Unraveling the Role of Humic Acid in the Oxidation of Phenolic Contaminants by Soluble Manganese Oxo-Anions.

Humic acid (HA) is ubiquitous in natural aquatic environments and effectively accelerates decontamination by permanganate (Mn(VII)). However, the detailed mechanism remains uncertain. Herein, the intrinsic mechanisms of HA's impact on phenolics oxidation by Mn(VII) and its intermediate manganese oxo-anions were systematically studied. Results suggested that HA facilitated the transfer of a single electron from Mn(VII), resulting in the sequential formation of Mn(VI) and Mn(V). The formed Mn(V) was further reduced to Mn(III) through a double electron transfer process by HA. Mn(III) was responsible for the HA-boosted oxidation as the active species attacking pollutants, while Mn(VI) and Mn(V) tended to act as intermediate species due to their own instability. In addition, HA could serve as a stabilizer to form a complex with produced Mn(III) and retard the disproportionation of Mn(III). Notably, manganese oxo-anions did not mineralize HA but essentially changed its composition. According to the results of Fourier-transform ion cyclotron resonance mass spectrometry and the second derivative analysis of Fourier-transform infrared spectroscopy, we found that manganese oxo-anions triggered the decomposition of C-H bonds on HA and subsequently produced oxygen-containing functional groups (i.e., C-O). This study might shed new light on the HA/manganese oxo-anion process.

Comparative analysis of UV-initiated ARPs for degradation of the emerging substitute of perfluorinated compounds: Does defluorination mean the sole factor?

Due to the increasing attention for the residual of per- and polyfluorinated compounds in environmental water, Sodium p-Perfluorous Nonenoxybenzenesulfonate (OBS) have been considered as an alternative solution for perfluorooctane sulfonic acid (PFOS). However, recent detections of elevated OBS concentrations in oil fields and Frontal polymerization foams have raised environmental concerns leading to the decontamination exploration for this compound. In this study, three advanced reduction processes including UV-Sulfate (UV-SF), UV-Iodide (UV-KI) and UV-Nitrilotriacetic acid (UV-NTA) were selected to evaluate the removal for OBS. Results revealed that hydrated electrons (eaq-) dominated the degradation and defluorination of OBS. Remarkably, the UV-KI exhibited the highest removal rate (0.005 s-1) and defluorination efficiency (35 %) along with the highest concentration of eaq- (K = -4.651). Despite that nucleophilic attack from eaq- on sp2 carbon and H/F exchange were discovered as the general mechanism, high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (HPLC/Q-TOF-MS) analysis with density functional theory (DFT) calculations revealed the diversified products and routes. Intermediates with lowest fluorine content for UV-KI were identified, the presence nitrogen-containing intermediates were revealed in the UV-NTA. Notably, the nitrogen-containing intermediates displayed the enhanced toxicity, and the iodine poly-fluorinated intermediates could be a potential-threat compared to the superior defluorination performance for UV-KI.

Influence of temperature on performance and mechanism of advanced synergistic nitrogen removal in lab-scale denitrifying filter with biogenic manganese oxides.

Temperature is a significant operational parameter of denitrifying filter (DF), which affects the microbial activity and the pollutants removal efficiency. This study investigated the influence of temperature on performance of advanced synergistic nitrogen removal (ASNR) of partial-denitrification anammox (PDA) and denitrification, consuming the hydrolytic and oxidation products of refractory organics in the actual secondary effluent (SE) as carbon source. When the test water temperature (TWT) was around 25, 20, 15 and 10 °C, the filtered effluent total nitrogen (TN) was 1.47, 1.70, 2.79 and 5.52 mg/L with the removal rate of 93.38%, 92.25%, 87.33% and 74.87%, and the effluent CODcr was 8.12, 8.45, 10.86 and 12.29 mg/L with the removal rate of 72.41%, 66.17%, 57.35% and 51.87%, respectively. The contribution rate of PDA to TN removal was 60.44%∼66.48%, and 0.77-0.96 mg chemical oxygen demand (CODcr) was actually consumed to remove 1 mg TN. The identified functional bacteria, such as anammox bacteria, manganese oxidizing bacteria (MnOB), hydrolytic bacteria and denitrifying bacteria, demonstrated that TN was removed by the ASNR, and the variation of the functional bacteria along the DF layer revealed the mechanism of the TWT affecting the efficiency of the ASNR. This technique presented a strong adaptability to the variation of the TWT, therefore, it has broad application prospect and superlative application value in advanced nitrogen removal of municipal wastewater.

