Differentiation of Pathways of Nitrated Byproduct Formation from Ammonium and Nitrite During Sulfate Radical Oxidation.

Recent studies found that both nitrite (NO2-) and ammonium (NH4+) lead to nitrophenolic byproducts in SO4•- oxidation processes, during which NO2• generated through the oxidation of the inorganic nitrogen by SO4•- is the key nitrating agent. This study demonstrates that the formation of phenoxy radicals to which NO2• can be incorporated immediately is another governing factor. Two types of sites having distinct reactivities in natural organic matter (NOM) molecules can be transformed to phenoxy radicals upon SO4•- oxidation. Fast sites associated with phenolic functionalities are primarily targeted in the reaction sequence involving NO2-, because both are preferentially oxidized. Following the depletion of NO2-, NH4+ becomes the main precursor of NO2• that interacts with slow sites associated with the carboxylic functionalities. Experimental data show that the formation of total organic nitrogen in 24 h reached 6.28 µM during SO4•- oxidation of NOM (4.96 mg/L organic carbon) in the presence of both NO2- (0.1 mM) and NH4+ (1.0 mM), while the sum of those formed in the presence of each alone was only 3.52 µM. Results of this study provide further insights into the mechanisms of nitrated byproduct formation when SO4•- is applied for environmental remediation.

New Insights into the Role of Nitrite in the Degradation of Tetrabromobisphenol S by Sulfate Radical Oxidation.

Tetrabromobisphenol S (TBBPS) is a brominated flame retardant and a contaminant of emerging concern. Several studies found that sulfate radical (SO4•-) oxidation is effective to degrade TBBPS. Here, we demonstrate that the presence of nitrite (NO2-) at environmentally relevant levels causes dramatic changes in the kinetics and pathways of TBBPS degradation by SO4•-. Initially, NO2- suppresses the reaction by competing with TBBPS for SO4•-. At the same time, SO4•- oxidizes NO2- to form nitrogen dioxide radicals (NO2•), which actively react with some key TBBPS degradation intermediates, thus greatly altering the transformation pathway. As a result, 2,6-dibromo-4-nitrophenol (DBNP) becomes the primary TBBPS product. As TBBPS undergoes degradation, the released bromide (Br-) is oxidized by SO4•- to form bromine radicals and free bromine. These reactive bromine species immediately combine with NO2• or NO2- to form nitryl bromide (BrNO2) that in turn attacks the parent TBBPS, resulting in its accelerated degradation and increased formation of toxic nitrophenolic byproducts. These results show that nitryl halides (e.g., BrNO2 or ClNO2) are likely formed yet inadequately recognized when SO4•- is applied to remediate halogenated pollutants in the subsurface environment where NO2- is ubiquitously found. These insights further underscore the potential risks of the application of SO4•- oxidation for the remediation of halogenated compounds in realistic environmental conditions.

Formation of brominated by-products during the degradation of tetrabromobisphenol S by Co2+/peroxymonosulfate oxidation.

Tetrabromobisphenol S (TBBPS), an emerging brominated flame retardant, can cause neurotoxic and cytotoxic effects to human physiology. In this study, the degradation of TBBPS in Co2+ activated peroxymonosulfate (PMS) oxidation process was explored. In particular, brominated by-products formed during the degradation of the TBBPS were examined. It was found that TBBPS could be effectively removed in the Co2+/PMS oxidation process. The pseudo-first-order rate constants were 0.13 min-1 at 0.2 mM PMS and 0.5 µM Co2+ initially. It appeared that TBBPS degradation occurred via and HO attacks, but played a dominant role. The presence of natural organic matter (NOM) greatly inhibited the transformation of the TBBPS, which can be explained by the scavenging of the radical species. ß-Scission, debromination, and cross-coupling were identified as the main reaction pathways of TBBPS degradation in the Co2+/PMS system. Further oxidation and ring-opening of the intermediates generated brominated by-products including bromoform, monobromoacetic acid, and dibromoacetic acid. The formation of the brominated by-products increased gradually in approximately 48 h. But, the presence of NOM reduced the yields of the brominated -by-products. The findings of this study indicate that organic bromine contaminants can be effectively removed but lead to brominated by-products in the activated PMS oxidation process, which should be taken into consideration when -based oxidation technology is applied.

