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1. Oxidation of Amino Acids by Peracetic Acid: Reaction Kinetics, Pathways and Theoretical Calculations

   https://doi.org/https://doi.org/10.1016/j.wroa.2018.09.002  

   Du, P. ; Liu, W. ; Cao, H. ; Zhao, H. ; Huang, C.-H. ( January 2018 , Water research. X)

   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. 

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2. Chloramination of Nitromethane: Incomplete Chlorination and Unexpected Substitution Reaction

   https://doi.org/10.1021/acs.est.2c09821  

   Shi, Jiaming Lily ; Kim, Euna ; Cardosa, Georgia B. ; McCurry, Daniel L. ( May 2023 , Environmental Science & Technology)

   Ozone is commonly used as a pre-disinfectant in potable water reuse treatment trains. Nitromethane was recently found as a ubiquitous ozone byproduct in wastewater, and the key intermediate toward chloropicrin during subsequent secondary disinfection of ozonated wastewater effluent with chlorine. However many utilities have switched from free chlorine to chloramines as a secondary disinfectant. The reaction mechanism and kinetics of nitromethane transformation by chloramines, unlike free chlorine, are unknown. In this work, the kinetics, mechanism, and products of nitromethane chloramination were studied. The expected principal product was chloropicrin, because chloramines are commonly assumed to react similarly, although more slowly, compared to free chlorine. Different molar yields of chloropicrin were observed at acidic, neutral, and basic conditions, and surprisingly, transformation products other than chloropicrin were found. Monochloronitromethane and dichloronitromethane were detected at basic pH, and the mass balance was initially poor at neutral pH. Much of the missing mass was later attributed to nitrate formation, from a newly-identified pathway involving monochloramine reacting as a nucleophile rather than halogenating agent, through a presumed SN2 mechanism. The study indicates that nitromethane chloramination, unlike chlorination, is likely to produce a range of products, whose speciation is a function of pH and reaction time. 

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3. Sunlight photolysis of SARS-CoV-2 N1 gene target in the water environment: considerations for the environmental surveillance of wastewater-impacted surface waters

   https://doi.org/10.2166/wh.2023.091  

   Dunn, Fiona B. ; Silverman, Andrea I. ( August 2023 , Journal of Water and Health)

   Wastewater surveillance of SARS-CoV-2 has been used around the world to supplement clinical testing data for situational awareness of COVID-19 disease trends. Many regions of the world lack centralized wastewater collection and treatment infrastructure, which presents additional considerations for wastewater surveillance of SARS-CoV-2, including environmental decay of the RT-qPCR gene targets used for quantification of SARS-CoV-2 virions. Given the role of sunlight in the environmental decay of RNA, we evaluated sunlight photolysis kinetics of the N1 gene target in heat-inactivated SARS-CoV-2 with a solar simulator under laboratory conditions. Insignificant photolysis of the N1 target was observed in a photosensitizer-free matrix. Conversely, significant decay of the N1 target was observed in wastewater at a shallow depth (<1 cm). Given that sunlight irradiance is affected by several environmental factors, first-order decay rate models were used to evaluate the effect of water column depth, time of the year, and latitude on decay kinetics. Decay rate constants were found to decrease significantly with greater depth of the well-mixed water column, at high latitudes, and in the winter. Therefore, sunlight-mediated decay of the N1 gene target is likely to be minimal, and is unlikely to confound results from wastewater-based epidemiology programs utilizing wastewater-impacted surface waters.

    

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4. Electrochemical nutrient removal from natural wastewater sources and its impact on water quality

   https://doi.org/10.1016/j.watres.2021.118001  

   Kékedy-Nagy, László ; English, Leah ; Anari, Zahra ; Abolhassani, Mojtaba ; Pollet, Bruno G. ; Popp, Jennie ; Greenlee, Lauren F. ( February 2022 , Water Research)

   In this study, a suite of natural wastewater sources is tested to understand the effects of wastewater composition and source on electrochemically driven nitrogen and phosphorus nutrient removal. Kinetics, electrode behavior, and removal efficiency were evaluated during electrochemical precipitation, whereby a sacrificial magnesium (Mg) anode was used to drive precipitation of ammonium and phosphate. The electrochemical reactor demonstrated fast kinetics in the natural wastewater matrices, removing up to 54% of the phosphate present in natural wastewater within 1 min, with an energy input of only 0.04 kWh.m−3. After 1 min, phosphate removal followed a zero-order rate law in the 1 min - 30 min range. The zero-order rate constant (k) appears to depend upon differences in wastewater composition, where a faster rate constant is associated with higher Cl− and NH4+ concentrations, lower Ca2+ concentrations, and higher organic carbon content. The sacrificial Mg anode showed the lowest corrosion resistance in the natural industrial wastewater source, with an increased corrosion rate (vcorr) of 15.8 mm.y−1 compared to 1.9–3.5 mm.y−1 in municipal wastewater sources, while the Tafel slopes (β) showed a direct correlation with the natural wastewater composition and origin. An overall improvement of water quality was observed where important water quality parameters such as total organic carbon (TOC), total suspended solids (TSS), and turbidity showed a significant decrease. An economic analysis revealed costs based upon experimental Mg consumption are estimated to range from 0.19 $.m−3 to 0.30 $.m−3, but costs based upon theoretical Mg consumption range from 0.09 $.m−3 to 0.18 $.m−3. Overall, this study highlights that water chemistry parameters control nutrient recovery, while electrochemical treatment does not directly produce potable water, and that economic analysis should be based upon experimentally-determined Mg consumption data. 

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5. Mechanism of proton transfer in class A β-lactamase catalysis and inhibition by avibactam

   https://doi.org/10.1073/pnas.1922203117  

   Pemberton, Orville A. ; Noor, Radwan E. ; Kumar M. V., Vasantha ; Sanishvili, Ruslan ; Kemp, M. Trent ; Kearns, Fiona L. ; Woodcock, H. Lee ; Gelis, Ioannis ; Chen, Yu ( March 2020 , Proceedings of the National Academy of Sciences)

   Gram-negative bacteria expressing class A β-lactamases pose a serious health threat due to their ability to inactivate all β-lactam antibiotics. The acyl–enzyme intermediate is a central milestone in the hydrolysis reaction catalyzed by these enzymes. However, the protonation states of the catalytic residues in this complex have never been fully analyzed experimentally due to inherent difficulties. To help unravel the ambiguity surrounding class A β-lactamase catalysis, we have used ultrahigh-resolution X-ray crystallography and the recently approved β-lactamase inhibitor avibactam to trap the acyl–enzyme complex of class A β-lactamase CTX-M-14 at varying pHs. A 0.83-Å-resolution CTX-M-14 complex structure at pH 7.9 revealed a neutral state for both Lys73 and Glu166. Furthermore, the avibactam hydroxylamine-O-sulfonate group conformation varied according to pH, and this conformational switch appeared to correspond to a change in the Lys73 protonation state at low pH. In conjunction with computational analyses, our structures suggest that Lys73 has a perturbed acid dissociation constant (pK_a) compared with acyl–enzyme complexes with β-lactams, hindering its function to deprotonate Glu166 and the initiation of the deacylation reaction. Further NMR analysis demonstrated Lys73 pK_ato be ∼5.2 to 5.6. Together with previous ultrahigh-resolution crystal structures, these findings enable us to follow the proton transfer process of the entire acylation reaction and reveal the critical role of Lys73. They also shed light on the stability and reversibility of the avibactam carbamoyl acyl–enzyme complex, highlighting the effect of substrate functional groups in influencing the protonation states of catalytic residues and subsequently the progression of the reaction.

    

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