Although a variety of analytical techniques have been developed to characterize metal speciation, few have been used successfully in the complicated matrices encountered in wastewater effluents and surface runoff. In this study, competitive ligand equilibrium-cathodic stripping voltammetry (CLE-CSV) and chelating resin column partitioninggraphite furnace atomic absorption spectroscopy (CRCP-GFAAS) are used to determine the speciation of Cu and Ni in point and non-point pollutant sources discharging into South San Francisco Bay. As expected, most of the dissolved Cu and Ni in wastewater effluents and surface runoff are complexed. Moderately strong metal-complexing ligands, which likely consist of activated sludge biopolymers and humic substances, are responsible for the complexation of only about 20% of the Ni and 5-50% of the Cu. The remaining Cu and Ni is complexed by ligands with apparent stability constants comparable to those of synthetic chelating agents. Strongly complexed Cu is present at concentrations below 40 nM and accounts for 5-60% of the Cu discharged by these sources. Strongly complexed Ni is present at concentrations ranging from approximately 10 to 100 nM and accounts for >75% of the Ni discharged by wastewater treatment plants and approximately 25% of the Ni in surface runoff. Strong Ni complexes, which are not removed during wastewater treatment, are extremely stable in seawater. The existence of strong metal-complexing ligands in wastewater effluent and, to a lesser degree, in surface runoff must be accounted for when evaluating metal treatability and biogeochemistry.