RESUMEN
Peracetic acid (PAA) is emerging as a versatile agent for generating long-lived and selectively oxidative organic radicals (R-Oâ¢). Currently, the conventional transition metal-based activation strategies still suffer from metal ion leaching, undesirable by-products formation, and uncontrolled reactive species production. To address these challenges, we present a method employing BiOI with a unique electron structure as a PAA activator, thereby predominantly generating CH3C(O)O⢠radicals. The specificity of CH3C(O)O⢠generation ensured the superior performance of the BiOI/PAA system across a wide pH range (2.0 to 11.0), even in the presence of complex interfering substances such as humic acids, chloride ions, bicarbonate ions, and real-world water matrices. Unlike conventional catalytic oxidative methods, the BiOI/PAA system degrades sulfonamides without producing any toxic by-products. Our findings demonstrate the advantages of CH3C(O)O⢠in water decontamination and pave the way for the development of eco-friendly water decontaminations based on organic peroxides.
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Peracetic acid (PAA) oxidation catalyzed by metal-free carbons is promising for advanced water decontamination. Nevertheless, developing reaction-oriented and high-performance carbocatalysts has been limited by the ambiguous understanding of the intrinsic relationship between carbon chemical/molecular structure and PAA transformation behavior. Herein, we comprehensively investigated the PAA activation using a family of well-defined sp2/sp3 carbon hybrids from annealed nanodiamonds (ANDs). The activity of ANDs displays a volcano-type trend, with respect to the sp2/sp3 ratio. Intriguingly, sp3-C-enriched AND exhibits the best catalytic activity for PAA activation and phenolic oxidation, which is different from persulfate chemistry in which the sp2 network normally outperforms sp3 hybridization. At the electron-rich sp2-C site, PAA undergoes a reduction reaction to generate a reactive complex (AND-PAA*) and induces an electron-transfer oxidation pathway. At the sp3-C site adjacent to CâO, PAA is oxidized to surface-confined OH* and O* successively, which ultimately evolves into singlet oxygen (1O2) as the primary reactive species. Benefiting from the dual nonradical regimes on sp2/sp3 hybrids, AND mediates a sustainable redox recycle with PAA to continuously generate reactive species to attack water contaminants, meanwhile maintaining structural/chemical integrity and exceptional reusability in cyclic runs.
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Ácido Peracético , Ácido Peracético/química , Catálisis , Nanodiamantes/química , Purificación del Agua/métodos , Oxidación-Reducción , Contaminantes Químicos del Agua/química , Agua/químicaRESUMEN
Peracetic acid (PAA)-based advanced oxidation processes (AOPs) have shown broad application prospects in organic wastewater treatment. Alkoxy radicals including CH3COO⢠and CH3COOO⢠are primary reactive species in PAA-AOP systems; however, their reaction mechanism on attacking organic pollutants still remains controversial. In this study, a Co(II)/PAA homogeneous AOP system at neutral pH was constructed to generate these two alkoxy radicals, and their different reaction mechanisms with a typical emerging contaminant (sulfacetamide) were explored. Dynamic electron distribution analysis was applied to deeply reveal the radical-meditated reaction mechanism based on molecular orbital analysis. Results indicate that hydrogen atom abstraction is the most favorable route for both CH3COO⢠and CH3COOO⢠attacking sulfacetamide. However, both radicals cannot react with sulfacetamide via the radical adduct formation route. Interestingly, the single-electron transfer reaction is only favorable for CH3COO⢠due to its lower ESUMO. In comparison, CH3COOO⢠can react with sulfacetamide via a similar radical self-sacrificing bimolecular nucleophilic substitution (SN2) route owing to its high ESOMO and easy escape of unpaired electrons from n orbitals of O atoms in the peroxy bond. These findings can significantly improve the knowledge of reactivity of CH3COO⢠and CH3COOO⢠on attacking organic pollutants at the molecular orbital level.
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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 â NC solid surface â 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.
