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.

Comparative removal of pharmaceuticals in aqueous phase by agricultural waste-based biochars.

The intensification of pharmaceutical use globally has led to an increase in the number of water bodies contaminated by drugs, and an effective strategy must be developed to address this issue. In this work, several biochars produced from Miscanthus straw pellets (MSP550, MSP700) and wheat straw pellets (WSP550, WSP700) at 550 and 700°C, respectively, were selected as adsorbents for removing various pharmaceuticals, such as pemetrexed (PEME), sulfaclozine (SCL), and terbutaline (TBL), from the aqueous phase. The biochar characterizations (physicochemical properties, textural properties, morphological structures, and zeta potentials) and adsorptive conditions (contact times, temperatures, and pH effect) were investigated. The infrared and Raman spectra of biochars before and after pharmaceutical adsorption, as well as quantum chemical computations, were carried out to explore the adsorption mechanisms. The results showed that the general adsorption abilities of biochars for pharmaceuticals were in the order of WSP700 > MSP700 > MSP550 > WSP550. Both the higher drug concentration and higher temperature improved biochar adsorption. By decreasing the pH, the adsorption amounts increased for PEME and SCL. However, TBL exhibited the best adsorption at pH 7, whereas a weakening of affinity occurred at lower or higher pH values. Electrostatic interactions and hydrogen bonding were the main adsorptive mechanisms between all biochars and pharmaceuticals. π-π interactions played a role in the adsorption process of low-temperature-prepared biochars (MSP550 and WSP550). This work can provide new insights into the control of pharmaceuticals from water with low-cost adsorbents. PRACTITIONER POINTS: Use of biochars for pharmaceuticals removal from aqueous phase. Characterization of biochars : physical and chemical properties, textural and surface properties. Simulation calculation for characterization of pharmaceuticals. Kinetic studies of pharmaceuticals adsorption on biochars. DRIFTS and Raman analysis for the understanding of adsorption process.

Formation of halogenated chloroxylenols through chlorination and their photochemical activity.

Trace organic contaminants usually go through multiple treatment units in a modern water treatment train. Structural modification triggered by pretreatment (e.g., prechlorination) may influence the further transformation and fate of contaminants in downstream units. However, knowledge on this aspect is still limited. In this contribution, we investigated the chlorination of chloroxylenol (PCMX), an antimicrobial agent extensively used during COVID-19 pandemic, and the photoreactivity of its halogenated derivatives. Results indicate that chlorination of PCMX mainly proceeded through electrophilic substitution to give chlorinated products, including Cl- and 2Cl-PCMX. The presence of bromide (Br-) resulted in brominated analogues. Owing to the bathochromic and "heavy atom" effects of halogen substituents, these products show increased light absorption and photoreactivity. Toxicity evaluation suggest that these halo-derivatives have higher persistence, bioaccumulation, and toxicity (PBT) than the parent PCMX. Results of this contribution advance our understanding of the transformation of PCMX during chlorination and the photochemical activity of its halogenated derivatives in subsequent UV disinfection process or sunlit surface waters.

The simultaneous degradation of prochloraz and tebuconazole in water with monitoring their degradation products using liquid chromatography-tandem mass spectrometry.