Enhancing the Fenton-like Catalytic Activity of nFe2O3 by MIL-53(Cu) Support: A Mechanistic Investigation.

A novel Fenton-like catalyst was synthesized by immobilizing nano-Fe2O3 (nFe2O3) on MIL-53(Cu). The pseudo-first-order rate constant of bisphenol A degradation in the nFe2O3/MIL-53(Cu)/H2O2 system reached 0.0123 min-1, while the values in MIL-53(Cu)/H2O2 and nFe2O3/H2O2 systems were only 0.0026 and 0.0040 min-1, respectively. The characterization of nFe2O3/MIL-53(Cu) reveals that the supreme catalytic activity of this material could be ascribed to iron-copper synergy, smaller size, and better dispersion of nFe2O3 particles. Moreover, a method of trapping Cu(I) by neocuproine was developed, which could shield Cu(I) from interacting with iron and H2O2, and thus allow quantitative differentiation of the contribution to the enhanced catalytic activity by each of the factors. Using this method, 19% of the enhancement was determined to be contributed by synergistic effect, while 24% of the enhancement was due to the smaller size and better dispersion of the nFe2O3 particles on MIL-53(Cu) support. In addition, the performance of nFe2O3/MIL-53(Cu) only dropped 10.7% after five treatment cycles in real wastewater, showing good potential in practical application. We believe this study sheds light on the tailored design of Fenton-like catalysts and elucidates the catalytic mechanisms of supported bimetallic catalysts.

Formation of Nitrophenolic Byproducts during Heat-Activated Peroxydisulfate Oxidation in the Presence of Natural Organic Matter and Nitrite.

Sulfate radical (SO4•-)-based advanced oxidation is a viable in situ remediation technology for degrading organic contaminants in the subsurface. In this study, we demonstrated that SO4•- could induce the activation of nitrite, an anion commonly present in the subsurface environment, leading to the formation of nitrophenolic byproducts. Fourier-transform infrared spectroscope and 15N nuclear magnetic resonance analysis revealed that the inorganic nitrite was incorporated into natural organic matter (NOM) to form organic nitrogen upon SO4•- oxidation. Nitrophenolic byproducts, including 2-hydroxy-5-nitrobenzoic acid, 4-nitrophenol, and 2,4-dinitrophenol, were identified using high-resolution mass spectrometry in combination with a 15N labeling technique. Formation of nitrated byproducts was ascribed to the scavenging of SO4•- by nitrite, which not only generated the nitrating agent NO2• but also inhibited the degradation of organic compounds, making them more available to the reactions with NO2•. The phenolic moieties in NOM served as the main reactive sites for NO2• attack. The nitration begins with H abstraction on the phenoxy oxygen, followed by the addition of another NO2• to its ortho or para site. Decarboxylation followed by NO2• addition can also generate nitrophenolic byproducts. To the best of our knowledge, this is the first study reporting the nitration of NOM and formation of toxic nitrophenolic byproducts during SO4•--based oxidation. It sheds light on the potential risks of this technology in subsurface remediation practices.

Perfluorooctanesulfonate Degrades in a Laccase-Mediator System.

Perfluorooctanesulfonate (PFOS) is a compound that has wide applications with extreme persistence in the environment and the potential to bioaccumulate, and could induce adverse effects to ecosystems. We investigated the degradation of PFOS by laccase-induced enzyme catalyzed oxidative humification reactions (ECOHRs) using 1-hydroxybenzotriazole (HBT) as a mediator. Approximately 59% of PFOS was transformed over 162 days of incubation, and the reaction appeared to follow a pseudo-first-order model with reaction rate constant of 0.0066/ d ( r2 = 0.87) under one condition tested. Using differential absorption spectra and theoretical simulation, we elucidated the interaction between Cu2+/Mg2+ and PFOS, and proposed that Cu2+ and Mg2+ could serve as a bridge to bring the negatively charged PFOS and laccase to proximity, thus increasing the chance of radicals that are released from laccase to reach and react with PFOS. In addition, density functional theory modeling showed that PFOS complexation to the metal ions could unlock its helical configuration and decrease the C-C bond energy of PFOS. These changes allow the attack of PFOS C-C backbone by radicals to become easier. On the basis of products identification, we proposed that direct attack of PFOS by the HBT radical initiated the free radical chain reaction processes and led to the formation of fluoride and partially fluorinated compounds. These results suggest that ECOHR is a potential pathway by which PFOS could be degraded in the environment, and it may make a viable approach to remediate PFOS contamination via amendment of appropriate enzymes and mediators.

