Accelerated photo-transformation of 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153) in water by dissolved organic matter.

The ubiquitous dissolved organic matter (DOM) has an important influence on transformation of organic contaminants through the production of reactive substances, such as (•)OH, (1)O(2), and (3)DOM*. The photolysis of a higher chlorinated polychlorinated biphenyl (PCB) congener (2,2',4,4',5,5'-hexachlorobiphenyl, PCB 153) under simulated sunlight in presence of humic acid (HA) was investigated. Degradation of PCB 153 was accelerated significantly by the addition of HA, with a rate constant of 0.0214, 0.0413, and 0.0358 h(-1) in the initial 18 h of irradiation in presence of 1, 5, and 20 mg/L HA, respectively. The main photodegradation products analyzed by gas chromatography mass spectrometry were 4-hydroxy-2,2',4',5,5'-pentaCB and 2,4,5-trichlorobenzoic acid. Main reactive species involved were determined by the electron spin-resonance spectroscopy, including (1)O(2) and (•)OH. Special scavengers were added to elucidate the photolysis mechanisms. By using the specific scavengers, it turned out that (•)OH accounted for 29.3 % of the degradation, and the intra-DOM reactive species ((1)O(2), (•)OH, and (3)DOM*) accounted for 59.6 % of the degradation. Photo-transformation sensitized by DOM, which involves both aqueous and intra-DOM reactions of PCBs with reactive species, may be one of the most important mechanisms for natural attenuation of PCBs.