Prochloraz and tebuconazole are well-known fungicides for broad applications, including medical, industrial, and agricultural. They are frequently used simultaneously which increases the probability of their co-existing in various water sources. In this study, the analysis of PCZ or TBZ in water was performed by a direct analysis using the liquid chromatography-tandem mass spectrometry technique (LC-MS/MS). The optimized method was fully validated according to the European guidelines, SANTE/11312/2021. The complete degradation of these fungicides (each of 2 mg/L) in their single presence in the water was accomplished just after 15 min using 4.2 mM persulfate at 50 °C, while a lower concentration of persulfate (1.4 mM) leads to a degradation of prochloraz and tebuconazole, in their single existence in water, at percentages of 97 % and 98 %, respectively, after 30 min at 50 °C. On the other hand, it takes a complete hour to degrade a mixture of prochloraz and tebuconazole at percentages of 99 % and 94 %, respectively, using 1.4 mM persulfate at 50 °C. Degradation products (DPds) of prochloraz and tebuconazole, either in their single or simultaneous existing in water, were also identified and monitored during the whole degradation process by LC-MS/MS using at least two mass transitions for each DPd at both positive and negative ionization modes. It was elucidated that the persulfate degradation of prochloraz was conducted by the cleavage of the imidazole ring and the subsequent formation of a trichlorophenol, while persulfate degradation of tebuconazole was mainly accomplished by the formation of a hydroxyl structure, cleavage of the tert-butyl chain, and the subsequent formation of a ketone structure. Furthermore, a new DPd of tebuconazole (m/z = 263 Da) with a diketone structure was identified and confirmed.

Simultaneous removal of pharmaceuticals and heavy metals from aqueous phase via adsorptive strategy: A critical review.

The coexistence of pharmaceuticals and heavy metals is regarded as a serious threat to aquatic environments. Adsorbents have been widely applied to the simultaneous removal of pharmaceuticals and metals from aqueous phase. Through a comprehensive review, behaviors that promote, inhibit, or have no effect on simultaneous adsorption of pharmaceuticals and heavy metals were found to depend on the system of contaminants and adsorbents and their environmental conditions, such as: characteristics of adsorbent and pollutant, temperature, pH, inorganic ions, and natural organic matter. Bridging and competition effects are the main reasons for promoting and inhibiting adsorption in coexisting systems, respectively. The promotion is more significant in neutral or alkaline conditions. After simultaneous adsorption, a solvent elution approach was most commonly used for regeneration of saturated adsorbents. To conclude, this work could help to sort out the theoretical knowledge in this field, and may provide new insights into the prevention and control of pharmaceuticals and heavy metals coexisting in wastewater.

Aquatic photolysis of the pharmaceutical ambroxol: The role of 2,4-dibromoaniline chromophore and heavy atom effect of bromine.

As one of the most effective expectorant class drugs, ambroxol (AMB) has been frequently used to treat acute and chronic bronchitis. Extensive use and human excretion result in the widespread occurrence of AMB in wastewater. Herein, we reported the photolysis of AMB in aqueous solution upon 254 nm ultraviolet radiation (UV254). Spectroscopic characterization showed that 2,4-dibromoaniline (DBA) moiety is the core chromophore of AMB. Quantum yield of DBA changed little at pH 4.0 - 9.0; however, AMB showed higher quantum yield at pH > 8.0. Both DBA and AMB have high photoreactivity, which can be attributed to the "heavy atom" effect of bromine substituents. The photolysis of AMB occurred through photoreduction, photoionization, photonucleophilic substitution, side-chain cleavage, and coupling reactions. Both AMB and DBA underwent debromination with yields reaching 80% under 3200 mJ cm-2 UV fluence. Photo-debromination occurred preferentially at the para-position. The presence of natural organic matter inhibited the photodegradation, mainly due to the light-screening effect. The photolysis of AMB was slightly enhanced in the presence of NO3- likely due to radical-induced oxidation. Bioluminescence inhibition assay revealed that photoproducts were not toxic. The results show that UV254 radiation with fluences relevant to advanced oxidation processes was effective for the abatement of AMB in wastewater. However, UV254 treatment of wastewater containing higher concentrations (˃ µg L-1) of AMB should be done with caution because the released Br- can be converted to toxic brominated disinfection byproducts and bromate in subsequent oxidation process.

Enhancement of sludge dewaterability by electrolysis coupled with peroxymonosulfate oxidation process: Performance, mechanisms and implications.