Binding Affinity and Mechanism of Six PFAS with Human Serum Albumin: Insights from Multi-Spectroscopy, DFT and Molecular Dynamics Approaches.

Per- and Polyfluoroalkyl Substances (PFAS) bioaccumulate in the human body, presenting potential health risks and cellular toxicity. Their transport mechanisms and interactions with tissues and the circulatory system require further investigation. This study investigates the interaction mechanisms of six PFAS with Human Serum Albumin (HSA) using multi-spectroscopy, DFT and a molecular dynamics approach. Multi-spectral analysis shows that perfluorononanoic acid (PFNA) has the best binding capabilities with HSA. The order of binding constants (298 K) is as follows: "Perfluorononanoic Acid (PFNA, 7.81 × 106 L·mol-1) > Perfluoro-2,5-dimethyl-3,6-dioxanonanoic Acid (HFPO-TA, 3.70 × 106 L·mol-1) > Perfluorooctanoic Acid (PFOA, 2.27 × 105 L·mol-1) > Perfluoro-3,6,9-trioxadecanoic Acid (PFO3DA, 1.59 × 105 L·mol-1) > Perfluoroheptanoic Acid (PFHpA, 4.53 × 103 L·mol-1) > Dodecafluorosuberic Acid (DFSA, 1.52 × 103 L·mol-1)". Thermodynamic analysis suggests that PFNA and PFO3DA's interactions with HSA are exothermic, driven primarily by hydrogen bonds or van der Waals interactions. PFHpA, DFSA, PFOA, and HFPO-TA's interactions with HSA, on the other hand, are endothermic processes primarily driven by hydrophobic interactions. Competitive probe results show that the main HSA-PFAS binding site is in the HSA structure's subdomain IIA. These findings are also consistent with the findings of molecular docking. Molecular dynamics simulation (MD) analysis further shows that the lowest binding energy (-38.83 kcal/mol) is fund in the HSA-PFNA complex, indicating that PFNA binds more readily with HSA. Energy decomposition analysis also indicates that van der Waals and electrostatic interactions are the main forces for the HSA-PFAS complexes. Correlation analysis reveals that DFT quantum chemical descriptors related to electrostatic distribution and characteristics like ESP and ALIE are more representative in characterizing HSA-PFAS binding. This study sheds light on the interactions between HSA and PFAS. It guides health risk assessments and control strategies against PFAS, serving as a critical starting point for further public health research.

Investigating sulfonamides - Human serum albumin interactions: A comprehensive approach using multi-spectroscopy, DFT calculations, and molecular docking.