Chlorination and chloramination of benzophenone-3 and benzophenone-4 UV filters.

The objective of this research was to explore the fundamental reactions between chlorine/chloramine and 2-hydroxyl-4-methoxyl benzophenone (BP3)/2-hydroxyl-4-methoxyl benzophenone-sulfonic acid (BP4), which were the most common reactions in benzophenone-type UV filters during drinking water treatment processes. Both BP3 and BP4 could react with free chlorine and chloramine, with reactions following pseudo-first-order kinetics in excess of chlorine (HClO) and chloramine (NH2Cl). Generally, chlorination was more rapid than chloramination. BP4 was less reactive than BP3 toward both chlorine and chloramine, due to the presence of an electron-accepting sulfonate group. Therefore, BP3 had a significantly higher disinfection by-products (DBP) formation potential than BP4. Chlorination of BP3 and BP4 generated remarkably higher levels of DBPs than chloramination, with high pH conditions facilitating the formation of chloroform but inhibiting the formation of haloacetic acid (HAAs). Comparison of the reaction behavior of two different BP-type UV filters, i.e., BP3 and BP4, revealed that certain functional groups significantly affected the reactivity of BP-type UV filters in chlorination and chloramination processes. This contribution may provide new insights into the reaction behavior of UV filters during drinking water disinfection process using chlorine and/or chloramine as disinfectant, and provide guidelines for drinking water safety management.

Natural Organic Matter Exposed to Sulfate Radicals Increases Its Potential to Form Halogenated Disinfection Byproducts.

Sulfate radical-based advanced oxidation processes (SR-AOPs) are considered as viable technologies to degrade a variety of recalcitrant organic pollutants. This study demonstrates that o-phthalic acid (PA) could lead to the formation of brominated disinfection byproducts (DBPs) in SR-AOPs in the presence of bromide. However, PA does not generate DBPs in conventional halogenation processes. We found that this was attributed to the formation of phenolic intermediates susceptible to halogenation, such as salicylic acid through the oxidation of PA by SO4(•-). In addition, reactive bromine species could be generated from Br(-) oxidation by SO4(•-). Similar in situ generation of phenolic functionalities likely occurred by converting carboxylic substituents on aromatics to hydroxyl when natural organic matter (NOM) was exposed to trace level SO4(•-). It was found that such structural reconfiguration led to a great increase in the reactivity of NOM toward free halogen and, thus, its DBP formation potential. After a surface water sample was treated with 0.1 µM persulfate for 48 h, its potential to form chloroform, trichloroacetic acid, and dichloroacetic acid increased from 197.8, 54.3, and 27.6 to 236.2, 86.6, and 57.6 µg/L, respectively. This is the first report on possible NOM reconfiguration upon exposure to low-level SO4(•-) that has an implication in DBP formation. The findings highlight potential risks associated with SO4(•-)-based oxidation processes and help to avoid such risks in design and operation.

Formation of Halogenated Polyaromatic Compounds by Laccase Catalyzed Transformation of Halophenols.

Laccases are a type of extracellular enzyme produced by fungi, bacteria, and plants. Laccase can catalyze one-electron oxidation of a variety of phenolic compounds using molecular oxygen as the electron acceptor. In this study, transformation of halophenols (XPs) in laccase-catalyzed oxidation processes was explored. We first examined the intrinsic reaction kinetics and found that the transformation of XPs appeared first order to the concentrations of both XPs and laccase. A numerical model was developed to describe the role of humic acid (HA) in this process. It was demonstrated that HA could reverse the oxidation of XPs by acting as the inner filtrator of XP radical intermediates formed upon reactions between the substrates and laccase. The extent of such reversion was proportional to HA concentration. MS analysis in combination with quantum chemistry computation suggested that coupling products were generated. XPs coupled to each via C-C or C-O-C pathways, generating hydroxyl polyhalogenated biphenyl ethers (OH-PCDEs) and hydroxyl polyhalogenated biphenyls, respectively. Many of these polyhalogenated products are known to be hazardous to the ecosystem and human health, but they are not synthetic chemicals. This study shed light on their genesis in the environmental media.

