Far-UVC 222 nm Treatment: Effects of Nitrate/Nitrite on Disinfection Byproduct Formation Potential.

Irradiation at far ultraviolet C (far-UVC) 222 nm by krypton chloride (KrCl*) excilamps can enhance microbial disinfection and micropollutant photolysis/oxidation. However, nitrate/nitrite, which absorbs strongly at 222 nm, may affect the formation of disinfection byproducts (DBPs). Herein, we evaluated model organic matter and real water samples and observed a substantial increase in the formation potential for trichloronitromethane (chloropicrin) (TCNM-FP), a nitrogenous DBP, by nitrate or nitrite after irradiation at 222 nm. At a disinfection dose of 100 mJ·cm-2, TCNM-FP of humic acids and fulvic acids increased from ∼0.4 to 25 and 43 µg·L-1, respectively, by the presence of 10 mg-N·L-1 nitrate. For the effect of nitrate concentration, the TCNM-FP peak was observed at 5-10 mg-N·L-1. Stronger fluence caused a greater increase of TCNM-FP. Similarly, the increase of TCNM-FP was also observed for wastewater and drinking water samples containing nitrate. Pretreatment using ozonation and coagulation, flocculation, and filtration or the addition of H2O2 can effectively control TCNM-FP. The formation potential of other DBPs was minorly affected by irradiation at 222 nm regardless of whether nitrate/nitrite was present. Overall, far-UVC 222 nm treatment poses the risk of increasing TCNM-FP of waters containing nitrate or nitrite at environmentally relevant concentrations and the mitigation strategies merit further research.

Unveiling the environmental significance of acetylperoxyl radical: Reactivity quantification and kinetic modeling.

Acetylperoxyl radical (CH3C(O)OO•) is among highly reactive organic radicals which are known to play crucial roles in atmospheric chemistry, aqueous chemistry and, most recently, peracetic acid (PAA)-based advanced oxidation processes. However, fundamental knowledge for its reactivity is scarce and severely hampers the understanding of relevant environmental processes. Herein, three independent experimental approaches were exploited for revelation and quantification of the reaction rates of acetylperoxyl radical. First, we developed and verified laser flash photolysis of biacetyl, ultraviolet (UV) photolysis of biacetyl, and pulse radiolysis of acetaldehyde, each as a clean source of CH3C(O)OO•. Then, using competition kinetics and selection of suitable probe and competitor compounds, the rate constants between CH3C(O)OO• and compounds of diverse structures were determined. The three experimental approaches complemented in reaction time scale and ease of operation, and provided cross-validation of the rate constants. Moreover, the formation of CH3C(O)OO• was verified by spin-trapped electron paramagnetic resonance, and potential influence of other reactive species in the systems was assessed. Overall, CH3C(O)OO• displays distinctively high reactivity and selectivity, reacting especially favorably with naphthyl and diene compounds (k ∼ 107-108 M-1 s-1) but sluggishly with N- and S-containing groups. Significantly, we demonstrated that incorporating acetylperoxyl radical-oxidation reactions significantly improved the accuracy in modeling the degradation of environmental micropollutants by UV/PAA treatment. This study is among the most comprehensive investigation for peroxyl radical reactivity to date, and establishes a robust methodology for investigating organic radical chemistry. The determined rate constants strengthen kinetic databases and improve modeling accuracy for natural and engineered systems.

Revisiting the synergistic oxidation of peracetic acid and permanganate(â ¦) towards micropollutants: The enhanced electron transfer mechanism of reactive manganese species.