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Diamante , Electrones , Ácido Peracético , Ácido Peracético/química , Diamante/química , Transporte de Electrón , Fluorocarburos/química , Caprilatos/química , Propiedades de Superficie , Purificación del Agua , Contaminantes Químicos del Agua/químicaRESUMEN
Extensive research has been conducted on the utilization of a metal-based catalyst to activate peracetic acid (PAA) for the degradation of micropollutants (MPs) in water. Mn(II) is a commonly employed catalyst for homogeneous advanced oxidation processes (AOPs), but its catalytic performance with PAA is poor. This study showed that the environmentally friendly chelator ethylenediamine-N,N'-disuccinic acid (EDDS) could greatly facilitate the activation of Mn(II) in PAA for complete atrazine (ATZ) degradation. In this process, the EDDS enhanced the catalytic activity of manganese (Mn) and prevented disproportionation of transient Mn species, thus facilitating the decay of PAA and mineralization of ATZ. By employing electron spin resonance detection, quenching and probe tests, and 18O isotope-tracing experiments, the significance of high-valent Mn-oxo species (Mn(V)) in the Mn(II)-EDDS/PAA system was revealed. In particular, the involvement of the Mn(III) species was essential for the formation of Mn(V). Mn(III) species, along with singlet oxygen (1O2) and acetyl(per)oxyl radicals (CH3C(O)Oâ¢/CH3C(O)OOâ¢), also contributed partially to ATZ degradation. Mass spectrometry and density functional theory methods were used to study the transformation pathway and mechanism of ATZ. The toxicity assessment of the oxidative products indicated that the toxicity of ATZ decreased after the degradation reaction. Moreover, the system exhibited excellent interference resistance toward various anions and humid acid (HA), and it could selectively degrade multiple MPs.
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Manganeso , Ácido Peracético , Manganeso/química , Ácido Peracético/química , Contaminantes Químicos del Agua/química , Oxidación-Reducción , Etilenodiaminas/químicaRESUMEN
Cu(II)-catalyzed peracetic acid (PAA) processes have shown significant potential to remove contaminants in water treatment. Nevertheless, the role of coexistent H2O2 in the transformation from Cu(II) to Cu(I) remained contentious. Herein, with the Cu(II)/PAA process as an example, the respective roles of PAA and H2O2 on the Cu(II)/Cu(I) cycling were comprehensively investigated over the pH range of 7.0-10.5. Contrary to previous studies, it was surprisingly found that the coexistent deprotonated H2O2 (HO2-), instead of PAA, was crucial for accelerating the transformation from Cu(II) to Cu(I) (kHO2-/Cu(II) = (0.17-1) × 106 M-1 s-1, kPAA/Cu(II) < 2.33 ± 0.3 M-1 s-1). Subsequently, the formed Cu(I) preferentially reacted with PAA (kPAA/Cu(I) = (5.84 ± 0.17) × 102 M-1 s-1), rather than H2O2 (kH2O2/Cu(I) = (5.00 ± 0.2) × 101 M-1 s-1), generating reactive species to oxidize organic contaminants. With naproxen as the target pollutant, the proposed synergistic role of H2O2 and PAA was found to be highly dependent on the solution pH with weakly alkaline conditions being more conducive to naproxen degradation. Overall, this study systematically investigated the overlooked but crucial role of coexistent H2O2 in the Cu(II)/PAA process, which might provide valuable insights for better understanding the underlying mechanism in Cu-catalyzed PAA processes.
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In this study, biochar derived from chestnut shells was synthesized through pyrolysis at varying temperatures from 300 °C to 900 °C. The study unveiled that the pyrolysis temperature is pivotal in defining the physical and chemical attributes of biochar, notably its adsorption capabilities and its role in activating peracetic acid (PAA) for the efficient removal of acetaminophen (APAP) from aquatic environments. Notably, the biochar processed at 900 °C, referred to as CN900, demonstrated an exceptional adsorption efficiency of 55.8 mg g-1, significantly outperforming its counterparts produced at lower temperatures (CN300, CN500, and CN700). This enhanced performance of CN900 is attributed to its increased surface area, improved micro-porosity, and a greater abundance of oxygen-containing functional groups, which are a consequence of the elevated pyrolysis temperature. These oxygen-rich functional groups, such as carbonyls, play a crucial role in facilitating the decomposition of the O-O bond in PAA, leading to the generation of reactive oxygen species (ROS) through electron transfer mechanisms. This investigation contributes to the development of sustainable and cost-effective materials for water purification, underscoring the potential of chestnut shell-derived biochar as an efficient adsorbent and catalyst for PAA activation, thereby offering a viable solution for environmental cleanup efforts.