Transformation of 17ß-Estradiol by Phanerochaete chrysosporium in Different Culture Media.

The removal of 17ß-estradiol (E2) by white-rot fungus Phanerochaete chrysosporium cultured in classic Kirk or potato medium was systematically investigated. Results demonstrated that E2 can be efficiently removed regardless of culture media type. However, the reaction intermediates and transformation pathways varied in different media. Estrone (E1) and estriol (E3) were sequentially generated as intermediates in the potato medium, but these intermediates were absent in Kirk medium. Such results were found to correlate to the peroxidases produced in Kirk medium. These enzymes catalyzed one-electron oxidation of E2 to form radicals that can undergo oxidative coupling. Similar enzymes were not detected in the potato medium, thus E2 underwent in vitro oxidation to form E1 and E3 sequentially. Adding glucose to the potato medium further accelerated such processes. The findings in this study provide insights into estrogen reactions mediated by P. chrysosporium and for potential development of biodegradation methods to reduce estrogen contamination levels.

Nitrite facilitated transformation of halophenols in ice.

This study investigated the expediated transformation of halophenols in the presence of nitrite (NO2-) under slightly acidic conditions in ice, whereas such transformation was negligible in liquid water at 4 °C. We proposed that this phenomenon was attributed to the freeze-concentration effect, incurring a pH drop and the aggregation of NO2- and halophenols within the liquid-like grain boundary layer amid ice crystals. Within this micro-environment, NO2- underwent protonation to generate reactive nitrous acid (HNO2) and nitrosonium ions (NO+) that facilitate the nitration and oxidation of halophenols. When 10 µÐœ halophenol was treated by freezing in the presence of 5 µÐœ NO2-, the total yields of nitrated products reached 2.4 µÐœ and 1.4 µÐœ within 12 h for 2-chlorophenol (2CP) and 2-bromophenol (2BP), respectively. NO+ drove oxidative coupling reactions, generating hydroxyl polyhalogenated diphenyl ethers (OH-PBDEs) and hydroxyl polyhalogenated diphenyls via C-O or C-C coupling. These two pathways were intricately intertwined. The presence of natural organic matter (NOM) mitigated the formation of nitrated products and completely suppressed the coupling products. This study offers valuable insights into the fate of halophenols in ice and suggests potential pathways for the formation of nitrophenolic compounds and OH-PBDEs in natural cold environments. These findings also open up a new avenue in environmental chemistry research.

Formation of nitrated naphthalene in the sulfate radical oxidation process in the presence of nitrite.

Polycyclic aromatic hydrocarbons (PAHs) have become a global environmental concern due to their potential hazardous implication for human health. In this study, we found that sulfate radical (SO4•-) could effectively degrade naphthalene (NAP), a representative PAH in groundwaters, generating 1-naphthol. This intermediate underwent further degradation, yielding ring-opening products including phthalic acid and salicylic acid. However, the presence of nitrite (NO2-), a prevalent ion in subsurface environments, was observed to compete with NAP for SO4•-, thus slowing down the NAP degradation. The reaction between NO2- and SO4•- generated a nitrogen dioxide radical (NO2•). Concurrently, in-situ formed 1-naphthol underwent further oxidization to the 1-naphthoxyl radical by SO4•-. The coupling of 1-naphthoxyl radicals with NO2• gave rise to a series of nitrated NAP, namely 2-nitro-1-naphthol, 4-nitro-1-naphthol, and 2,4-dinitro-1-naphthol. In addition, the in-situ formed phthalic acid and salicylic acid also underwent nitration, generating nitrophenolic products, although this pathway appeared less prominent than the nitration of 1-naphthol. When 10 µΜ NAP was subjected to heat activated peroxydisulfate oxidation in the presence of 10 µΜ NO2-, the total yield of nitrated products reached 0.730 µΜ in 120 min. Overall, the presence of NO2- dramatically altered the behavior of NAP degradation by SO4•- oxidation and contributed to the formation of toxic nitrated products. These findings raise awareness of the potential environmental risks associated with the application of SO4•--based oxidation processes for the remediation of PAHs-polluted sites in presence of NO2-.