With the rapid increase in waste activated sludge (WAS), it is urgent to develop appropriate dewatering processes to diminish sludge volume and improve disposal efficiency. In this study, an advanced oxidation process using electrolysis coupled with peroxymonosulfate (E/PMS) was applied to improve the dewaterability of WAS. The results indicated that the sludge water content (WC) and capillary suction time (CST) dropped from 98.4 ± 0.2% and 220.1 ± 2.3 s to 70.7 ± 0.8% and 63.0 ± 1.2 s, respectively, under the following conditions: an electrolysis voltage of 20 V, an electrolysis time of 20 min, and 200 mg/g TS PMS. The increase in sludge zeta potential, surface hydrophobicity, and flowability indicated a significant improvement in sludge dewaterability. SO4•-, O•H, and O21 generated in the E/PMS process were responsible for the improvement of WAS dewaterability. These reactive oxygen species damaged extracellular polymeric substances (EPS), decreased fluorescent EPS components, and transformed the extracellular protein secondary structures by influencing the H-bond actions that maintain the α-helix. The bound water content, and apparent viscosity of WAS were found to be reduced, which was also attributed to an increase in dewatering capacity. Additionally, E/PMS treatment enhanced the degradation of organic matter in sludge and reduced the toxicity of the filtrate as well as the bioavailability of heavy metals. The cost analysis found that the E/PMS process was relatively economical and has great potential for practical application.

Direct and nitrite-sensitized indirect photolysis of effluent-derived phenolic contaminants under UV254 irradiation.

UV254 photolysis has increasingly been utilized for disinfection of water-born pathogens in wastewater. During disinfection, wastewater-derived trace organic contaminants, such as pharmaceuticals and personal care products (PPCPs), may be subjected to direct photolysis and indirect photolysis sensitized by wastewater constituents such as nitrite (NO2-). Herein, we reported the direct photolysis and NO2--sensitized indirect photolysis of four phenolic contaminants commonly observed in wastewaters (i.e., bisphenol A (BPA), acetaminophen (ATP), salbutamol (SAL), and 2,4-dihydroxybenzophenone (BP1)). Spectroscopic characterization and quantum yield measurement were carried out to evaluate the photochemical reactivity of these phenolic compounds. In NO2--sensitized photolysis, the relative contribution of direct and indirect photolysis was quantified by light screening factor calculation and radical quenching studies. The experimental results highlight the important roles of HO˙ and NO2˙ in the NO2--sensitized photolysis of phenolic compounds. A series of intermediate products, including hydroxylated, nitrated, nitrosated, dimerized, and alkyl chain cleavage products, were identified by solid phase extraction (SPE) combined with high-resolution mass spectrometry (HRMS) analyses. On the basis of identified products, the underlying mechanisms and transformation pathways for NO2--sensitized photolysis of these phenolic compounds were elucidated. The second-order rate constants of BPA, SAL, BP1 with NO2˙ were calculated to be 2.25 × 104, 1.35 × 104 and 2.44 × 104 M-1 s-1, respectively, by kinetic modeling. Suwanee River natural organic matter (SRNOM) played complex roles in the direct and NO2--sensitized photolysis of phenolic compounds by serving as a photosensitizer, light screening and radical quenching agent. Wastewater constituents, such as NO3- and EfOM, could accelerate direct and NO2--sensitized photolysis of BPA, SAL, and BP1 in the wastewater matrix. Our results suggest that NO2- at the WWTP effluent-relevant level can sensitize the photolysis of effluent-derived phenolic contaminants during the UV254 disinfection process; however, the formation of potentially carcinogenic and mutagenic nitrated/nitrosated derivatives should be scrutinized.

Aquatic photolysis of 2,4-dichloro-6-nitrophenol-the toxic nitrated byproduct of 2,4-dichlorophenol.