Synergistic actions of peroxides and high-valent metals have garnered increasing attentions in wastewater treatment. However, how peroxides interact with the reactive metal species to enhance the reactivity remains unclear. Herein, we report the synergistic oxidation of peracetic acid (PAA) and permanganate(Ⅶ) towards micropollutants, and revisit the underlying mechanism. The PAA-Mn(VII) system showed remarkable efficiency with a 28-fold enhancement on sulfamethoxazole (SMX) degradation compared to Mn(Ⅶ) alone. Extensive quenching experiments and electron spin resonance (ESR) analysis revealed the generation of unexpected Mn(V) and Mn(VI) beyond Mn(III) in the PAA-Mn(VII) system. The utilization efficiency of Mn intermediates was quantified using 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulfonate (ABTS), and the results indicated that PAA could enhance the electron transfer efficiency of reactive manganese (Mn) species, thus accelerating the micropollutant degradation. Density functional theory (DFT) calculations showed that Mn intermediates could coordinate to the O1 of PAA with a low energy gap, enhancing the oxidation capacity and stability of Mn intermediates. A kinetic model based on first principles was established to simulate the time-dependent concentration profiles of the PAA-Mn complexes and quantify the contributions of the PAA-Mn(III) complex (50.8 to 59.3 %) and the PAA-Mn(Ⅴ/Ⅵ) complex (40.7 to 49.2 %). The PAA-Mn(VII) system was resistant to the interference from complex matrix components (e.g., chloride and humic acid), leading to the high efficiency in real wastewater. This work provides new insights into the interaction of PAA with reactive manganese species for accelerated oxidation of micropollutants, facilitating its application in wastewater treatment.

Revisiting the Electron Transfer Mechanisms in Ru(III)-Mediated Advanced Oxidation Processes with Peroxyacids and Ferrate(VI).

The potential of Ru(III)-mediated advanced oxidation processes has attracted attention due to the recyclable catalysis, high efficiency at circumneutral pHs, and robust resistance against background anions (e.g., phosphate). However, the reactive species in Ru(III)-peracetic acid (PAA) and Ru(III)-ferrate(VI) (FeO42-) systems have not been rigorously examined and were tentatively attributed to organic radicals (CH3C(O)O•/CH3C(O)OO•) and Fe(IV)/Ru(V), representing single electron transfer (SET) and double electron transfer (DET) mechanisms, respectively. Herein, the reaction mechanisms of both systems were investigated by chemical probes, stoichiometry, and electrochemical analysis, revealing different reaction pathways. The negligible contribution of hydroxyl (HO•) and organic (CH3C(O)O•/CH3C(O)OO•) radicals in the Ru(III)-PAA system clearly indicated a DET reaction via oxygen atom transfer (OAT) that produces Ru(V) as the only reactive species. Further, the Ru(III)-performic acid (PFA) system exhibited a similar OAT oxidation mechanism and efficiency. In contrast, the 1:2 stoichiometry and negligible Fe(IV) formation suggested the SET reaction between Ru(III) and ferrate(VI), generating Ru(IV), Ru(V), and Fe(V) as reactive species for micropollutant abatement. Despite the slower oxidation rate constant (kinetically modeled), Ru(V) could contribute comparably as Fe(V) to oxidation due to its higher steady-state concentration. These reaction mechanisms are distinctly different from the previous studies and provide new mechanistic insights into Ru chemistry and Ru(III)-based AOPs.

Efficacy and Mechanism of Antibiotic Resistance Gene Degradation and Cell Membrane Damage during Ultraviolet Advanced Oxidation Processes.

Combinations of UV with oxidants can initiate advanced oxidation processes (AOPs) and enhance bacterial inactivation. However, the effectiveness and mechanisms of UV-AOPs in damaging nucleic acids (e.g., antibiotic resistance genes (ARGs)) and cell integrity represent a knowledge gap. This study comprehensively compared ARG degradation and cell membrane damage under three different UV-AOPs. The extracellular ARG (eARG) removal efficiency followed the order of UV/chlorine > UV/H2O2 > UV/peracetic acid (PAA). Hydroxyl radical (•OH) and reactive chlorine species (RCS) largely contributed to eARG removal, while organic radicals made a minor contribution. For intracellular ARGs (iARGs), UV/H2O2 did not remove better than UV alone due to the scavenging of •OH by cell components, whereas UV/PAA provided a modest synergism, likely due to diffusion of PAA into cells and intracellular •OH generation. Comparatively, UV/chlorine achieved significant synergistic iARG removal, suggesting the critical role of the RCS in resisting cellular scavenging and inactivating ARGs. Additionally, flow cytometry analysis demonstrated that membrane damage was mainly attributed to chlorine oxidation, while the impacts of radicals, H2O2, and PAA were negligible. These results provide mechanistic insights into bacterial inactivation and fate of ARGs during UV-AOPs, and shed light on the suitability of quantitative polymerase chain reaction (qPCR) and flow cytometry in assessing disinfection performance.