Formation of brominated and nitrated byproducts during unactivated peroxymonosulfate oxidation of phenol.

Brominated and nitrated byproducts generated from bromide (Br-) and nitrite (NO2-), respectively, by sulfate radical (SO4•-) oxidation have raised increasing concern. However, little is known about the concurrent generation of brominated and nitrated byproducts in the unactivated peroxymonosulfate (PMS) oxidation process. This study revealed that Br- can facilitate the transformation of NO2- to nitrated byproducts during unactivated PMS oxidation of phenol. In the co-existence of 0.1 mM Br- and 0.5 mM NO2-, the total yield of identified nitrated byproducts reached 2.316 µM in 20 min, while none was found with NO2- alone. Nitryl bromide (BrNO2) as the primary nitrating agent was formed via the reaction of NO2- with free bromine in situ generated through the oxidation of Br- by PMS. BrNO2 rapidly reacted with phenol or bromophenols, generating highly toxic nitrophenols or nitrated bromophenols, respectively. Increasing NO2- concentration led to more nitrated byproducts but less brominated byproducts. This study advances our understanding of the transformation of Br- and NO2- in the unactivated PMS oxidation process. It also provides important insights into the potentially underestimated environmental risks when PMS is applied to degrade organic contaminants under realistic environments, particularly when Br- and NO2- co-exist.

Ketoprofen products induced photosensitization of sulfonamide antibiotics: The cocktail effects of pharmaceutical mixtures on their photodegradation.

Indirect photolysis induced by naturally occurring sensitizers constitutes an important pathway accounting for the transformation and fate of many recalcitrant micropollutants in sunlit surface waters. However, the photochemical transformation of micropollutants by photosensitizing pharmaceuticals has been less investigated. In this study, we demonstrated that the non-steroidal anti-inflammatory drug ketoprofen (KTF) and its photoproducts, 3-acetylbenzophenone (AcBP) and 3-ethylbenzophenone (EtBP), could sensitize the photodegradation of coexisting sulfonamide antibiotics, e.g., sulfamethoxazole (SMX), under artificial 365 nm ultraviolet (UV) and sunlight irradiation. Key reactive species including triplet excited state and singlet oxygen (1O2) responsible for photosensitization were identified by laser flash photolysis (LFP) and electron paramagnetic resonance (EPR) techniques, respectively. High-resolution mass spectrometry (HRMS) and structure-related reactivity analyses revealed that the sensitized photolysis of SMX occurred mainly through single electron transfer. The rate constants of sulfonamides sensitized by AcBP photolysis followed the order of sulfisoxazole (SIX)＞sulfathiazole (STZ)＞SMX＞sulfamethizole (SMT). Exposure to sunlight also enhanced the photolysis of SMX in the presence of KTF or AcBP, and water matrix had limited impact on such process. Overall, our results reveal the feasibility and mechanistic aspects of photosensitization of coexisting contaminants by pharmaceuticals (or their photoproducts) and provide new insights into the cocktail effects of pharmaceutical mixtures on their photochemical behaviors in aqueous environment.

Aqueous photolysis of naproxen exposed to UV and natural sunlight: Formation of excited triplet and photosensitizing product.

Photochemical transformation is an important attenuation process for the non-steroidal anti-inflammatory drug naproxen (NPX) in both engineered and natural waters. Herein, we investigated the photolysis of NPX in aqueous solution exposed to both ultraviolet (UV, 254 nm) and natural sunlight irradiation. Results show that N2 purging significantly promoted NPX photolysis under UV irradiation, suggesting the formation of excited triplet state (3NPX*) as a critical transient. This inference was supported by benzophenone photosensitization and transient absorption spectra. Sunlight quantum yield of NPX was only one fourteenth of that under UV irradiation, suggesting the wavelength-dependence of NPX photochemistry. 3NPX* formed upon irradiation of NPX underwent photodecarboxylation leading to the formation of 2-(1-hydroxyethyl)-6-methoxynaphthalene (2HE6MN), 2-(1-hydroperoxyethyl)-6-methoxynaphthalene (2HPE6MN), and 2-acetyl-6-methoxynaphthalene (2A6MN). Notably, the conjugation and spin-orbit coupling effects of carbonyl make 2A6MN a potent triplet sensitizer, therefore promoting the photodegradation of the parent NPX. In hospital wastewater, the photolysis of NPX was influenced because the photoproduct 2A6MN and wastewater components could competitively absorb photons. Bioluminescence inhibition assay demonstrated that photoproducts of NPX exhibited higher toxicity than the parent compound. Results of this study provide new insights into the photochemical behaviors of NPX during UV treatment and in sunlit surface waters.