2,4-Dichloro-6-nitrophenol (DCNP) is a toxic nitrated byproduct of 2,4-dichlorophenol (2,4-DCP) commonly found in agriculturally impacted waters (e.g., paddy waters). DCNP has both genotoxicity and developmental toxicity and can cause endocrine disrupting effects on aquatic species. Herein, we investigated the photolysis of DCNP under UV254 irradiation in aqueous solutions. Results show that the anionic form of DCNP (DCNP-) is more photoreactive than the neutral form (DCNP0) due to its higher molar absorption coefficient and quantum yield. The presence of Suwannee River natural organic matter (SRNOM) inhibits the direct photolysis of DCNP through light screening. A series of photoproducts were identified by solid phase extraction (SPE) and high resolution-mass spectrometry (HR-MS) analysis. The photolysis of DCNP generates several photoproducts, including photoreduction, photonucleophilic substitution, photoionization, and dimerization intermediates. The primary photochemical mechanisms include photoionization from the singlet state and heterolytic C-Cl bond splitting in the triplet state. This contribution may shed some light on the photochemical transformation and fate of DCNP in UV-based engineering systems or natural sunlit surface waters.

Aquatic photolysis of ketoprofen generates products with photosensitizing activity and toxicity.

Ketoprofen (KTF) is a nonsteroidal anti-inflammatory drug frequently detected in natural and engineering waters. Because KTF is particularly photolabile (half-life ∼4 min), knowledge of the fate and ecological risks of KTF photoproducts in the aquatic environment is especially essential. Herein, we systematically investigated the photophysics, photochemistry, and photosensitization of KTF photoproducts in aqueous solution under 365 nm irradiation (UV365). Results show that KTF photolyzed rapidly and formed 3-ethyl-α-hydroxylbenzophenone (EtOH-BP), 3-ethyl-α-hydroperoxylbenzophenone (EtOOH-BP), 3-acetylbenzophenone (AcBP), and 3-ethylbenzophenone (EtBP), as identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS) and high-resolution mass spectrometry (HRMS). The presence of O2 significantly affected the evolution of photoproducts during KTF photolysis. The photophysical properties of EtBP and AcBP were characterized by spectroscopic approaches. In particular, transient absorption spectra obtained by nanosecond laser flash photolysis (LFP) indicated that EtBP and AcBP were excited to triplet states with lifetimes of 28 and 2.4 µs, respectively. EtBP underwent further photodegradation, giving rise to EtOH-BP, EtOOH-BP, and AcBP upon UV365 irradiation. The reaction is proposed to proceed through an excimer precursor (3[EtBP···EtBP]*) followed by intramolecular H-abstraction. In contrast, AcBP was relatively photostable, particularly under aerated condition. Both EtBP and AcBP have strong photosensitizing activity, as evidenced by the triplet probe 4-(N,N-dimethylamino)benzonitrile (DMABN). ECOSAR program suggested that the photoproducts are more ecotoxic and bioaccumulative than the parent KTF. Results of this study underscore the need to scrutinize the formation and fate of KTF photoproducts in sunlit surface waters.

Accelerated oxidation of the emerging brominated flame retardant tetrabromobisphenol S by unactivated peroxymonosulfate: The role of bromine catalysis and formation of disinfection byproducts.

