Polychlorinated dibenzo dioxin. atmospheric hydroxylation

Brubaker WW, RA Hites (1997) Polychlorinated dibenzo-/)-dioxins and dibenzofurans gas-phase hydroxyl radical reactions and related atmospheric removal. Environ Sci Technol 31 1805-1810. 

For polychlorinated biphenyls (PCBs), rate constants were highly dependent on the number of chlorine atoms, and calculated atmospheric lifetimes varied from 2 d for 3-chlorobiphenyl to 34 d for 236-25 pentachlorobiphenyl (Anderson and Hites 1996). It was estimated that loss by hydroxy-lation in the atmosphere was a primary process for the removal of PCBs from the environment. It was later shown that the products were chlorinated benzoic acids produced by initial reaction with a hydroxyl radical at the 1-position followed by transannular dioxygenation at the 2- and 5-positions followed by ring fission (Brubaker and Hites 1998). Reactions of hydroxyl radicals with polychlorinated dibenzo[l,4]dioxins and dibenzofurans also play an important role for their removal from the atmosphere (Brubaker and Hites 1997). The gas phase and the particulate phase are in equilibrium, and the results show that gas-phase reactions with hydroxyl radicals are important for the... 

Brubacker, W. W. Jr., and R. A. Hites, Polychlorinated dibenzo-p-dioxins and dibenzofurans Gas phase hydroxyl radical reactions and related atmospheric removal , Environ. Sci. Technol., 31, 1805-1810 (1997). 

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