Benthic fluxes of copper, copper complexing ligands and thiol compounds in the shallow waters of Venice Lagoon (Italy) were determined using benthic chambers and compared to porewater concentrations to confirm their origin. Benthic copper fluxes were small due to small concentration differences between the porewaters and the overlying water, and the equilibrium concentration was the same at both sites, suggesting that the sediments acted to buffer the copper concentration. Thiol fluxes were approximately 10 x greater at 50-60 pmol cm(-2)h(-1), at the two sites. Porewater measurements demonstrated that the sediments were an important source of the thiols to the overlying waters. The overlying waters were found to contain at least two ligands, a strong one, L1 (log K'(CuL1) = 14.2) and a weaker one, L2 (log K'(CuL2) = 12.5). The concentration of L1 remained relatively constant during the incubation and similar to that of copper, whereas that of L2 was in great excess of copper, its concentration balanced by porewater releases and breakdown, probably due to uptake by microorganisms, similar to that of the thiol compounds. Similarity of the thiol and L2 concentrations and similar complex stability with copper suggest that L2 was dominated by the thiols. The free copper concentration ([Cu ]) in the Lagoon waters was lowered by a factor of 10(5) as a result of the organic complexation.