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Acetaminofén , Carbón Orgánico , Ácido Peracético , Pirólisis , Contaminantes Químicos del Agua , Carbón Orgánico/química , Acetaminofén/química , Contaminantes Químicos del Agua/química , Ácido Peracético/química , Adsorción , Purificación del Agua/métodosRESUMEN
In this study, electrochemistry was used to enhance the advanced oxidation of Fe(â ¡)/PAA (EC/Fe(â ¡)/PAA) to disintegrate waste activated sludge, and its performance and mechanism was compared with those of EC, PAA, EC/PAA and Fe(â ¡)/PAA. Results showed that the EC/Fe(â ¡)/PAA process effectively improved sludge disintegration and the concentrations of soluble chemical oxygen demand, polysaccharides and nucleic acids increased by 62.85%, 41.15% and 12.21%, respectively, compared to the Fe(â ¡)/PAA process. Mechanism analysis showed that the main active species produced in the EC/Fe(â ¡)/PAA process were â¢OH, R-O⢠and FeIVO2+. During the reaction process, sludge flocs were disrupted and particle size was reduced by the combined effects of active species oxidation, electrochemical oxidation and PAA oxidation. Furthermore, extracellular polymeric substances (EPS) was degraded, the conversion of TB-EPS to LB-EPS and S-EPS was promoted and the total protein and polysaccharide contents of EPS were increased. After sludge cells were disrupted, intracellular substances were released, causing an increase in nucleic acids, humic acids and fulvic acids in the supernatant, and resulting in sludge reduction. EC effectively accelerated the conversion of Fe(â ¢) to Fe(â ¡), which was conducive to the activation of PAA, while also enhancing the disintegration of EPS and sludge cells. This study provided an effective approach for the release of organic matter, offering significant benefits in sludge resource utilization.
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Aguas del Alcantarillado , Aguas del Alcantarillado/química , Eliminación de Residuos Líquidos/métodos , Oxidación-Reducción , Técnicas Electroquímicas/métodos , Hierro/química , Análisis de la Demanda Biológica de OxígenoRESUMEN
In this research, the effects of peracetic acid (PAA), polymeric flocculants, and their combined conditioning on improving the dewatering performance were comprehensively evaluated. The results showed that sludge cake moisture content, capillary suction time (CST), and specific resistance to filtration (SRF) were 70.6%, 48.1 s, and 3.42 × 1012 m/kg after adding 0.10 g/gMLSS PAA for 50 min, representing reductions of 12.60%, 40.32%, and 33.98%, respectively. Additionally, conditioning of sludge with polyferric sulfate (PFS), polyaluminum chloride (PAC), and cationic polyacrylamide (CPAM) enhanced sludge properties in the following order: CPAM > PAC > PFS. After the PAA oxidation and re-flocculation process, the optimal dosages of PFS, PAC, and CPAM were reduced to 1.5 g/L, 0.9 g/L, and 0.04 g/L, respectively. The sludge dewatering performance significantly improved, with sludge cake moisture content measuring 65.8%, 66.3%, and 61.7%, respectively. Moreover, the spatial multi-porous skeleton structures were formed via re-flocculation to improve the sludge dewatering. Furthermore, economic evaluation validated that the pre-oxidation and re-flocculation process could be considered an economically viable option. These research findings could serve as a valuable reference for practical engineering applications.
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Floculación , Ácido Peracético , Aguas del Alcantarillado , Aguas del Alcantarillado/química , Ácido Peracético/química , Oxidación-Reducción , Polímeros/química , Filtración , Eliminación de Residuos Líquidos/métodos , Porosidad , Resinas Acrílicas/químicaRESUMEN
Peracetic acid (PAA) combined with free ammonia (FA) pretreatment can be utilized to promote anaerobic fermentation (AF) of waste activated sludge (WAS) to produce short-chain fatty acids (SCFAs), and the resulting SCFAs are desirable carbon sources (C-sources) for polyhydroxyalkanoate (PHA) biosynthesis. This work aimed to determine the optimum conditions for PAA + FA pretreatment of sludge AF and the feasibility of using anaerobic fermentation liquor (AFL) for PHA production. To reveal the mechanisms of integrated pretreatment, the impacts of PAA + FA pretreatment on different stages of sludge AF and changes in the microbial community structure were explored. The experimental results showed that the maximum SCFA yield reached 491.35 ± 6.02 mg COD/g VSS on day 5 after pretreatment with 0.1 g PAA/g VSS +70 mg FA/L, which was significantly greater than that resulting from PAA or FA pretreatment alone. The mechanism analysis showed that PAA + FA pretreatment promoted sludge solubilization but strongly inhibited methanogenesis. According to the analysis of the microbial community, PAA + FA pretreatment changed the microbial community structure and promoted the enrichment of bacteria related to hydrolysis and acidification, and Proteiniclasticum, Macellibacteroides and Petrimonas became the dominant hydrolytic and acidifying bacteria. Finally, after alkali treatment, the AFL was utilized for batch-mode PHA production, and a maximum PHA yield of 55.05 wt% was achieved after five operation periods.