Prehydrated Electrons Activated by Continuous Electron Transfer Stemmed from Peracetic Acid Homolysis Mediated by Diamond Surface Defects for Enhanced PFOA Destruction.

Research on the use of peracetic acid (PAA) activated by nonmetal solid catalysts for the removal of dissolved refractory organic compounds has gained attention recently due to its improved efficiency and suitability for advanced water treatment (AWT). Among these catalysts, nanocarbon (NC) stands out as an exceptional example. In the NC-based peroxide AWT studies, the focus on the mechanism involving multimedia coordination on the NC surface (reactive species (RS) path, electron reduction non-RS pathway, and singlet oxygen non-RS path) has been confined to the one-step electron reaction, leaving the mechanisms of multichannel or continuous electron transfer paths unexplored. Moreover, there are very few studies that have identified the nonfree radical pathway initiated by electron transfer within PAA AWT. In this study, the complete decomposition (kobs = 0.1995) and significant defluorination of perfluorooctanoic acid (PFOA, deF% = 72%) through PAA/NC has been confirmed. Through the use of multiple electrochemical monitors and the exploration of current diffusion effects, the process of electron reception and conduction stimulated by PAA activation was examined, leading to the discovery of the dynamic process from the PAA molecule → NC solid surface → target object. The vital role of prehydrated electrons (epre-) before the entry of resolvable electrons into the aqueous phase was also detailed. To the best of our knowledge, this is the first instance of identifying the nonradical mechanism of continuous electron transfer in PAA-based AWT, which deviates from the previously identified mechanisms of singlet oxygen, single-electron, or double-electron single-path transfer. The pathway, along with the strong reducibility of epre- initiated by this pathway, has been proven to be essential in reducing the need for catalysts and chemicals in AWT.

Paxlovid use is associated with lower risk of cardiovascular diseases in COVID-19 patients with autoimmune rheumatic diseases: a retrospective cohort study.

BACKGROUND: Paxlovid has been shown to be effective in reducing mortality and hospitalization rates in patients with coronavirus disease 2019 (COVID-19). It is not known whether Paxlovid can reduce the risk of cardiovascular diseases (CVD) in COVID-19-surviving patients with autoimmune rheumatic diseases (AIRDs). METHODS: TriNetX data from the US Collaborative Network were used in this study. A total of 5,671,395 patients with AIRDs were enrolled between January 1, 2010, and December 31, 2021. People diagnosed with COVID-19 were included in the cohort (n = 238,142) from January 1, 2022, to December 31, 2022. The Study population was divided into two groups based on Paxlovid use. Propensity score matching was used to generate groups with matched baseline characteristics. The hazard ratios (HRs) and 95% confidence intervals of cardiovascular outcomes, admission rate, mortality rate, and intensive care unit (ICU) admission rate were calculated between Paxlovid and non-Paxlovid groups. Subgroup analyses on sex, age, race, autoimmune diseases group, and sensitivity analyses for Paxlovid use within the first day or within 2-5 days of COVID-19 diagnosis were performed. RESULTS: Paxlovid use was associated with lower risks of cerebrovascular complications (HR = 0.65 [0.47-0.88]), arrhythmia outcomes (HR = 0.81 [0.68-0.94]), ischemic heart disease, other cardiac disorders (HR = 0.51 [0.35-0.74]) naming heart failure (HR = 0.41 [0.26-0.63]) and deep vein thrombosis (HR = 0.46 [0.24-0.87]) belonging to thrombotic disorders in AIRD patients with COVID-19. Compared with the Non-Paxlovid group, risks of major adverse cardiac events (HR = 0.56 [0.44-0.70]) and any cardiovascular outcome mentioned above (HR = 0.76 [0.66-0.86]) were lower in the Paxlovid group. Moreover, the mortality (HR = 0.21 [0.11-0.40]), admission (HR = 0.68 [0.60-0.76]), and ICU admission rates (HR = 0.52 [0.33-0.80]) were significantly lower in the Paxlovid group than in the non-Paxlovid group. Paxlovid appears to be more effective in male, older, and Black patients with AIRD. The risks of cardiovascular outcomes and severe conditions were reduced significantly with Paxlovid prescribed within the first day of COVID-19 diagnosis. CONCLUSIONS: Paxlovid use is associated with a lower risk of CVDs and severe conditions in COVID-19-surviving patients with AIRD.