The environmental and health risks associated with sulfonamide antibiotics (SAs) are receiving increasing attention. Through multi-spectroscopy, density functional theory (DFT), and molecular docking, this study investigated the interaction features and mechanisms between six representative SAs and human serum albumin (HSA). Multi-spectroscopy analysis showed that the six SAs had significant binding capabilities with HSA. The order of binding constants at 298 K was as follows: sulfadoxine (SDX): 7.18 × 105 L mol-1 > sulfamethizole (SMT): 6.28 × 105 L mol-1 > sulfamerazine (SMR): 2.70 × 104 L mol-1 > sulfamonomethoxine (SMM): 2.54 × 104 L mol-1 > sulfamethazine (SMZ): 3.06 × 104 L mol-1 > sulfadimethoxine (SDM): 2.50 × 104 L mol-1. During the molecular docking process of the six SAs with HSA, the binding affinity range is from -7.4 kcal mol-1 to -8.6 kcal mol-1. Notably, the docking result of HSA-SDX reached the maximum of -8.6 kcal mol-1, indicating that SDX may possess the highest binding capacity to HSA. HSA-SDX binding, identified as a static quenching and exothermic process, is primarily driven by hydrogen bonds (H bonds) or van der Waals (vdW) interactions. The quenching processes of SMR/SMZ/SMM/SDX/SMT to HSA are a combination of dynamic and static quenching, indicating an endothermic reaction. Hydrophobic interactions are primarily accountable for SMR/SMZ/SMM/SDX/SMT and HSA binding. Competition binding results revealed that the primary HSA-SAs binding sites are in the subdomain IB of the HAS structure, consistent with the results of molecule docking. The correlation analysis based on DFT calculations revealed an inherent relationship between the structural chemical features of SAs and the binding performance of HSA-SAs. The dual descriptor (DD) and the electrophilic Fukui function were found to have a significant relationship (0.71 and -0.71, respectively) with the binding constants of HSA-SAs, predicting the binding performance of SAs and HSA. These insights have substantial scientific value for evaluating the environmental risks of SAs as well as understanding their impact on biological life activities.

Nitrogen-Doped Carbon Dots Encapsulated a Polyoxomolybdate-Based Coordination Polymer as a Sensitive Platform for Trace Tetracycline Determination in Water.

The requirement of simple, efficient and accurate detection of tetracycline (TC) in water environments poses new challenges for sensing platform development. Here, we report a simple method for TC sensing via fluorescence detection based on metal-organic coordination polymers (MOCPs, (4-Hap)4(Mo8O26)) coated with nitrogen-doped carbon dots (NCDs). These NCDs@(4-Hap)4(Mo8O26) composites showed excellent luminescence features of NCDs with stable bright-blue emission under UV light. The results of the sensing experiment showed that the fluorescence of NCDs@(4-Hap)4(Mo8O26) can be quenched by TC (166 µM) with 94.1% quenching efficiency via the inner filter effect (IFE) in a short time (10 s), with a detection limit (LOD) of 33.9 nM in a linear range of 8-107 µM. More significantly, NCDs@(4-Hap)4(Mo8O26) showed a high selectivity for TC sensing in the presence of anions and metal cations commonly found in water environments and can be reused in at least six cycles after washing with alcohol. The potential practicality of NCDs@(4-Hap)4(Mo8O26) was verified by sensing TC in real water samples with the standard addition method, and satisfactory recoveries from 91.95% to 104.72% were obtained.

Synergy between UV light and trichloroisocyanuric acid on methylisothiazolinone degradation: Performance, kinetics and degradation pathway.

Methylisothiazolinone (MIT) is widely used in daily chemicals, fungicides, and other fields and its toxicity has posed a threat to water system and human health. In this study, ultraviolet (UV)/trichloroisocyanuric acid (TCCA), which belongs to advanced oxidation processes (AOP), was adopted to degrade MIT. Total chlorine attenuation detection proved that TCCA has medium UV absorption and a strong quantum yield (0.49 mol E-1). At a pH of 7.0, 93.5% of MIT had been decontaminated after 60 min in UV/TCCA system (kobs = 4.4 × 10-2 min-1, R2 = 0.978), which was much higher than that in the UV alone system and TCCA alone system, at 65% (1.7 × 10-2 min-1, R2 = 0.995) and 10% (1.8 × 10-3 s-1, R2 = 0.915), respectively. This system also behaved well in degrading other five kinds of contaminants. Tert-butanol (TBA) and carbonate (CO32-) were separately used in quenching experiments, and the degradation efficiency of MIT decreased by 39.5% and 46.5% respectively, which confirmed that HO• and reactive chlorine species (RCS) were dominant oxidants in UV/TCCA system. With TCCA dosage increasing in a relatively low concentration range (0.02-0.2 mM) and pH decreasing, the effectiveness of this AOP system would be strengthened. The influences of coexisting substances (Cl-, SO42-, CO32-, NO2- and NO3-) were explored. MIT degradation pathways were proposed and sulfur atom oxidation and carboxylation were considered as the dominant removal mechanisms of MIT. Frontier orbital theory and Fukui indexes of MIT were employed to further explore the degradation mechanism.