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Amoníaco , Ácidos Grasos Volátiles , Fermentación , Polihidroxialcanoatos , Aguas del Alcantarillado , Polihidroxialcanoatos/biosíntesis , Amoníaco/metabolismo , Ácidos Grasos Volátiles/metabolismo , Anaerobiosis , Eliminación de Residuos Líquidos/métodos , Reactores BiológicosRESUMEN
SARS-CoV-2 is primarily a respiratory virus that can potentially be transmitted through fomites. Sodium hypochlorite (NaOCl) and peracetic acid (PAA) are widely used disinfectants on surfaces in diverse settings such as hospitals and food production facilities. The objectives of this study were to investigate the virucidal efficacy of NaOCl and PAA against SARS-CoV-2 using the ASTM standard methods. In the suspension assay, NaOCl and PAA (5, 50, and 200 ppm) were tested against SARS-CoV-2 in the presence/absence of soil load after 1 min of contact time. In the carrier assay, NaOCl and PAA were tested at 200, 400, 600, and 1,000 ppm for 1 min and 200 and 1,000 ppm for 5 and 10 min. Stainless steel (SS) and high-density polyethylene (HDPE) disks were used as carriers. The virus was suspended in soil load and the disinfectants were prepared in 300 ppm of hard water. Virus quantification was done by TCID50 assay using Vero-E6 cell line. NaOCl and PAA were effective (> 3 log reduction in infectious virus) at 50 ppm in the absence of soil load. However, in the presence of soil load, 200 ppm was required for > 3 log reduction in virus infectivity. In contrast, NaOCl and PAA at 200 ppm and with a 1-min contact time were not effective against SARS-CoV-2 on either SS or HDPE surfaces. PAA at 200 ppm for 10 min was effective against SARS-CoV-2 on SS and HDPE surfaces, whereas NaOCl required 1,000 ppm for 10 min to be effective against SARS-CoV-2 on both surfaces. IMPORTANCE In the context of the COVID-19 pandemic, the World Health Organization (WHO) recommended the use of chlorine-based products such as sodium hypochlorite (NaOCl) at 1,000 ppm for a minimum of 1 min to disinfect environmental surfaces. However, this recommendation was not based on validated studies on the actual SARS-CoV-2 itself. In fact, over half of the chemical disinfectants, including many peracetic acid products, listed in EPA List N were approved based on "kills a harder-to-kill pathogen" without further validation on SARS-CoV-2. Research on SARS-CoV-2 is restricted to BSL3 laboratories and the urgency of tackling the pandemic might explain the lack of studies on the actual virus. Our results show that the WHO recommendation of 1 min contact time with 1,000 ppm NaOCl is not effective against SARS-CoV-2 on surfaces. Also, our results indicate that PAA is effective against SARS-CoV-2 on surfaces and can be used as safer and more environmentally friendly alternative to NaOCl at a lower concentration.
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COVID-19 , Desinfectantes , Humanos , Hipoclorito de Sodio/farmacología , Ácido Peracético/farmacología , SARS-CoV-2 , Pandemias , Polietileno , Desinfectantes/farmacologíaRESUMEN
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.