New insight into the intravenous immunoglobulin treatment in Multisystem Inflammatory Syndrome in children and adults.

Within 6 months of the coronavirus pandemic, a new disease entity associated with a multisystem hyperinflammation syndrome as a result of a previous infection with the SARS-CoV-2 virus is increasingly being identified in children termed Multisystem Inflammatory Syndrome in Children (MIS-C) and more recently in adults(MIS-A). Due to its clinical similarity with Kawasaki Disease, some institutions have used intravenous immunoglobulins and steroids as first line agents in the management of the disease. We seek to find how effective intravenous immunoglobulin therapy is across these two disease entities. A comprehensive English literature search was conducted across PubMed, MEDLINE, and EMBASE databases using the keywords multisystem inflammatory syndrome in children/adults and treatment. All major online libraries concerning the diagnosis and treatment of MIS-C and MIS-A were searched. Relevant papers were read, reviewed, and analyzed. The use of intravenous immunoglobulins (IVIG) and steroids for the treatment of multisystemic inflammatory syndrome in children(MIS-C) is well established and recommended by multiple pediatric governing institutions. However, there is still no optimal treatment guideline or consensus on the use of IVIG in adults. The use of IVIG in both the child and adult populations may lower the risk of treatment failure and the need for adjunctive immunomodulatory therapy. Despite the promising results of IVIG use for the management of MIS-C and MIS-A, considering the pathophysiological differences between MIS-C and MIS-A, healthcare professionals need to further assess the differences in disease risk and treatment. The optimal dose, frequency, and duration of treatment are still unknown, more research is needed to establish treatment guidelines.

The association between non-alcoholic fatty liver disease and atopic dermatitis: a population-based cohort study.

Background: In previous studies, it was reported that non-alcoholic fatty liver disease (NAFLD) incidence and prevalence increased in children with atopic dermatitis. Nevertheless, the actual association between the two diseases has not been fully proven in large-scale studies, and real-world evidence is missing. The objective of this nationwide, longitudinal cohort study was to evaluate the association between NAFLD and atopic dermatitis. Methods: The National Health Insurance Research Database in Taiwan was utilized in this study. Patients with records of NAFLD diagnosis were recruited as the experimental group, and patients having less than three outpatient visits or one inpatient visiting record due to NAFLD were excluded from the study design. Non-NAFLD controls were matched based on a 1:4 propensity score matching. Potential confounders including age, gender, comorbidity, and medical utilization status were considered as covariates. The risk of future atopic dermatitis would be evaluated based on multivariate Cox proportional hazard regression. Results: Compared with people without NAFLD, a decreased risk of atopic dermatitis in NALFD patients had been observed (aHR = 0.93, 95% CI 0.87-0.98). The trend was especially presented in young NAFLD patients. In patients younger than 40 years old, a 20% decreased risk of atopic dermatitis was reported (aHR = 0.80, 95% CI 0.70-0.92). Conclusion: People with NAFLD were not associated with an increased risk of atopic dermatitis. Conversely, a 0.93-fold risk was noted in NAFLD patients, compared with NAFLD-free controls. Future studies are warranted to evaluate further the mechanism regarding the interplay between the inflammatory mechanisms of NAFLD and atopic dermatitis.