Insights into the electron transfer regime of permanganate activation on carbon nanomaterial reduced from carbon dioxide.

Simultaneously eliminating novel contaminants in the water environment while also achieving high-value utilization of CO2 poses a significant challenge in water purification. Herein, a CO2-reduced carbon catalyst (CRC) was synthesized via the chemical vapor deposition method for permanganate (PM) activation, fulfilling the ultra-efficient removal of bisphenol A (BPA). The primary mechanism responsible for the BPA degradation in the CRC/PM process is electron transfer. Hydroxyl groups and defect structures on CRC act as electron mediators, facilitating the transfer of electrons from contaminants to PM. On the basis of the quantitative structure-activity relationship, the elimination performance of the CRC/PM process exhibited variability in accordance with the inherent characteristics of pollutants. In addition, the yield of manganese intermediates was also observed in the CRC/PM process, which only serve as redox intermediates rather than active species attacking organics. Ascribed to nonradical mechanisms, the CRC/PM system exhibited remarkable stability and demonstrated significant resistance to the presence of background substances. Moreover, BPA degradation pathways were clarified via mass spectrometry analysis and density functional theory calculations, with intermediate products exhibiting lower toxicity. This study provided new insights into the employment of carbon catalysts derived from CO2 for PM nonradical activation to degrade contaminants in various water matrices.

Advanced synergetic nitrogen removal of municipal wastewater using oxidation products of refractory organic matters in secondary effluent by biogenic manganese oxides as carbon source.

Due to the high operational cost and secondary pollution of the conventional advanced nitrogen removal of municipal wastewater, a novel concept and technique of advanced synergetic nitrogen removal of partial-denitrification anammox and denitrification was proposed, which used the oxidation products of refractory organic matters in the secondary effluent of municipal wastewater treatment plant (MWWTP) by biogenic manganese oxides (BMOs) as carbon source. When the influent NH4+-N in the denitrifying filter was about 1.0, 2.0, 3.0, 4.0, 5.0 and 7.0 mg/L, total nitrogen (TN) in the effluent decreased from about 22 mg/L to 11.00, 7.85, 6.85, 5.20, 4.15 and 2.09 mg/L, and the corresponding removal rate was 49.15, 64.82, 69.40, 76.70, 81.36 and 90.58%, respectively. The proportional contribution of the partial-denitrification anammox pathway to the TN removal was 12.00, 26.45, 39.70, 46.04, 54.97 and 64.01%, and the actual CODcr consumption of removing 1 mg TN was 0.75, 1.43, 1.26, 1.17, 1.08 and 0.99 mg, respectively, which was much lower than the theoretical CODcr consumption of denitrification. Furthermore, CODcr in the effluent decreased to 8.12 mg/L with a removal rate of 72.40%, and the removed organic matters were mainly non-fluorescent organic matters. Kinds of denitrifying bacteria, anammox bacteria, hydrolytic bacteria and manganese oxidizing bacteria (MnOB) were identified in the denitrifying filter, which demonstrated that the advanced synergetic nitrogen removal was achieved. This novel technology presented the advantages of high efficiency of TN and CODcr removal, low operational cost and no secondary pollution.

Advanced nitrogen removal performance and microbial community structure of a lab-scale denitrifying filter with in-situ formation of biogenic manganese oxides.

