Photolysis of carboxylate anions adsorbed onto highly crystalline goethite (??-FeOOH) with 300-400-nm light produces Fe2+(aq) and ??OH from surface and solution redox reactions. The production of Fe2+(aq) and ??OH was studied in N2-purged and aerated aqueous suspensions, respectively, of goethite containing equimolar (10-3 M) concentrations of oxalate and benzoate (ob + g), succinate and benzoate (sb + g), benzoate alone (b + g), and goethite alone (g). The hydroxyl radical was measured by fluorescence analysis of salicylate formed in a reaction between benzoate and ??OH. Fe2+(aq) was determined colorimetrically. A proposed reaction mechanism includes the photoexcitation of Fe(III) surface complexes with OH-, HCO3-, and RCOO- ligands to form Fe2+(aq) and corresponding ligand radicals. Additional ??OH is made by the O2 oxidation of Fe2+(aq) (Haber-Weiss mechanism). Comparison of Fe2+(aq) and ??OH yields permitted an estimate of the relative importance of pathways leading to ??OH.