The fate of arsenic in aquatic systems is influenced by dissolved natural organic matter (DOM). Using UV-A and visible light from a medium-pressure mercury lamp, the photosensitized oxidation of As(III) to As(V) in the presence of Suwannee River humic acid was investigated. Pseudo-first-order kinetics was observed. For 5 mg L(-1) of dissolved organic carbon (DOC) and 1.85 mEinstein m(-2) s(-1) UV-A fluence rate, the rate coefficient k degrees exp was 21.2 +/- 3.2 10(-5) s(-1), corresponding to a half-life <1 h. Rates increased linearly with DOC and they increased by a factor of 10 from pH 4 to 8. Based on experiments with radical scavengers, heavy water, and surrogates for DOM, excited triplet states and/or phenoxyl radicals seem to be important photooxidants in this system (rather than singlet oxygen, hydrogen peroxide, hydroxyl radicals, and superoxide). Photoirradiation of natural samples from freshwater lakes, rivers, and rice field water (Bangladesh) showed similar photoinduced oxidation rates based on DOC. Fe(III) (as polynuclear Fe(III)-(hydr)oxo complexes or Fe(III)-DOC complexes) accelerates the rate of photoinduced As(III) oxidation in the presence of DOC by a factor of 1.5-2.