Photochemical degradation of bisphenol S and its tetrahalogenated derivatives in water.

Bisphenol S (BPS), a widely used plasticizer, is known to have potential endocrine disrupting effects to organisms. Its tetrahalogenated derivatives, tetrachlorobisphenol S (TCBPS) and tetrabromobisphenol S (TBBPS), are flame retardants exhibiting high neurodevelopmental toxicity and cytotoxicity. Halogen substitution has been shown to significantly affect the optical and photochemical properties of organic compounds. In this study, we conducted a comparative investigation into the photochemical behaviors of BPS, TCBPS, and TBBPS in aqueous solutions under both laboratory UV and natural sunlight irradiation. Spectroscopic titration results indicated that the pKa of TCBPS (4.16) and TBBPS (4.13) are approximately 3.7 units smaller than that of BPS (7.85), indicating that the halogenated derivatives are mainly present as the phenolate anions under circumneutral conditions. The halogen substituents also cause a significant bathochromic shift in the absorption spectra of TCBPS and TBBPS compared to BPS, leading to the enhanced absorption of sunlight. Meanwhile, TCBPS and TBBPS showed higher quantum yields than BPS, attributed to the "heavy atom" effect of halogen substituents. GCSOLAR modeling predicted half-lives for BPS, TCBPS, and TBBPS in surface water in Nanjing (32°2'7.3''N, 118°50'21''E) under noon sunlight in clear mid-autumn days as 810.2, 3.4, and 0.7 min, respectively. Toxicity evaluation suggest potential ecological risks of BPS/TCBPS/TBBPS and their photoproducts to aquatic organisms. Our findings highlight direct photolysis as an important mechanism accounting for the attenuation of tetrahalogenated bisphenols in both sunlit surface waters and UV based water treatment processes.engineered (e.g., UV disinfection) and natural aquatic environments (e.g., surface fresh waters).

Oxidation of emerging contaminants by S(IV) activated ferrate: Identification of reactive species.

Studies on the Fe(VI)/S(IV) process have focused on improving the efficiency of emerging contaminants (ECs) degradation under alkaline conditions. However, the performance and mechanisms under varying pH levels remain insufficiently investigated. This tudy delved into the efficiency and mechanism of Fe(VI)/S(IV) process using sulfamethoxazole (SMX) and ibuprofen (IBU) as model contaminants. We found that pH was crucial in governing the generation of reactive species, and both Fe(V/IV) and SO4•- were identified in the reaction system. Specifically, an increase in pH favored the formation of SO4•-, while the formation of Fe(VI) to Fe(V/IV) became more significant at lower pH. At pH 3.2, Fe(III) resulting from the Fe(VI) self-decay reactedwith HSO3-to produce SO4•-and •OH. Under near-neutral conditions, the coexistance of Fe(V/IV) and SO4•- in abundance contributed to the optimal oxidation of both pollutants in the Fe(VI)/S(IV) process, with the removal exceeding 74% in 5 min. Competitive quenching experiments showed that the contributions of Fe(V/IV) to SMX and IBU destruction dimished, while the contributions of radicals increased with an increase in pH. However, this evolution was slower during SMX degradation compared to IBU degradation. A comprehensive understnding of pH as the key factor is essential for the optimization of the sulfite-activated Fe(VI) oxidation process in water treatment.

Photo-transformation of isoproturon under UV-A irradiation: The synergy of nitrite and natural organic matter.

