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Peracetic acid (PAA) is a sanitizer with increasing use in food, medical and water treatment industries. Amino acids are important components in targeted foods for PAA treatment and ubiquitous in natural waterbodies and wastewater effluents as the primary form of dissolved organic nitrogen. To better understand the possible reactions, this work investigated the reaction kinetics and transformation pathways of selected amino acids towards PAA. Experimental results demonstrated that most amino acids showed sluggish reactivity to PAA except cysteine (CYS), methionine (MET), and histidine (HIS). CYS showed the highest reactivity with a very rapid reaction rate. Reactions of MET and HIS with PAA followed second-order kinetics with rate constants of 4.6 ± 0.2, and 1.8 ± 0.1 M−1s−1 at pH 7, respectively. The reactions were faster at pH 5 and 7 than at pH 9 due to PAA speciation. Low concentrations of H2O2 coexistent with PAA contributed little to the oxidation of amino acids. The primary oxidation products of amino acids with PAA were [O] addition compounds on the reactive sites at thiol, thioether and imidazole groups. Theoretical calculations were applied to predict the reactivity and regioselectivity of PAA electrophilic attacks on amino acids and improved mechanistic understanding. As an oxidative disinfectant, the reaction of PAA with organics to form byproducts is inevitable; however, this study shows that PAA exhibits lower and more selective reactivity towards biomolecules such as amino acids than other common disinfectants, causing less concern of toxic disinfection byproducts. This attribute may allow greater stability and more targeted actions of PAA in various applications. 

This study proposes a novel disinfection process by sequential application of peracetic acid (PAA) and ultra-violet light (UV), on the basis of elucidation of disinfection mechanisms under UV/PAA. Results show that hydroxyl radicals, generated by UV-activated PAA, contribute to the enhanced inactivation of Escherichia coli under UV/PAA compared to PAA alone or UV alone. Furthermore, the location of hydroxyl radical generation is a critical factor. Unlike UV/H2O2, which generates hydroxyl radicals mainly in the bulk solution, the hydroxyl radicals under UV/PAA are produced close to or inside E. coli cells, due to PAA diffusion. Therefore, hydroxyl radicals exert significantly stronger disinfection power under UV/PAA than under UV/H2O2 conditions. Pre-exposing E. coli to PAA in the dark followed by application of UV (i.e., a PAA-UV/PAA process) promotes diffusion of PAA to the cells and achieves excellent disinfection efficiency while saving more than half of the energy cost associated with UV compared to simultaneous application of UV and PAA. The effectiveness of this new disinfection strategy has been demonstrated not only in lab water but also in wastewater matrices. 

Peracetic acid (PAA) is a disinfection oxidant used in many industries including wastewater treatment. β-Lactams, a group of widely prescribed antibiotics, are frequently detected in wastewater effluent and in the natural aquatic environment. The reaction kinetics and transformation of seven β-lactams (cefalexin (CFX), cefadroxil (CFR), cefapirin (CFP), cephalothin (CFT), ampicillin (AMP), amoxicillin (AMX) and penicillin G (PG)) toward PAA were investigated to elucidate the behavior of β-lactams during PAA oxidation processes. The reaction follows second-order kinetics and is much faster at pH 5 and 7 than at pH 9 due to speciation of PAA. Reactivity to PAA follows the order of CFR ~ CFX > AMP ~ AMX > CFT ~ CFP ~ PG and is related to β-lactam’s nucleophilicity. The thioether sulfur of β-lactams is attacked by PAA to generate sulfoxide products. Presence of the phenylglycinyl amino group on β-lactams can significantly influence electron distribution and the highest occupied molecular orbital (HOMO) location and energy in ways that enhance the reactivity to PAA. Reaction rate constants obtained in clean water matrix can be used to accurately model the decay of β-lactams by PAA in surface water matrix and only slightly overestimate the decay in wastewater matrix. Results of this study indicate that the oxidative transformation of β-lactams by PAA can be expected under appropriate wastewater treatment conditions. 

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.