Photoinduced oxidation of antimony(III) in the presence of humic acid

Interactions of antimony with natural organic matter (NOM) are important for the fate of Sb in aquatic systems. The kinetics of the photosensitized oxidation of Sb(III) to Sb(V) in the presence of Suwannee River Humic Acid (SRHA) was investigated using UV-A and visible light (medium-pressure mercury lamp). At a concentration of 5 mg L(-1) dissolved organic carbon (DOC) the light-induced reaction was 9000 times faster (rate coefficient k(exp) = 7.0 +/- 0.05 x 10(-4) s(-1)) than the dark reaction and followed pseudo-first-order kinetics. Rates increased linearly with the concentration of DOC. Between pH 4 and 8 rates increased by a factor of 5. Further results and kinetic considerations indicate that singlet oxygen, hydroxyl radicals, hydrogen peroxide, and hydroperoxyl radicals/superoxide are not important photooxidants in this system, while other NOM-derived reactive species, in particular excited triplet states and/or phenoxyl radicals, seem to be relevant. The dependence of rate coefficients on Sb(III)/DOC ratio was consistent with a two binding site model including (i) a strong binding site at low concentration inducing fast oxidation, (ii) a weak binding site at high concentration inducing slower oxidation, and (iii) the even slower oxidation of Sb(OH)3. Photoirradiation of natural water samples spiked with Sb(III) showed that the oxidation rates could be well predicted based on DOC.