Degradation and Defluorination of Per- and Polyfluoroalkyl Substances by Direct Photolysis at 222 nm.

The susceptibility of 19 representative per- and polyfluoroalkyl substances (PFAS) to direct photolysis and defluorination under far-UVC 222 nm irradiation was investigated. Enhanced photolysis occurred for perfluorocarboxylic acids (PFCAs), fluorotelomer unsaturated carboxylic acids (FTUCAs), and GenX, compared to that at conventional 254 nm irradiation on a similar fluence basis, while other PFAS showed minimal decay. For degradable PFAS, up to 81% of parent compound decay (photolysis rate constant (k222 nm) = 8.19-34.76 L·Einstein-1; quantum yield (Φ222 nm) = 0.031-0.158) and up to 31% of defluorination were achieved within 4 h, and the major transformation products were shorter-chain PFCAs. Solution pH, dissolved oxygen, carbonate, phosphate, chloride, and humic acids had mild impacts, while nitrate significantly affected PFAS photolysis/defluorination at 222 nm. Decarboxylation is a crucial step of photolytic decay. The slower degradation of short-chain PFCAs than long-chain ones is related to molar absorptivity and may also be influenced by chain-length dependent structural factors, such as differences in pKa, conformation, and perfluoroalkyl radical stability. Meanwhile, theoretical calculations indicated that the widely proposed HF elimination from the alcohol intermediate (CnF2n+1OH) of PFCA is an unlikely degradation pathway due to high activation barriers. These new findings are useful for further development of far-UVC technology for PFAS in water treatment.

Simultaneous detection and quantification of multiple pathogen targets in wastewater.

Wastewater-based epidemiology has emerged as a critical tool for public health surveillance, building on decades of environmental surveillance work for pathogens such as poliovirus. Work to date has been limited to monitoring a single pathogen or small numbers of pathogens in targeted studies; however, few studies consider simultaneous quantitative analysis of a wide variety of pathogens, which could greatly increase the utility of wastewater surveillance. We developed a novel quantitative multi-pathogen surveillance approach (35 pathogen targets including bacteria, viruses, protozoa, and helminths) using TaqMan Array Cards (TAC) and applied the method on concentrated wastewater samples collected at four wastewater treatment plants in Atlanta, GA from February to October of 2020. From sewersheds serving approximately 2 million people, we detected a wide range of targets including many we expected to find in wastewater (e.g., enterotoxigenic E. coli and Giardia in 97% of 29 samples at stable concentrations) as well as unexpected targets including Strongyloides stercoralis (a human threadworm rarely observed in the USA). Other notable detections included SARS-CoV-2, but also several pathogen targets that are not commonly included in wastewater surveillance like Acanthamoeba spp., Balantidium coli, Entamoeba histolytica, astrovirus, norovirus, and sapovirus. Our data suggest broad utility in expanding the scope of enteric pathogen surveillance in wastewaters, with potential for application in a variety of settings where pathogen quantification in fecal waste streams can inform public health surveillance and selection of control measures to limit infections.

Mechanistic Insight for Disinfection Byproduct Formation Potential of Peracetic Acid and Performic Acid in Halide-Containing Water.

