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Peracetic acid (PAA) is a widely used disinfectant, and combined UV light with PAA (i.e. UV/PAA) can be a novel advanced oxidation process for elimination of water contaminants. This study is among the first to evaluate the photolysis of PAA under UV irradiation (254 nm) and degradation of pharmaceuticals by UV/PAA. PAA exhibited high quantum yields (Φ254nm = 1.20 and 2.09 mol·Einstein−1 for the neutral (PAA0) and anionic (PAA-) species, respectively) and also showed scavenging effects on hydroxyl radicals (k•OH/PAA0 = (9.33±0.3)×108 M−1·s−1 and k•OH/PAA- = (9.97±2.3)×109 M−1·s−1). The pharmaceuticals were persistent with PAA alone but degraded rapidly by UV/PAA. The contributions of direct photolysis, hydroxyl radicals, and other radicals to pharmaceutical degradation under UV/PAA were systematically evaluated. Results revealed that •OH was the primary radical responsible for the degradation of carbamazepine and ibuprofen by UV/PAA, whereas CH3C(=O)O• and/or CH3C(=O)O2• contributed significantly to the degradation of naproxen and 2-naphthoxyacetic acid by UV/PAA in addition to •OH. The carbon-centered radicals generated from UV/PAA showed strong reactivity to oxidize certain naphthyl compounds. The new knowledge obtained in this study will facilitate further research and development of UV/PAA as a new degradation strategy for water contaminants.
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Photolysis Products of Fluorinated Pharmaceuticals: A Combined Fluorine Nuclear Magnetic Resonance Spectroscopy and Mass Spectrometry Approach
Abstract The aqueous photolysis of four pharmaceuticals with varying fluorinated functional groups was assessed under neutral, alkaline, advanced oxidation, and advanced reduction conditions with varying light sources. Solar simulator quantum yields were 2.21 × 10−1 mol Ei−1for enrofloxacin, 9.36 × 10−3 mol Ei−1for voriconazole, and 1.49 × 10−2 mol Ei−1for flecainide. Florfenicol direct photolysis was slow, taking 150 h for three degradation half‐lives. Bimolecular rate constants between pharmaceuticals and hydroxyl radicals were 109to 1010 M−1 s−1. Using a combined quantitative fluorine nuclear magnetic resonance spectroscopy (19F‐NMR) and mass spectrometry approach, fluorine mass balances and photolysis product structures were elucidated. Enrofloxacin formed a variety of short‐lived fluorinated intermediates that retained the aryl F motif. Extended photolysis time led to complete aryl F mineralization to fluoride. The aliphatic F moiety on florfenicol was also mineralized to fluoride, but the resulting product was a known antibiotic (thiamphenicol). For voriconazole, the two aryl Fs contributed more to fluoride production compared with the heteroaromatic F, indicating higher stability of the heteroaromatic F motif. The two aliphatic CF3moieties in the flecainide structure remained intact under all conditions, further supporting the stability of these moieties found in per‐ and polyfluoroalkyl substances under a variety of conditions. The advanced treatment conditions generating hydroxyl radicals or hydrated electrons accelerated the degradation, but not the defluorination, of flecainide. The combination of19F‐NMR and mass spectrometry proved powerful in allowing identification of fluorinated products and verifying the functional groups present in the intermediates and products. The results found in the present study will aid in the understanding of which fluorinated functional groups should be incorporated into pharmaceuticals to ensure organofluorine byproducts are not formed in the environment and help determine the water‐treatment processes that effectively remove specific pharmaceuticals and more generally fluorinated motifs.Environ Toxicol Chem2023;00:1–12. © 2023 The Authors.Environmental Toxicology and Chemistrypublished by Wiley Periodicals LLC on behalf of SETAC.
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- Award ID(s):
- 2304963
- PAR ID:
- 10477585
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Environmental Toxicology and Chemistry
- ISSN:
- 0730-7268
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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