Comparative rates of photolysis of polychlorinated dibenzofurans in organic solvents and in aqueous solutions.

A generator-column technique was used to prepare aqueous solutions of polychlorinated dibenzofurans (PCDFs). The photolysis rate constants of 2,7-di-, 2,3,7,8-tetra-, and 1,2,7,8-tetra-CDF in aqueous solution irradiated at 300 nm were 1.3, 0.45, and 0.36 h[sup [minus]1], respectively. These photolysis rates were 4-15 times faster than the photolysis rates in organic solutions and, in the cases of 2,7-di CDF and 1,2,7,8-tetra-CDF, 20 times faster than in 60% acetonitrile/water. Thus, a solvent mixture of acetonitrile and water should not be used to study the photolysis of PCDFs in aqueous solution. The contribution of dechlorination to the overall loss of the PCDF compounds was determined. It was found that 10%, 70%, and 50% of photodecomposed 2,7-di-, 1,2,7,8-tetra-, and 2,3,7,8-tetra-CDF, respectively, were dechlorinated under 300-nm irradiation in hexane, compared with <1%, 17%, and 20% in water. Dechlorination may therefore be a major process in the photodecomposition of higher chlorinated PCDFs in hydrocarbon solvents but not in water. These results suggest that the mechanism of photolysis of PCDFs in water differs from that in organic solvents. It was also found that the sunlight photolysis rates of PCDFs in natural water were enhanced by indirect or sensitized photoreactions of chemicals naturally occurring in water. 34 refs.,more » 2 figs., 4 tabs.« less