Peracetic acid (PAA) and performic acid (PFA) are two major peroxyacid (POA) oxidants of growing usage. This study reports the first systematic evaluation of PAA, PFA, and chlorine for their disinfection byproduct (DBP) formation potential in wastewater with or without high halide (i.e., bromide or iodide) concentrations. Compared with chlorine, DBP formation by PAA and PFA was minimal in regular wastewater. However, during 24 h disinfection of saline wastewater, PAA surprisingly produced more brominated and iodinated DBPs than chlorine, while PFA effectively kept all tested DBPs at bay. To understand these phenomena, a kinetic model was developed based on the literature and an additional kinetic investigation of POA decay and DBP (e.g., bromate, iodate, and iodophenol) generation in the POA/halide systems. The results show that PFA not only oxidizes halides 4-5 times faster than PAA to the corresponding HOBr or HOI but also efficiently oxidizes HOI/IO- to IO3-, thereby mitigating iodinated DBP formation. Additionally, PFA's rapid self-decay and slow release of H2O2 limit the HOBr level over the long-term oxidation in bromide-containing water. For saline water, this paper reveals the DBP formation potential of PAA and identifies PFA as an alternative to minimize DBPs. The new kinetic model is useful to optimize oxidant selection and elucidate involved DBP chemistry.

Enhanced Direct Photolysis of Organic Micropollutants by Far-UVC Light at 222 nm from KrCl* Excilamps.

Krypton chloride (KrCl*) excilamps emitting at far-UVC 222 nm represent a promising technology for microbial disinfection and advanced oxidation of organic micropollutants (OMPs) in water treatment. However, direct photolysis rates and photochemical properties at 222 nm are largely unknown for common OMPs. In this study, we evaluated photolysis for 46 OMPs by a KrCl* excilamp and compared it with a low-pressure mercury UV lamp. Generally, OMP photolysis was greatly enhanced at 222 nm with fluence rate-normalized rate constants of 0.2-21.6 cm2·µEinstein-1, regardless of whether they feature higher or lower absorbance at 222 nm than at 254 nm. The photolysis rate constants and quantum yields were 10-100 and 1.1-47 times higher, respectively, than those at 254 nm for most OMPs. The enhanced photolysis at 222 nm was mainly caused by strong light absorbance for non-nitrogenous, aniline-like, and triazine OMPs, while notably higher quantum yield (4-47 times of that at 254 nm) occurred for nitrogenous OMPs. At 222 nm, humic acid can inhibit OMP photolysis by light screening and potentially by quenching intermediates, while nitrate/nitrite may contribute more than others to screen light. Overall, KrCl* excilamps are promising in achieving effective OMP photolysis and merit further research.

Enhanced Oxidation of Antibiotics by Ferrate Mediated with Natural Organic Matter: Role of Phenolic Moieties.

The increasing presence of antibiotics in water sources threatens public health and ecosystems. Various treatments have been previously applied to degrade antibiotics, yet their efficiency is commonly hindered by the presence of natural organic matter (NOM) in water. On the contrary, we show here that nine types of NOM and NOM model compounds improved the removal of trimethoprim and sulfamethoxazole by ferrate(VI) (FeVIO42-, Fe(VI)) under mild alkaline conditions. This is probably associated with the presence of phenolic moieties in NOMs, as suggested by first-order kinetics using NOM, phenol, and hydroquinone. Electron paramagnetic resonance reveals that NOM radicals are generated within milliseconds in the Fe(VI)-NOM system via single-electron transfer from NOM to Fe(VI) with the formation of Fe(V). The dominance of the Fe(V) reaction with antibiotics resulted in their enhanced removal despite concurrent reactions between Fe(V) and NOM moieties, the radicals, and water. Kinetic modeling considering Fe(V) explains the enhanced kinetics of antibiotics abatement at low phenol concentrations. Experiments with humic and fulvic acids of lake and river waters show similar results, thus supporting the enhanced abatement of antibiotics in real water situations.

Selective Transformation of Micropollutants in Saline Wastewater by Peracetic Acid: The Overlooked Brominating Agents.

