Multiple transformation pathways of p-arsanilic acid to inorganic arsenic species in water during UV disinfection

p-Arsanilic acid（p-ASA） is widely used in China as livestock and poultry feed additive for promoting animal growth.The use of organoarsenics poses a potential threat to the environment because it is mostly excreted by animals in its original form and can be transformed by UV–Vis light excitation.This work examined the initial rate and efficiency of p-ASA phototransformation under UV-C disinfection lamp.Several factors influencing p-ASA phototransformation,namely,p H,initial concentration,temperature,as well as the presence of Na Cl,NH4＋,and humic acid,were investigated.Quenching experiments and LC–MS were performed to investigate the mechanism of p-ASA phototransformation.Results show that p-ASA was decomposed to inorganic arsenic（including As（Ⅲ） and As（V））and aromatic products by UV-C light through direct photolysis and indirect oxidation.The oxidation efficency of p-ASA by direct photosis was about 32%,and those by HOU and1O2 were 19% and 49%,respectively.Cleavage of the arsenic–benzene bond through direct photolysis,HOU oxidation or1O2 oxidation results in simultaneous formation of inorganic As（Ⅲ）,As（IV）,and As（V）.Inorganic As（Ⅲ） is oxidized to As（IV） and then to As（V） by1O2 or HOU.As（IV） can undergo dismutation or simply react with oxygen to produce As（V） as well.Reactions of the organic moieties of p-ASA produce aniline,aminophenol and azobenzene derivatives as main products.The photoconvertible property of p-ASA implies that UV disinfection of wastewaters from poultry and swine farms containing p-ASA poses a potential threat to the ecosystem,especially agricultural environments.

Photooxidation of arsenic(Ⅲ) to arsenic(Ⅴ) on the surface of kaolinite clay

As one of the most toxic heavy metals, the oxidation of inorganic arsenic has drawn great attention among environmental scientists. However, little has been reported on the solar photochemical behavior of arsenic species on top-soil. In the present work, the influencing factors（p H, relative humidity（RH）, humic acid（HA）, trisodium citrate, and additional iron ions） and the contributions of reactive oxygen species（ROS, mainly HO^- and HO2^-/O2^-） to photooxidation of As（Ⅲ） to As（Ⅴ） on kaolinite surfaces under UV irradiation（λ = 365 nm）were investigated. Results showed that lower p H facilitated photooxidation, and the photooxidation efficiency increased with the increase of RH and trisodium citrate.Promotion or inhibition of As（Ⅲ） photooxidation by HA was observed at low or high dosages, respectively. Additional iron ions greatly promoted the photooxidation, but excessive amounts of Fe^2＋competed with As（Ⅲ） for oxidation by ROS. Experiments on scavengers indicated that the HOUradical was the predominant oxidant in this system.Experiments on actual soil surfaces proved the occurrence of As（Ⅲ） photooxidation in real topsoil. This work demonstrates that the photooxidation process of As（Ⅲ） on the soil surface should be taken into account when studying the fate of arsenic in natural soil newly polluted with acidic wastewater containing As（Ⅲ）.