Proteins often stabilize food emulsions and are also able to promote or delay lipid oxidation in complex systems. The purpose of this work was to investigate the relationship between metal ion availability and oxidative stability of oil-in-water emulsions stabilized by bovine serum albumin (BSA) or sodium caseinate (NaCas). Emulsions with similar and stable droplet size distributions were prepared with stripped sunflower oil (30 vol %) and protein solutions (20 g L(-)(1); pH = 6.5). In the absence of the water-soluble metal chelator EDTA, oxygen uptake, conjugated dienes, and volatile compounds developed faster in NaCas-stabilized emulsions than in those prepared with BSA. This effect is attributed to the chelating properties of NaCas and to electrostatic interactions that attract some metal ions at the interface where they could initiate lipid oxidation. When EDTA (100 muM) was present, oxidation was delayed to a greater extent in emulsions made with NaCas than in BSA stabilized emulsions. These conditions probably enabled NaCas to exert free-radical-scavenging activity.