PCDD/Fs in the Venice Lagoon, Italy, was compiled and used to calculate fugacities for the environmental compartments of sediment, suspended particulate matter (SPM), water and air and then used to estimate fugacity ratios and assess the likely net direction of flux between media. The bottom sediment: SPM fugacity ratios for different PCDD/Fs indicate conditions close to equilibrium, suggestive of the close coupling of SPM with re-suspended sediment. Sediment/water and the sediment/air fugacity ratios suggest that net flux directions vary depending on the congener and the location within the lagoon. Net sediment–water–air movement (i.e. re-mobilisation/volatilisation) is suggested for the lighter congeners from the industrial canals, where the highest PCDD/F concentrations in the lagoon occur. The tendency to volatilise increases with decreasing congener molecular weight. In contrast, net deposition (air–water–sediment) appears to be occurring for the heaviest (hepta- and octa-) substituted PCDD/Fs. OCDF represents a marker of the industrial district of the lagoon, decreasing in concentration and as a fraction of total PCDD/Fs with increasing distance. The fugacity-based quantitative water air sediment interaction (QWASI) mass-balance model was applied to the central part of the lagoon. The key parameters for the determination of the model output, identified by a sensitivity analysis, were: the sediment active depth, the sediment re-suspension and deposition rates, and the total input of PCDD/Fs to the system. The QWASI model also indicates the tendency for the lighter PCDD/Fs to be released from surface sediment to the water column.