Tetrabromobisphenol S (TBBPS) is an emerging brominated flame retardant (BFR) that can cause endocrinological abnormalities in aquatic species and is neurotoxic and cytotoxic to humans. Herein, we investigated the oxidation of TBBPS by unactivated peroxymonosulfate (PMS) in aqueous solution. Results show that PMS was capable of oxidizing TBBPS without activation, and the transformation of TBBPS was pH-dependent. Interestingly, the unactivated PMS oxidation of TBBPS exhibited an autocatalytic behavior. Radical quenching experiments and electron paramagnetic resonance (EPR) analyzes ruled out the involvement of hydroxyl radical (HO•) and sulfate radical (SO4•­) as reactive species. While the generation of singlet oxygen (1O2) was confirmed in PMS solution, it was also not responsible for TBBPS oxidation. The bromine substituents are believed to be responsible for the autocatalysis observed during PMS oxidation. We propose that the initial oxidation of TBBPS by PMS resulted in the release of bromide ions (Br-) via debromination, which could be rapidly oxidized to hypobromous acid (HOBr). 3,5-Dimethyl-1H-pyrazole (DMPZ) trapping coupled with liquid chromatography-mass spectrometry (LC-MS) analysis evidenced the formation of HOBr in PMS/TBBPS system. Therefore, the presence of Br-, albeit at trace level, could significantly accelerate the oxidation of TBBPS in PMS solution via HOBr formation. The intermediate products of TBBPS were identified by solid phase extraction (SPE) coupled with high resolution-mass spectrometry (HR-MS). The oxidation of TBBPS by unactivated PMS was likely initiated through a single electron transfer mechanism, and the transformation pathways included ß-scission, debromination, and cross-coupling reactions. Further oxidation and ring-opening of the intermediates yielded three brominated disinfection byproducts (Br-DBPs), including bromoform (CHBr3), mono-, and di-bromoacetic acids (MBAA and DBAA), as quantified by gas chromatography (GC). The presence of natural organic matter (NOM) inhibited the oxidation of TBBPS and reduced the yields of Br-DBPs. Our results indicate that unactivated PMS was efficient in the abatement of TBBPS in aqueous solution due to the accelerated oxidation by bromine catalysis; however, the formation of brominated intermediate products and Br-DBPs should be scrutinized due to their potential carcinogenicity and mutagenicity.

Cu(II) assisted peroxymonosulfate oxidation of sulfonamide antibiotics: The involvement of Cu(III).

Cu(II) is generally considered to be a poor activator for PMS decomposition, thus the potential impact of trace Cu(II) on PMS induced oxidation of typical pollutants is always overlooked. In this study, we reported that trace Cu(II) could significantly promote PMS induced degradation of four selected sulfonamide antibiotics (SAs), namely, sulfamehoxazole (SMX), sulfathiazole (STZ), sulfamerazine (SMZ), and sulfamonomethoxine (SMM). Different from conventional PMS-induced oxidation process, high-valent Cu(III) was ascertained as the primary reactive intermediate for SAs degradation, which was confirmed by raman tests and electron paramagnetic resonance (EPR). High concentrations of Cu(II) or PMS were beneficial to degradation of the selected contaminants. In PMS/Cu(II) oxidation system, all the selected SAs could undergo several different degradation pathways including continuous oxidation of aniline group, hydroxylation and S-N bond cleavage. In particular, for six-membered SAs, such as SMZ and SMM, a SO2 extrusion pathway was also detected. The potential mechanism for Cu(III) formation was also proposed, which was believed to be highly related to the nature of the SAs. Hydroxylamine-SAs (N4-OH-SAs), generated from direct PMS oxidation of SAs, was deduced as the "promoter" for the whole oxidation process. And the generation of Cu(III) was likely to proceed through the interaction between PMS and Cu(I), which possibly derived from the reduction of Cu(II) by N4-OH-SAs. The results obtained in this study validated the contribution of Cu(III) to the elimination of pollutants and expanded our understanding of the oxidation process of PMS in the presence of trace amounts of Cu(II).

Trace level nitrite sensitized photolysis of the antimicrobial agents parachlormetaxylenol and chlorophene in water.

