Hydroxyl radical mediated degradation of phenylarsonic acid

Phenyl-substituted arsonic acids have been widely used as feed additives in the poultry industry. While very few studies have been reported on the environmental impact of these compounds, they have been introduced into the environment through land application of poultry litter in large quantities (about 10(6) kg/year). Phenylarsonic acid (PA) was used as a model for problematic arsonic acids. Dilute aqueous solutions of PA were subjected to gamma radiolysis under hydroxyl radical generating conditions, which showed rapid degradation of PA. Product studies indicate addition of (OH)-O-center dot to the phenyl ring forms the corresponding phenols as the primary products. Arsenite, (H3AsO3)-O-III, and arsenate, (H3AsO4)-O-V, were also identified as products. The optimized structures and relative calculated energies (using GAUSSIAN 98, the B3LYP/6-31G(d) method) of the various transient intermediates are consistent with the product studies. Pulse radiolysis was used to determine the rate constants of PA with (OH)-O-center dot (k = 3.2 x 10(9) M-1 s(-1)) and SO4 center dot- (k = 1.0 x 10(9) M-1 s(-1)). PA reacts slower toward O center dot- (k = 1.9 x 10(7) M-1 s(-1)) and N-3(center dot) (no detectable transient), due to the lower oxidation potential of these two radicals. Our results indicate advanced oxidative processes employing (OH)-O-center dot and SO4 center dot- can be effective for the remediation of phenyl-substituted arsonic acids.