Peracetic acid (PAA) is an emerging alternative disinfectant for saline waters; HOBr or HOCl is known as the sole species contributing to halogenation reactions during PAA oxidation and disinfection. However, new results herein strongly indicated that the brominating agents (e.g., BrCl, Br2, BrOCl, and Br2O) are generated at concentrations typically lower than HOCl and HOBr but played significant roles in micropollutants transformation. The presence of Cl- and Br- at environmentally relevant levels could greatly accelerate the micropollutants (e.g., 17α-ethinylestraiol (EE2)) transformation by PAA. The kinetic model and quantum chemical calculations collectively indicated that the reactivities of bromine species toward EE2 follow the order of BrCl > Br2 > BrOCl > Br2O > HOBr. In saline waters with elevated Cl- and Br- levels, these overlooked brominating agents influence bromination rates of more nucleophilic constituents of natural organic matter and increase the total organic bromine. Overall, this work refines our knowledge regarding the species-specific reactivity of brominating agents and highlights the critical roles of these agents in micropollutant abatement and disinfection byproduct formation during PAA oxidation and disinfection.

Water decontamination via nonradical process by nanoconfined Fenton-like catalysts.

There is an urgent need to develop effective and sustainable solutions to reduce water pollution. Heterogeneous Fenton-like catalysts are frequently used to eliminate contaminants from water. However, the applicability of these catalysts is limited due to low availability of the reactive species (RS). Herein, nanoconfinement strategy was applied to encapsulate short-lived RS at nanoscale to boost the utilization efficiency of the RS in Fenton-like reactions. The nanoconfined catalyst was fabricated by assembling Co3O4 nanoparticles in carbon nanotube nanochannels to achieve exceptional reaction rate and excellent selectivity. Experiments collectively suggested that the degradation of contaminants was attributed to singlet oxygen (1O2). Density functional theory calculations demonstrated the nanoconfined space contributes to quantum mutation and alters the transition state to lower activation energy barriers. Simulation results revealed that the enrichment of contaminant on the catalyst reduced the migration distance and enhanced the utilization of 1O2. The synergy between the shell layer and core-shell structure further improved the selectivity of 1O2 towards contaminant oxidation in real waters. The nanoconfined catalyst is expected to provide a viable strategy for water pollution control.

Picolinic Acid-Mediated Catalysis of Mn(II) for Peracetic Acid Oxidation Processes: Formation of High-Valent Mn Species.

Metal-based advanced oxidation processes (AOPs) with peracetic acid (PAA) have been extensively studied to degrade micropollutants (MPs) in wastewater. Mn(II) is a commonly used homogeneous metal catalyst for oxidant activation, but it performs poorly with PAA. This study identifies that the biodegradable chelating ligand picolinic acid (PICA) can significantly mediate Mn(II) activation of PAA for accelerated MP degradation. Results show that, while Mn(II) alone has minimal reactivity toward PAA, the presence of PICA accelerates PAA loss by Mn(II). The PAA-Mn(II)-PICA system removes various MPs (methylene blue, bisphenol A, naproxen, sulfamethoxazole, carbamazepine, and trimethoprim) rapidly at neutral pH, achieving >60% removal within 10 min in clean and wastewater matrices. Coexistent H2O2 and acetic acid in PAA play a negligible role in rapid MP degradation. In-depth evaluation with scavengers and probe compounds (tert-butyl alcohol, methanol, methyl phenyl sulfoxide, and methyl phenyl sulfone) suggested that high-valent Mn species (Mn(V)) is a likely main reactive species leading to rapid MP degradation, whereas soluble Mn(III)-PICA and radicals (CH3C(O)O• and CH3C(O)OO•) are minor reactive species. This study broadens the mechanistic understanding of metal-based AOPs using PAA in combination with chelating agents and indicates the PAA-Mn(II)-PICA system as a novel AOP for wastewater treatment.

The Minus Approach Can Redefine the Standard of Practice of Drinking Water Treatment.