Advanced nitrogen removal faces the challenges of high operational cost resulted from the additional carbon source and secondary pollution caused by inaccurate carbon source dosage in municipal wastewater. To address these problems, a novel carbon source was developed, which was the oxidation products of refractory organic matters in the secondary effluent of municipal wastewater treatment plant (MWWTP) by in-situ generated biogenic manganese oxides (BMOs) in the denitrifying filter. In the steady phase, the effluent chemical oxygen demand (CODcr), NO3--N and total nitrogen (TN) in the denitrifying filter 2# with BMOs was 11.27, 9.03 and 10.36 mg/L, and the corresponding removal efficiency was 54.79%, 51.85% and 48.03%, respectively, which was significantly higher than those in the control denitrifying filter 1# that the removal efficiency of CODcr, NO3--N and TN was only 32.30%, 28.58% and 29.36%, respectively. Kinds of denitrifying bacteria (Candidatus Competibacter, Defluviicoccus, Dechloromonas, Candidatus Competibacter, Dechloromonas, Pseudomonas, Thauera, Acinetobacter, Denitratisoma, Anaerolineae and Denitratisoma) and anammox bacteria (Pirellula, Gemmata, Anammoximicrobium and Brocadia) were identified in the denitrifying filters 1# and 2#, which explained why the actual CODcr consumption (1.55 and 1.44 mg) of reducing 1 mg NO3--N was much lower than the theoretical CODcr consumption. While manganese oxidizing bacteria (MnOB, Bacillus, Crenothrix and Pedomicrobium) was only identified in the denitrifying filter 2#. This novel technology presented the advantages of no additional carbon source, low operational cost and no secondary pollution. Therefore, the novel technology has superlative application value and broad application prospect.

A Novel Source of Radicals from UV/Dichloroisocyanurate for Surpassing Abatement of Emerging Contaminants Versus Conventional UV/Chlor(am)ine Processes.

Ultraviolet (UV)/chlor(am)ine processes are emerging advanced oxidation processes (AOPs) for water decontamination and raising continuous attention. However, limitations appear in the UV/hypochlorite and UV/monochloramine for removing specific contaminants ascribed to the differences in the sorts and yields of free radicals. Here, this study reports UV/dichloroisocyanurate (NaDCC) as a novel source of radicals. NaDCC was demonstrated to be a well-balanced compound between hypochlorite and monochloramine, and it had significant UV absorption and a medium intrinsic quantum yield. The UV/NaDCC produced more substantial hydroxyl radicals (·OH) and reactive chlorine species (RCSs, including Cl·, ClO·, and Cl2·-) than conventional UV/chlor(am)ine, thereby generating a higher oxidation efficiency. The reaction mechanisms, environmental applicability, and energy requirements of the UV/NaDCC process for emerging contaminants (ECs) abatement were further investigated. The results showed that ·OH and ·NH2 attacked ECs mostly through hydrogen atom transfer (HAT) and radical adduct formation, whereas Cl· destroyed ECs mainly through HAT and single electron transfer, with ClO· playing a certain role through HAT. Kinetic model analyses revealed that the UV/NaDCC outperformed the conventional UV/chlor(am)ine in a variety of water matrices with superior degradation efficiency, significantly saving up to 96% electrical energy per order. Overall, this study first demonstrates application prospects of a novel AOP using UV/NaDCC, which can compensate for the deficiency of the conventional UV/chlor(am)ine AOPs.

Generality and diversity on the kinetics, toxicity and DFT studies of sulfate radical-induced transformation of BPA and its analogues.