Nitrite (NO2-)-sensitized photolysis plays an important role in the attenuation of effluent-derived trace organic contaminants (e.g., anilines, phenolic compounds, etc.) in surface waters. However, the kinetics, mechanisms, and influencing factors of photolysis of many emerging contaminants sensitized by NO2- still remain largely unknown. Herein, we report that NO2--sensitized photolysis of the antimicrobial agents parachlormetaxylenol (PCMX) and chlorophene (CP) in aqueous solution under ultraviolet 365 nm (UV365) radiation. A nonlinear increase in photolysis rate constants of PCMX and CP was observed with increasing NO2- concentration. Radical quenching studies and kinetic modeling revealed that hydroxyl radical (HO•) and nitrogen dioxide radicals (NO2•) contributed dominantly to the removal of PCMX and CP. Solid phase extraction (SPE) combined with high resolution-mass spectrometry (HR-MS) analysis identified a series of intermediate products including hydroxylated, nitrated, nitrosated, and dimerized derivatives. Experiments with isotopically labelled nitrite (15NO2-) showed that the nitro- and nitroso-substituents of intermediate products were derived from the nitrite nitrogen. Based on the identified products and theoretical computations, the mechanisms and pathways of NO2--sensitized photolysis of PCMX and CP are elucidated. Deoxygenation partially inhibited the formation of 4-chloro-3,5-dimethyl-2-nitrophenol (nitro-PCMX) while the presence of HO• scavenger such as isopropanol (i-PrOH) suppressed the further transformation of nitro-PCMX. The presence of Mississippi River natural organic matter (MRNOM) inhibited the removal of PCMX and CP, likely due to light screening and radical quenching. However, appreciable degradation of PCMX and CP was still observed in wastewater and wetland water matrices. Results of this study shed some light on the transformation and fate of PCMX and CP in NO2--rich wastewater effluents or effluent-impacted surface waters under solar radiation.

Fluoroquinolone antibiotics sensitized photodegradation of isoproturon.

Fluoroquinolone (FQ) antibiotics are a group of contaminants of emerging environmental concern. In the present study, we demonstrated that norfloxacin (NORF) and ofloxacin (OFLO), two typical FQs, have photochemical reactivity analogous to chromophoric dissolved natural organic matter (DOM) in surface waters and can sensitize the photodegradation of isoproturon (IPU), a phenylurea herbicide. Such photochemical reactivity is ascribed to the quinolone chromophore that is excited to a triplet state (3FQ*) upon UV-A irradiation. 3FQ* further reacts with dissolved oxygen to give rise to singlet oxygen. 3FQ* steady-state concentrations of 6.72 × 10-15 and 1.27 × 10-15 M were measured in 10 µM NORF and OFLO solutions, respectively, under UV365nm irradiation. The degradation of IPU was due to the reaction with 3FQ*, with bimolecular rate constants of 6.07 × 109 and 1.51 × 1010 for 3NORF* and 3OFLO*, respectively. Intriguingly, NORF and OFLO per se were unstable and photolyzed during UV-A irradiation, but the photochemical reactivities of the solutions were not lost accordingly. High-resolution mass spectrometry analysis revealed that defluorination and piperazine moiety oxidation were the main photolysis pathways, while the core quinolone structure remained intact. Thus, the photolysis products largely inherited the photochemical reactivity of the parent compounds. Since all FQs share the same quinolone structure, similar photochemical reactivity is expected. The presence of FQs in surface water would affect the transformation and fate of coexisting compounds. To the best of our knowledge, this is the first study examining the environmental behavior of FQs as photosensitizers. The findings greatly advance the understandings of the influence of FQs in aquatic environment.

Aqueous photodecomposition of the emerging brominated flame retardant tetrabromobisphenol S (TBBPS).

