Effects of a redox-active diketone on the photochemical transformation of roxarsone: Mechanisms and environmental implications. (December 2022)

• Record Type: Journal Article
• Authors: Wei, Shuangshuang; Zhou, Chang; Zhang, Guoyang; Zheng, Hongcen; Chen, Zhihao; Zhang, Shujuan
• Is Part Of: Chemosphere. Volume 308:Part 2(2022)
• Publication Date: 2022-12
• Subjects: Acetylacetone -- Organoarsenics -- Photodegradation -- Dissolved oxygen -- Photoionization; Pollution -- Periodicals; Pollution -- Physiological effect -- Periodicals; Environmental sciences -- Periodicals; Atmospheric chemistry -- Periodicals; 551.511
• DOI: 10.1016/j.chemosphere.2022.136326
• Languages: English
• ISSNs: 0045-6535

Abstract

Abstract: Organoarsenical antibiotics pose a severe threat to the environment and human health. In aquatic environment, dissolved organic matter (DOM)-mediated photochemical transformation is one of the main processes in the fate of organoarsenics. Dicarbonyl is a typical redox-active moiety in DOM. However, the knowledge on the photoconversion of organoarsenics by DOM, especially the contributions of dicarbonyl moieties is still limited. Here, we systematically investigated the photochemical transformation of three organoarsenics with the simplest β -diketone, acetylacetone (AcAc), as a model dicarbonyl moiety of DOM. The presence of AcAc significantly enhanced the photochemical conversion of roxarsone (ROX), whereas only minor effects were observed for 3-amino-4-hydroxyphenylarsonic acid (HAPA) and arsanilic acid (ASA), because the latter two (with an amino (-NH2 ) group) are more photoactive than ROX (with a nitro (-NO2 ) group). The results demonstrate that AcAc was a potent photo-activator and the reduction of –NO2 to –NH2 might be a rate-limiting step in the phototransformation of ROX. At a 1:1 M ratio of AcAc to ROX, the photochemical transformation rate of ROX was increased by 7 folds. In O2 -rich environment, singlet oxygen, peroxide radicals, and ·OH were the main reactive species that led to the breakage of the C–As bond in ROX and the oxidation of the released arsono group to arsenate, whereas the triplet-excited state of AcAc ( 3 AcAc*) and carbon-centered radicals from the photolysis of AcAc dominated in the reductive transformation of ROX. In anoxic environment, 3-amino-4-hydroxyphenylarsonic acid was one of the main reductive transformation intermediates of ROX, whose photolysis rate was about 35 times that of ROX. The knowledge obtained here is of great significance to better understand the fate of organoarsenics in natural environment. Graphical abstract: Image 1 Highlights: AcAc affected the fate of organoarsenics through enhanced photodegradation. The electron-donating property of substituents matters in the photodegradation. Organic arsenics with amino are easily degraded via a photoionization pathway. The degradation of ROX by AcAc undergoes oxidation and reduction pathways.