Insight into UV-LED/PS/Fe(Ⅲ) and UV-LED/PMS/Fe(Ⅲ) for p-arsanilic acid degradation and simultaneous arsenate immobilization

Abstract

As a feed additive, p-arsanilic acid (p-ASA) is hardly metabolized in animal bodies and is excreted chemically unchanged via feces and urine, which can be transformed into more toxic inorganic arsenic species and other organic by-products upon degradation in the aquatic environment. In this study, UV-LED/persulfate (PS)/Fe(Ⅲ) and UV-LED/peroxymonosulfate (PMS)/Fe(Ⅲ) processes were developed to remove p-ASA and immobilize the formed inorganic arsenic via tuning solution pH. UV-LED/PMS/Fe(Ⅲ) (90.8%) presented the best performance for p-ASA degradation at pH 3.0, and the p-ASA degradation in these processes both followed the pseudo-first-order kinetics. The ∙OH played the major role in UV-LED/PS/Fe(Ⅲ) and UV-LED/PMS/Fe(Ⅲ) systems. Solution pH greatly affected the p-ASA degradation and the maximum removal can be achieved at pH 3.0 due to the presence of more Fe(OH)(H2O)52+. The dosages of Fe(III) and PMS (PS), SO42− and HCO3− significantly influenced the performance of p-ASA oxidation, while HA, Cl− and NO3− slightly affected the p-ASA degradation. According to quantum chemical calculation, radical addition on the C atom in the C-As bond of p-ASA was corroborated to be the dominant reaction pathway by SO4∙− and ∙OH. Additionally, the reactive sites and reasonable degradation pathways of p-ASA were proposed based on DFT calculation and HPLC/MS analysis. The release of inorganic arsenic in both processes can be effectively immobilized and the toxicity of the reaction solution dramatically reduced by adjusting solution pH to 6.0. UV-LED/PMS/Fe(Ⅲ) process was found to be more cost-effective than UV-LED/PS/Fe(Ⅲ) process at the low oxidant dosages.