As an emerging brominated flame retardant (BFR), tetrabromobisphenol S (TBBPS) has been frequently detected in the environmental media and organisms. Knowledges on the transformation and fate of TBBPS in both environment and engineering systems are essential to its ecological risk assessment. Herein, we reported the photochemical decomposition of TBBPS in aqueous solution upon 254 nm ultraviolet irradiation (UV254). Results show that TBBPS was highly photoreactive, most likely due to the presence of four ortho-bromine substituents. The molar absorption coefficient and quantum yield of TBBPS were found to be pH-dependent, with the monoanionic form being most photoreactive. A series of photoproducts were identified by solid phase extraction (SPE) combined with liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI(+)-MS/MS. The photolysis of TBBPS likely proceeded through photonucleophilic substitution, photoreductive debromination, and ß-scission reactions. A ketocarbene, possibly derived from the lower lying excited triplet state, was proposed to be involved in the photolysis of TBBPS. Ion chromatography analysis revealed that debromination occurred quickly, and the yield of bromide (Br-) approached 100% after 90 min irradiation. The presence of SRNOM and MRNOM inhibited the photodegradation rate of TBBPS, which is likely due to the light-screening and physical quenching effects of natural organic matter (NOM). Our results reveal that photolysis is an important process for the attenuation of TBBPS in aquatic system; however, naturally occurring species such as NOM can appreciably retard the decay of TBBPS.

Sulfate radical-based oxidation of the aminopyralid and picloram herbicides: The role of amino group on pyridine ring.

The widespread utilization of pesticides has attracted increasing attention to their environmental impacts and effective removal strategies. In the present study, the degradation of herbicides picloram (PCLO) and aminopyralid (AMP) with similar structures were investigated systematically by thermo activated persulfate. Overweight SO4•- was determined to be the predominant oxidizing species by quenching experiment. Obtained by laser-flash photolysis (LFP), reaction rate constants of SO4•- towards AMP and PCLO were determined at 1.56 × 109 M-1s-1 and 1.21 × 109 M-1s-1, respectively. Product analysis revealed that both substances underwent similar oxidation paths, namely, successive oxidation on pyridine ring and formation of coupling-products as well as further hydroxylation and decarboxylation. Amino group on the pyridine ring was identified as the main reactive site, which was further confirmed by DFT calculation. It was susceptible attacked by SO4•- to form deamination, nitration, and self-coupling products. These couples could be further oxidatively dehydrated to form azo and a series of azo derivatives. EOCSAR program predicted significant hazards on aquatic species during the formation of these couplings and azo derivatives. Our work emphasized the potential ability and toxicity of contaminates to produce azo substances in the presence of amino groups on the pyridine ring.

Direct oxidation of antibiotic trimethoprim by unactivated peroxymonosulfate via a nonradical transformation mechanism.

Application of activated peroxymonosulfate (PMS) to generate sulfate radical or hydroxyl radical is a promising strategy for wastewater treatment, while our knowledge on the background reaction, namely, the direct interaction between PMS and target contaminants is quite limited. In this contribution, the degradation kinetics, stoichiometry, products and mechanism of the reaction between unactivated PMS and trimethoprim (TMP), one of the most commonly detected micro-pollutants in the aquatic system were investigated systematically. The results indicated that TMP was susceptible to degradation by direct PMS oxidation via a non-radical process. By recording the decay of two reactants simultaneously, the stoichiometric ratio between PMS and TMP was estimated to be approximately 1. Higher PMS levels exhibited a promotion effect on PMS decay. And the degradation was pH-dependent, basic conditions were favorable for TMP degradation, which could be well modeled based on the species-specific reactions. The two amine groups on the pyrimidine ring were identified as the reactive sites. After direct attacks by PMS, they would be oxidized to form hydroxylamine-products, namely, N8-OH-TMP and N9-OH-TMP. These two hydroxylamine-products were quite stable and resistant to further oxidation by PMS, preventing the formation of more toxic nitroso- and nitro-products. The new findings in the present work would provide beneficial information on the strategy choice for the elimination of specific pollutants, like TMP, as PMS also exhibits relatively high reactivity towards them.

Direct photodegradation of 36 organic micropollutants under simulated solar radiation: Comparison with free-water surface constructed wetland and influence of chemical structure.