Isoproturon (IPU), a widely utilized phenylurea herbicide, is recognized as an emerging contaminant. Previous studies have predominantly attributed the degradation of IPU in natural waters to indirect photolysis by natural organic matter (NOM). Here, we demonstrate that nitrite (NO2-) also serves as an important photosensitizer that induces the photo-degradation of IPU. Through radical quenching tests, we identify hydroxyl radicals (•OH) and nitrogen dioxide radicals (NO2•) originating from NO2- photolysis as key players in IPU degradation, resulting in the generation of a series of hydroxylated and nitrated byproducts. Moreover, we demonstrate a synergistic effect on the photo-transformation of IPU when both NOM and NO2- are present in the reaction mixture. The observed rate constant (kobs) for IPU removal increases to 0.0179 ± 0.0002 min-1 in the co-presence of NO2- (50 µM) and NOM (2.5 mgC/L), surpassing the sum of those in the presence of each alone (0.0135 ± 0.0004 min-1). NOM exhibits multifaceted roles in the indirect photolysis of IPU. It can be excited by UV and transformed to excited triplet states (3NOM*) which oxidize IPU to IPU•+ that undergoes further degradation. Simultaneously, NOM can mitigate the reaction by reducing the IPU•+ intermediate back to the parent IPU. However, the presence of NO2- alters this dynamic, as IPU•+ rapidly couples with NO2•, accelerating IPU degradation and augmenting the formation of mono-nitrated IPU. These findings provide in-depth understandings on the photochemical transformation of environmental contaminants, especially phenylurea herbicides, in natural waters where NOM and NO2- coexist.

Photodegradation of phenylurea herbicides sensitized by norfloxacin and the influence of natural organic matter.

The photochemical activity of fluoroquinolone antibiotics (FQs) has gained attention due to the discovery of their phototoxicity and photocarcinogenicity in clinics. This study reveals that norfloxacin (NOR) can sensitize the photodegradation of phenylurea (PU) herbicides. This is attributed to the formation of an excited triplet of norfloxacin (3NOR*) by UV-A irradiation of its quinolone chromophore, which can further react with O2 to form singlet oxygen (1O2). The second-order rate of 3NOR* with PU ranges from 1.54 × 1010 to 2.76 × 1010 M-1s-1. The steady-state concentrations of 3NOR* were calculated as (4.29-31.2)× 10-16 M at 10 µM NOR under UV365nm irradiation. Natural organic matter (NOM) inhibited the degradation of PU induced by 3NOR*. In the presence of 10 mg L-1 NOM, the pseudo-first-order rate constants (kobs,NOM) of the degradation of diuron (DIU), isoproturon (IPU), monuron (MOU), and chlorotoluron (CLU) decreased by 65%, 19%, 36%, and 62%, respectively. NOM mainly acts as a reductant which reacted with the radical intermediates of the PU generated by 3NOR*oxidation, thus reversing the oxidation. The inhibitory effect increases with increasing NOM concentration. Results of this study underscore the role of NOR as a photosensitizer in accelerating the abatement of PU pesticides in sunlit surface waters. This study significantly advances the understandings of the behavior of NOR in aquatic environments.

Degradation of tetracyclines by peracetic acid and UV/peracetic acid: Reactive species and theoretical computations.

As an environment-friendly oxidant and disinfectant, peracetic acid (PAA) and PAA based-advanced oxidation processes (AOPs) for the treatment of emerging micropollutants have raised increasing interest, owing to their ease of activation and less generation of harmful disinfection byproducts. Tetracyclines (TCs) antibiotics as a group of wide-spectrum antibiotics are frequently detected in sewage effluents, while the knowledge of PAA-based advanced oxidation reactions to remove the substrates is quite limited. In this work, we systematically investigated the kinetics and underlying transformation mechanisms of three TCs including tetracycline (TTC), oxytetracycline (OTC), and chlortetracycline (CTC) in the UV-activated PAA oxidation process. The results indicated that three TCs can be efficiently decayed by UV/PAA. The pseudo-first-order reaction rate constants (kobs) of TCs followed the order: kCTC (0.453 min-1) ≫ kTTC (0.164 min-1) > kOTC (0.158 min-1). Quenching experiments showed that the removal of CTC was mainly ascribed to the direct oxidation of PAA, while TTC and OTC were more susceptible to free radicals. The kobs values of the three TCs by PAA oxidation presented a fairly well correlation to the global nucleophilicity and the activation energies of the TC molecules, highlighting the structure-specific reactions of TCs to PAA. Based on product identification and theoretical calculation, N-demethylation and hydroxylation were proposed as the main pathways for TCs degradation by PAA non-radical oxidation. The combination of PAA and UV irradiation can further improve the degradation efficiency of TCs and contribute to reducing the diffusion and transmission of resistance genes in the environment.