The international campaign to ban bisphenol A (BPA) has resulted in increasing application of BPA substitutes. However, investigations have mainly been confined to the removal of single contaminant from the water, resulting in an inefficient burden. Furthermore, systematic study and synthetical discussion of bisphenol analogues (BPs) kinetics and transformation pathways were largely underemphasized. Chemical oxidation of BPA and four typical alternatives (i.e., bisphenol AF, bisphenol E, bisphenol F and bisphenol S) in a UV-activated persulfate system was examined in this study. The effects of persulfate (PS) dosage, pH and water matrix constituents (i.e., bicarbonate, chloride and natural organic matter) were comprehensively examined using a combination of laboratory experiments and mathematical modeling. According to our findings, the removal characteristics of different BPs employing SO4•--induced removal technology, including degradation mechanisms and influencing trends by water matrix, revealed similarly. The second order-rate constants of SO4•- reacting with BPs served as the main variables mediating the variation in degradation kinetics. Frontier molecular orbital theory and density functional theory suggested BPs molecules possessed the same susceptible positions to free radicals. In the UV-activated PS process, transformation pathways included hydroxylation, electron-transfer, substitution, and rearrangement triggered by ortho-cleavage, with certain intermediates exhibiting higher toxicity than the parent chemicals. The findings of this study provided valuable information to estimate potential environmental risks of using BPA alternatives.

Feasibility of micropollutants removal by solar-activated persulfate: Reactive oxygen species formation and influence on DBPs.

As a natural source of visible light and a type of renewable energy, solar energy is extensively used in the field of photochemistry. In this study, solar was employed to activate persulfate (PS) to degrade typical micropollutants. The removal kinetics of aspirin (ASA) and flunixin meglumine (FMME) in the solar/PS system were well fitted by pseudo-first-order models (R2 > 0.99). In the system containing 1.0 mM PS activated by solar irradiation at a fluence of 1.14 × 10-4 E·m-2·s-1, 72.6% and 97.5% of ASA and FMME were degraded, and the corresponding kinetic constants were 6.8-9.8 × 10-2 and 1.6-9.8 × 10-1 min-1, respectively. Qualitative and quantitative analyses of the reactive oxygen species (ROS) indicated that sulfate radical (SO4·-) played a major role in degradation, with the maximum contributions of 77.7% and 88.8% for the degradation of ASA and FMME, whereas the maximum contributions of hydroxyl radical (·OH) were only 11.6% and 6.5%, respectively. The contributions of singlet oxygen (1O2) were less than 15% at pH 5.5, but increased to 25.6% and 45.5% at pH 8.5, respectively. Solar/PS pre-oxidation increased disinfection byproducts (DBPs) (95.8% for trihalomethanes (THMs) and 47.9% for haloacetic acids (HAAs) at pH 7.0) after chlorination in deionized water, and an opposite trend was found in systems coexisting with natural organic matter (NOM). Residual PS after oxidation resulted in a high aquatic toxicity, with an inhibition rate of 18.70% to algae growth. Economic analysis showed that the electrical energy per order values of the system ranged from 23.5 to 86.5 kWh·m-3·order-1, indicating that the solar/PS system shows promise for practical applications.

Ozonation Treatment Increases Chlorophenylacetonitrile Formation in Downstream Chlorination or Chloramination.

Chlorophenylacetonitriles (CPANs) are an emerging group of aromatic nitrogenous disinfection byproducts (DBPs). However, their dominant precursors and formation pathways remain unclear, which hinders the further development of effective control strategies. For the first time, CPAN precursors were screened by conducting formation potential (FP) tests on real water samples from six drinking water treatment plants (DWTPs). The average overall removal of CPAN precursors across all six DWTPs was only 10%. Moreover, ozonation increased CPAN precursors by 140% on average. Fluorescence spectroscopy showed a dramatic reduction in aromatic proteins, tyrosine-like proteins, and tryptophan-like proteins following ozonation. Low-apparent-molecular-weight (AMW) (<1 kDa) substances were correlated with the CPAN FP in these samples. We therefore hypothesized that protein fragments with low AMW, such as amino acids, are important CPAN precursors during downstream chlor(am)ination. Two aromatic free amino acids, tyrosine and tryptophan, were selected to investigate the formation of CPANs during chlor(am)ination. Both amino acids were found to act as CPAN precursors for the first time. CPAN formation pathways from these model precursors were proposed based on the frontier molecular orbital theory and intermediate products identified using high-resolution mass spectrometry. This study provides a powerful theoretical foundation for controlling CPAN formation in drinking water.