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Contaminantes Químicos del Agua , Purificación del Agua , Bromo , Ácido Peracético , Aguas Residuales , Bromatos , Desinfección/métodos , Purificación del Agua/métodosRESUMEN
Environmental-friendly and low-cost catalysts for peracetic acid (PAA) activation are vital to promote their application for micropollutant degradation in water. In this study, powdered activated carbon (PAC) was reported to improve the degradation of sulfamethoxazole (SMX). The improvement of SMX degradation in the PAC/PAA system was expected to be because of the PAA activation rather than the co-existing H2O2 activation. Non-radical oxidation pathways, including the mediated electron-transfer process and singlet oxygen (1O2), were evidenced to play the dominant roles in the degradation of micro-organic pollutants. The graphitization of PAC, persistent free radicals, and electron-donating groups like C-OH were proposed to contribute to the activation of PAA. High SMX degradation could be achieved in the acidic and neutral conditions in the PAC/PAA system. Overall, higher dosages of PAC (0-0.02 g/L) and PAA (0-100 µM) benefited the degradation of SMX. The presence of HCO3- could lower the SMX degradation significantly, while Cl-, PO43-, and humic acid (HA) only reduced the SMX degradation efficiency a little. Overall, this study offered an efficient non-radical PAA activation method using PAC, which can be effectively used to degrade micro-organic pollutants.
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Ácido Peracético , Contaminantes Químicos del Agua , Sulfametoxazol , Peróxido de Hidrógeno , Carbón Orgánico , Oxidación-ReducciónRESUMEN
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.
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Desinfectantes , Contaminantes Químicos del Agua , Purificación del Agua , Ácido Peracético , Desinfección/métodos , Peróxido de Hidrógeno , Aguas Residuales , Cloro , Bromuros , Oxidantes , Cloruros , Halogenación , Purificación del Agua/métodos , Contaminantes Químicos del Agua/análisisRESUMEN
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)OOâ¢) 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.
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Ácido Peracético , Contaminantes Químicos del Agua , Peróxido de Hidrógeno , Aguas Residuales , Oxidación-ReducciónRESUMEN
This study provided an in-depth understanding of enhanced algae inactivation by combining ultraviolet and peracetic acid (UV/PAA) and selecting Microcystis aeruginosa as the target algae species. The electron paramagnetic resonance (EPR) tests and scavenging experiments provided direct evidence on the formed reactive species (RSs) and indicated the dominant role of RSs including singlet oxygen (1O2) and hydroxyl (HOâ¢) and organic (ROâ¢) radicals in algae inactivation. Based on the algae inactivation kinetic model and the determined steady-state concentration of RSs, the contribution of RSs was quantitatively assessed with the second-order rate constants for the inactivation of algae by HOâ¢, ROâ¢, and 1O2 of 2.67 × 109, 3.44 × 1010, and 1.72 × 109 M-1 s-1, respectively. Afterward, the coexisting bi/carbonate, acting as a shuttle, that promotes the transformation from HO⢠to RO⢠was evidenced to account for the better performance of the UV/PAA system in algae inactivation under the natural water background. Subsequently, along with the evaluation of the UV/PAA preoxidation to modify coagulation-sedimentation, the possible application of the UV/PAA process for algae removal was advanced.
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Contaminantes Químicos del Agua , Purificación del Agua , Rayos Ultravioleta , Ácido Peracético/farmacología , Agua , Peróxido de Hidrógeno , Oxidación-ReducciónRESUMEN
Identifying reactive species in advanced oxidation process (AOP) is an essential and intriguing topic that is also challenging and requires continuous efforts. In this study, we exploited a novel AOP technology involving peracetic acid (PAA) activation mediated by a MnII-nitrilotriacetic acid (NTA) complex, which outperformed iron- and cobalt-based PAA activation processes for rapidly degrading phenolic and aniline contaminants from water. The proposed MnII/NTA/PAA system exhibited non-radical oxidation features and could stoichiometrically oxidize sulfoxide probes to the corresponding sulfone products. More importantly, we traced the origin of O atoms from the sulfone products by 18O isotope-tracing experiments and found that PAA was the only oxygen-donor, which is different from the oxidation process mediated by high-valence manganese-oxo intermediates. According to the results of theoretical calculations, we proposed that NTA could tune the coordination circumstance of the MnII center to elongate the O-O bond of the complexed PAA. Additionally, the NTA-MnII-PAA* molecular cluster presented a lower energy gap than the MnII-PAA complex, indicating that the MnII-peroxy complex was more reactive in the presence of NTA. Thus, the NTA-MnII-PAA* complex exhibited a stronger oxidation potential than PAA, which could rapidly oxidize organic contaminants from water. Further, we generalized our findings to the CoII/PAA oxidation process and highlighted that the CoII-PAA* complex might be the overlooked reactive cobalt species. The significance of this work lies in discovering that sometimes the metal-peroxy complex could directly oxidize the contaminants without the further generation of high-valence metal-oxo intermediates and/or radical species through interspecies oxygen and/or electron transfer.