Chlorine-based disinfection for drinking water treatment (DWT) was one of the 20th century's great public health achievements, as it substantially reduced the risk of acute microbial waterborne disease. However, today's chlorinated drinking water is not unambiguously safe; trace levels of regulated and unregulated disinfection byproducts (DBPs), and other known, unknown, and emerging contaminants (KUECs), present chronic risks that make them essential removal targets. Because conventional chemical-based DWT processes do little to remove DBPs or KUECs, alternative approaches are needed to minimize risks by removing DBP precursors and KUECs that are ubiquitous in water supplies. We present the "Minus Approach" as a toolbox of practices and technologies to mitigate KUECs and DBPs without compromising microbiological safety. The Minus Approach reduces problem-causing chemical addition treatment (i.e., the conventional "Plus Approach") by producing biologically stable water containing pathogens at levels having negligible human health risk and substantially lower concentrations of KUECs and DBPs. Aside from ozonation, the Minus Approach avoids primary chemical-based coagulants, disinfectants, and advanced oxidation processes. The Minus Approach focuses on bank filtration, biofiltration, adsorption, and membranes to biologically and physically remove DBP precursors, KUECs, and pathogens; consequently, water purveyors can use ultraviolet light at key locations in conjunction with smaller dosages of secondary chemical disinfectants to minimize microbial regrowth in distribution systems. We describe how the Minus Approach contrasts with the conventional Plus Approach, integrates with artificial intelligence, and can ultimately improve the sustainability performance of water treatment. Finally, we consider barriers to adoption of the Minus Approach.

Oxidation of Pharmaceuticals by Ferrate(VI)-Amino Acid Systems: Enhancement by Proline.

The occurrence of micropollutants in water threatens public health and ecology. Removal of micropollutants such as pharmaceuticals by a green oxidant, ferrate(VI) (FeVIO42-, Fe(VI)) can be accomplished. However, electron-deficient pharmaceuticals, such as carbamazepine (CBZ) showed a low removal rate by Fe(VI). This work investigates the activation of Fe(VI) by adding nine amino acids (AA) of different functionalities to accelerate the removal of CBZ in water under mild alkaline conditions. Among the studied amino acids, proline, a cyclic AA, had the highest removal of CBZ. The accelerated effect of proline was ascribed by demonstrating the involvement of highly reactive intermediate Fe(V) species, generated by one-electron transfer by the reaction of Fe(VI) with proline (i.e., Fe(VI) + proline → Fe(V) + proline•). The degradation kinetics of CBZ by a Fe(VI)-proline system was interpreted by kinetic modeling of the reactions involved that estimated the rate of the reaction of Fe(V) with CBZ as (1.03 ± 0.21) × 106 M-1 s-1, which was several orders of magnitude greater than that of Fe(VI) of 2.25 M-1 s-1. Overall, natural compounds such as amino acids may be applied to increase the removal efficiency of recalcitrant micropollutants by Fe(VI).

Bacteria and Virus Inactivation: Relative Efficacy and Mechanisms of Peroxyacids and Chlor(am)ine.

Peroxyacids (POAs) are a promising alternative to chlorine for reducing the formation of disinfection byproducts. However, their capacity for microbial inactivation and mechanisms of action require further investigation. We evaluated the efficacy of three POAs (performic acid (PFA), peracetic acid (PAA), and perpropionic acid (PPA)) and chlor(am)ine for inactivation of four representative microorganisms (Escherichia coli (Gram-negative bacteria), Staphylococcus epidermidis (Gram-positive bacteria), MS2 bacteriophage (nonenveloped virus), and Φ6 (enveloped virus)) and for reaction rates with biomolecules (amino acids and nucleotides). Bacterial inactivation efficacy (in anaerobic membrane bioreactor (AnMBR) effluent) followed the order of PFA > chlorine > PAA ≈ PPA. Fluorescence microscopic analysis indicated that free chlorine induced surface damage and cell lysis rapidly, whereas POAs led to intracellular oxidative stress through penetrating the intact cell membrane. However, POAs (50 µM) were less effective than chlorine at inactivating viruses, achieving only ∼1-log PFU removal for MS2 and Φ6 after 30 min of reaction in phosphate buffer without genome damage. Results suggest that POAs' unique interaction with bacteria and ineffective viral inactivation could be attributed to their selectivity toward cysteine and methionine through oxygen-transfer reactions and limited reactivity for other biomolecules. These mechanistic insights could inform the application of POAs in water and wastewater treatment.