Staged assessment for the involving mechanism of humic acid on enhancing water decontamination using H2O2-Fe(III) process.

Humic acid (HA) as a natural coordinating agent was employed to modify the Fenton-like process by promoting the redox cycle of Fe(III)/Fe(II) and enhancing the pH tolerance. However, the roles of coordinating stages of HA-Fe(III) and the dynamic changes of iron species remain unclear. In this study, HA was introduced into the H2O2-Fe(III) process to investigate the accelerating roles of coordinating stages and systematically reveal the mechanism via the reactive oxygen species (ROS) identification, HA-Fe(III)/Fe(II) redox cycles tracking, electrochemical and kinetic analysis. Results suggested that two reaction stages were separated concerning the enhancement for HA in H2O2-Fe(III) process, including coordinating stage (slow rate) and promoting the redox stage (fast rate). HA-Fe(III) was identified as the major contributor, along with hydroxyl radical (·OH) and superoxide radical (·O2-) as the dominant ROS with formation rates calculated as 7.0 × 10-9 and 2.1 × 10-3 M s-1 via the steady-state model. Based on the density-functional theory (DFT) calculations and HPLC-MS/MS analysis, three degradation pathways of 2,4-Dichlorophenol were proposed with ten intermediate products identified, and the ecotoxicity was evaluated through Ecological Structure Activity Relationships (ECOSAR) program. This study unveiled the mechanism of HA on enhancing water decontamination via H2O2-Fe(III) process in stages.

[Kinetics and Mechanism of Sucralose Degradation in Water Using UV-activated Persulfate Process].

The degradation of emerging pollutant artificial sweetener sucralose (SUC) using UV/persulfate (UV/PS). The effects of several process parameters, including UV light intensity, PS dosage, pH, and anion concentration, were also investigated. The degradation products and their toxicity during the UV/PS process were further analyzed and evaluated. It is reported that, compared with single UV or PS, the degradation of SUC by UV/PS was more obvious. The degradation rate constants increased with an increase in the light intensity and PS dosage. The SUC degradation could be improved under neutral conditions. The background ions NO3- and HCO3- could inhibit the degradation process, while Cl- and SO42- ions could accelerate the process. Sixteen intermediate products were identified using high-resolution mass spectrometry (HRMS) and GC-MS. Hydroxylation, oxidation, ether cracking, and other reactions were involved. A degradation path was further proposed. Moreover, luminescent bacteria toxicity test and ECOSAR prediction showed that the intermediates with higher toxicity could be produced during UV/PS, which could pose a potential threat to the ecological environment.

Kinetic mechanism of ozone activated peroxymonosulfate system for enhanced removal of anti-inflammatory drugs.

Peroxymonosulfate (PMS) was employed as an activator of ozone (O3) to degrade non-steroidal anti-inflammatory drugs (NSAIDs) (aspirin (ASA) and phenacetin (PNT)) in study. The combination of PMS in O3 system promoted the O3 decomposition and NSAIDs removal significantly. O3 molecule, hydroxyl radical (OH) and sulfate radical (SO4-) were responsible for the removal of target pollutants in O3/PMS system. The second-rate constants between O3, OH and SO4- with ASA were determined to be 7.32, 4.18 × 109 and 3.46 × 108 M-1·s-1, and 37.3, 4.99 × 109 and 5.64 × 108 M-1·s-1 for PNT, respectively. The pattern of pollutant removal and contributions of oxidative species were fitted by experiments and two models. Nevertheless, the wide variety of two models suggested that a comprehensive model for O3/PMS based on a first-principles approach was not yet possible, due to the number of radicals and subsequent chain reaction, such as SO5- or O3-. In addition, the formation of five typical CX3R -type disinfection by products was evaluated from post­chlorine tests and theoretically calculation by frontier electron density calculation. The calculated toxicity of typical CX3R -type DBPs was found to decrease with the increase of pH. The results of this study provide a basis for exploring the mechanism of pollutant degradation in O3 system.