Micropollutants such as pharmaceuticals and pesticides are still found in treated municipal effluent and are discharged into the natural environment. Natural direct photodegradation may be one pathway for removing these micropollutants in treatment processes such as free-water surface constructed wetlands (CW). This work was set out to evaluate the half-life (t1/2) of direct photodegradation of 36 micropollutants under controlled conditions of light exposure close to solar radiation. The results allowed to classify the micropollutants into three groups (fast, medium and slow). Seven micropollutants were classified in the fast group with t1/2 between 0.05 h and 0.79 h, 24 in the medium group with t1/2 between 5.3 h and 49.7 h, and five in the slow group with t1/2 between 56 h and 118 h. The t1/2 values obtained in laboratory were compared with those from a CW receiving treated wastewater. Correction factors were calculated to adjust the in situ data for the light intensity in laboratory and improved the correspondence especially for the micropollutants of the fast and medium groups. Finally, an innovative method based on statistical tests highlighted the chemical functions characteristic of micropollutants sensitive to photodegradation (OH-CË­O, CË­N-O-, =N-OH, -CH=N, -O-PË­O, -CË­C-) and with low sensitivity (-O-R, -Cl).

Formation of chloronitrophenols upon sulfate radical-based oxidation of 2-chlorophenol in the presence of nitrite.

Sulfate radical (SO4-)-based advanced oxidation processes (SR-AOPs) are promising in-situ chemical oxidation technologies widely applied for soil/groundwater remediation. The presence of non-target water constituents may interfere the abatement of contaminants by SR-AOPs as well as result in the formation of unintended byproducts. Herein, we reported the formation of toxic chloronitrophenols during thermally activated persulfate oxidation of 2-chlorophenol (2CP) in the presence of nitrite (NO2-). 2-Chloro-4-nitrophenol (2C4NP) and 2-chloro-6-nitrophenol (2C6NP) were identified as nitrated byproducts of 2CP with total yield up to 90%. The formation of nitrated byproducts is a result of coupling reaction between 2CP phenoxyl radical (ClPhO) and nitrogen dioxide radical (NO2). As a critical step, the formation of ClPhO was supported by density functional theory (DFT) computation. Both 2C4NP and 2C6NP could convert to 2-chloro-4,6-dinitrophenol (2C46DNP) upon further treatment via a denitration-renitration process. The formation rate of 2C4NP and 2C6NP was closely dependent on the concentration of NO2-, solution pH, and natural water constituents. ECOSAR calculation suggests that chloronitrophenols are generally more hydrophobic and ecotoxic than 2CP. Our result therefore reveals the potential risks in the abatement of chlorophenols by SR-AOP, particularly when high level of NO2- is present in water matrix.

New insights into clopyralid degradation by sulfate radical: Pyridine ring cleavage pathways.

Contamination by herbicides such as clopyralid (CLP) poses a significant threat to human health and ecological systems. In the present study, efficient removal of CLP was achieved by thermo activated persulfate, among which sulfate radical was identified as the predominant oxidizing species responsible for the decontamination. Based on high resolution LC-MS, derivatization method and density functional theory (DFT) computation, the detailed oxidation pathways and mechanisms were proposed. The primary oxidation pathways included dechlorination-hydroxylation, decarboxylation and the formation of quinone-like moieties. Afterwards, numerous intermediate byproducts ranging from high molecular to very small ones were identified, suggesting the pyridine ring was damaged during the thermo activated persulfate process. The detected products containing six and five carbons indicated the pyridine ring cleavage would take place on the quinone-structure intermediate. Further oxidation could continue by breaking each bond on the ring-cleavage product, yielding a series of short-chain carbonyl chemicals, carboxylic acids and inorganic ions. In addition, the presence of dissolved oxygen (DO) was favorable to CLP degradation, indicating DO played an important role in applying such technology. The degradation rate constants of CLP increased appreciably with increasing temperature, and acidic pH facilitated the CLP degradation. The results obtained in this work would increase our understanding on the environmental fates of nitrogen heterocyclic compounds during sulfate radical (SO4•-)-based advanced oxidation processes (SR-AOPs).