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Complejos de Coordinación , Contaminantes Químicos del Agua , Ácido Peracético , Oxígeno , Metales , Complejos de Coordinación/química , Cobalto , Oxidación-Reducción , Agua , Peróxido de HidrógenoRESUMEN
Recently, advanced oxidation processes (AOPs) based upon peracetic acid (PAA) with high efficiency for degrading aqueous organic contaminants have attracted extensive attention. Herein, a novel metal-free N-doped carbonaceous catalyst, namely, carbonized polyaniline (CPANI), was applied to activate PAA to degrade phenolic and pharmaceutical pollutants. The results showed that the CPANI/PAA system could effectively degrade 10 µM phenol in 60 min with low concentrations of PAA (0.1 mM) and catalyst (25 mg L-1). This system also performed well within a wide pH range of 5-9 and displayed high tolerance to Cl-, HCO3- and humic acid. The nonradical pathway [singlet oxygen (1O2)] was found to be the dominant pathway for degrading organic contaminants in the CPNAI/PAA system. Systematic characterization revealed that the graphitic N, pyridinic N, carbonyl groups (CO) and defects played the role of active sites on CPANI during the activation of PAA. The catalytic capacity of spent CPANI could be conveniently recovered by thermal treatment. The findings will be helpful for the application of metal-free carbonaceous catalyst/PAA processes in decontaminating water.
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Peróxido de Hidrógeno , Contaminantes Químicos del Agua , Ácido Peracético , Metales , Oxidación-Reducción , Fenoles , AguaRESUMEN
Since limitedly existing researches suggested Cu(II) had deficiently catalytic ability to PAA, in this work, we tested the oxidation performance of Cu(II)/PAA system on diclofenac (DCF) degradation under neutral conditions. It was found that overwhelming DCF removal could be obtained in Cu(II)/PAA system at pH 7.4 using phosphate buffer solution (PBS) compared to poor loss of DCF without PBS, and the apparent rate constant of DCF removal in PBS/Cu(II)/PAA system was 0.0359 min-1, 6.53 times of that in Cu(II)/PAA system. Organic radicals (i.e., CH3C(O)O⢠and CH3C(O)OOâ¢) were evidenced as the dominant contributors to DCF destruction in PBS/Cu(II)/PAA system. PBS motivated the reduction of Cu(II) to Cu(I) through chelation effect, and then the activation of PAA by Cu(I) was facilitated. Besides, due to the steric hindrance of Cu(II)-PBS complex (CuHPO4), PAA activation was mediated from non-radical-generating pathway to radical-generating pathway, leading to desirably effective DCF removal by radicals. The transformation of DCF mainly experienced hydroxylation, decarboxylation, formylation and dehydrogenation in PBS/Cu(II)/PAA system. This work proposes the potential of coupling of phosphate and Cu(II) in optimizing PAA activation for organic pollutants elimination.
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Ácido Peracético , Contaminantes Químicos del Agua , Diclofenaco , Fosfatos , Contaminantes Químicos del Agua/análisis , Oxidación-Reducción , Peróxido de HidrógenoRESUMEN
This study evaluated the effects of irrigating solutions containing 5% boric acid + 1% citric acid or 1% peracetic acid + high concentration hydrogen peroxide on root cleaning and bond strength of cementation systems after 24 h and 6 months of glass fiber post cementation. One hundred and twenty roots were endodontically treated. The specimens were randomized into one of four treatments (n = 10): DW (distilled water); NaOCl2.5% + EDTA17% (2.5% sodium hypochlorite solution + 17% EDTA); PA1% + HP (1% peracetic acid solution + high concentration of hydrogen peroxide); BA5% + CA1% (5% boric acid associated with 1% citric acid). The cleaning efficacy in the cervical, middle, and apical thirds of the post-space, and the push-out bond strength at 24 h and 6 months after post cementation were evaluated by Kruskal-Wallis and two-way ANOVA tests, respectively. BA5% + CA1% showed statistically significantly superior cleaning efficacy compared to the other solutions. This irrigation protocol also resulted in higher bond strength at 24 h and 6 months, regardless of the root third considered, and this was statistically significantly higher than those seen for DW and PA1% + HP. For BA5% + CA1% irrigation protocol, type 1 adhesive failure was the most prevalent. Post-space irrigation with BA5% + CA1% provided both higher cleaning efficacy and better bond strength.