Crucial roles of oxygen and superoxide radical in bisulfite-activated persulfate oxidation of bisphenol AF: Mechanisms, kinetics and DFT studies.

Though natural reducing agents have been demonstrated as desirable catalysts for environmental remediation, the mechanism of catalytic activation of persulfate (PS) by bisulfite (S(IV)) remains unclear. In this study, an emerging contaminant bisphenol AF (BPAF) was employed as the target compound to examine the activation and degradation mechanism in PS/S(IV) system. Sulfate radical (SO4•-) was evidenced as the dominant radical accounting for BPAF degradation via quantitative analysis, while hydroxyl radical (•OH) and singlet oxygen (1O2) were minor contributors. Superoxide radical (O2•-) was identified as an intermediate radical in promoting BPAF removal through quenching experiments and electron paramagnetic resonance analysis. Tests in oxygen-rich and oxygen-deficient systems were conducted and the results were contrasted to elucidate the important role of oxygen in BPAF degradation and SO4•--formation. In addition, the effect of Dissolved Oxygen (DO) was simulated using two separate kinetic models. Decomposition mechanism of BPAF was afterwards clarified via the density-functional theory calculations using Fukui index to predict the vulnerable sites and the intermediate products. This study provides a mechanistic understanding of the activation of PS/S(IV) system on the BPAF removal, especially the critical role of DO and O2•- in SO4•- generation.

Mechanism insight of acetaminophen degradation by the UV/chlorine process: kinetics, intermediates, and toxicity assessment.

The removal of acetaminophen (AAP) in aqueous solution by the UV/chlorine process was evaluated. The effect of chlorine dose, the initial AAP concentration, pH value, and UV intensity on the reaction were also investigated. The degradation mechanism and the ecological risk were further discussed. The results indicated that AAP degradation fitted pseudo-first-order kinetics. Compared with UV alone or dark chlorination, the combination of UV and chlorine significantly accelerated the degradation process. The AAP degradation was positively affected by chlorine dose and UV intensity, while negatively affected by the initial AAP concentration and ammonia nitrogen concentration during the UV/chlorine process. The frontier orbital theory analysis shows that the C5 position in the benzene ring of AAP is likely to be the first site attacked by HO• and Cl• radical to form the products. Twelve intermediates were identified by Q-TOF and GC-MS. The possible degradation pathways were also proposed. Luminescent bacteria experiment and ECOSAR prediction both revealed that acute toxicity of AAP degradation could only be partially reduced. Ecological risks during the UV/chlorine process need to be further evaluated.

Transformation of naproxen during the chlorination process: Products identification and quantum chemistry validation.

The by-products produced by pharmaceutically active compounds (PhACs) during chlorination are attracting wide concern. Thus, the transformation and toxicity of naproxen (NAP) during the chlorination process were assessed in this study. The transformation of NAP was found to follow pseudo-first-order kinetics, and the first-order rate constant was improved by increasing the NaOCl dose. High-resolution mass spectrometry (HRMS) was successfully applied to identify 14 chlorination products. This study represents the first elucidation and report of the exact structure of the primary chlorine substitution product ((2S)-2-(5-chloro-6-methoxy-2-naphthyl)propionic acid) based on HRMS and 1H NMR. Chlorine will primarily substitute the hydrogen atom on the C7 position of the naphthalene ring to form the mono-chlorine substitution product, as further validated at the theoretical level by quantum chemical calculations. A series of HOCl-induced reactions, including substitution, demethylation, and dehydrogenation, led to the transformation of NAP during the chlorination process. ECOSAR program revealed that the potential aquatic toxicity of the transformation products is significantly higher than that of the parent NAP. Their introduction into the environment may still pose potential risks.