Formation of dichloroacetic acid and dichloroacetamide from phenicol antibiotic abatement during ozonation and post-chlor(am)ination.

This study investigated the formation of dichloroacetamide (DCAM) and dichloroacetic acid (DCAA) from the abatement of three phenicol antibiotics (PABs, chloramphenicol, thiamphenicol, and florfenicol) during ozonation and post-chlor(am)ination. Results show that the three PABs have a low ozone reactivity (kO3 = 0.11‒0.12 M-1 s-1), and therefore are mainly abated through the hydrogen abstraction mechanism by hydroxyl radicals (•OH) during ozonation. During PAB degradation, the carboxamide moiety in the parent molecules can be cleaved off by •OH attack and thus gives rise to DCAM. The formed DCAM can then be further oxidized by O3 and/or •OH to DCAA as a more stable transformation product (TP). When the three PABs were adequately abated (abatement efficiency of ∼82 %‒95 %), the molar yields of DCAM and DCAA were determined to be 2.79 %‒4.71 % and 32.9 %‒37.2 %, respectively. Furthermore, post-chloramination of the ozonation effluents increased the yields of DCAM and DCAA slightly to 4.20 %‒6.45 % and 39.0 %‒41.1 %, respectively. In comparison, post-chlorination eliminated DCAM in the solutions, but significantly increased DCAA yields to ∼100 % due to the further conversion of DCAM and other ozonation TPs to DCAA by chlorine oxidation. The results of this study indicate that high yields of DCAM and DCAA can be generated from PAB degradation during ozonation, and post-chlorination and post-chloramination will result in very different fates of DCAM and DCAA in the disinfected effluent. The formation and transformation of DCAM and DCAA during PAB degradation need to be taken into account when selecting multi-barrier treatment processes for the treatment of PAB-containing water.

Clarification of the role of singlet oxygen for pollutant abatement during persulfate-based advanced oxidation processes: Co3O4@CNTs activated peroxymonosulfate as an example.

Singlet oxygen (1O2) has often been identified by the popularly used quenching method as a more important reactive species (RS) than sulfate radicals (SO4•-) and hydroxyl radicals (•OH) for pollutant abatement during persulfate-based advanced oxidation processes (PS-AOPs), especially those activated by carbon-based catalysts. However, latest studies have demonstrated that the quenching method actually can often mislead the interpretations of the role of RS for pollutant abatement during AOPs due to various confounding effects caused by adding high-concentration quenchers in the system. To clarify the role of 1O2 in PS-AOPs, this study developed a probe compound-based experimental and kinetic model to quantify the concentrations and exposures of 1O2, SO4•-, and •OH, as well as their relative contributions to pollutant abatement during a cobalt oxide incorporated carbon nanotubes activated peroxymonosulfate (Co3O4@CNTs/PMS) process. Results show that during the Co3O4@CNTs/PMS process, the exposures and transient concentrations of 1O2 were about 19.6 and 41.3 times higher than those of SO4•- and •OH, respectively. However, the relative contribution of 1O2 to the abatement of most pollutants tested in this study (e.g., sulfisoxazole, sulfamethoxyprazine, trimethoprim, and metoprolol) is generally negligible (f1O2 ≤ 8%) compared to that of SO4•- and •OH ( [Formula: see text]  = 15%-98% and f•OH = 2%-78%) because of the significantly lower reactivity of 1O2 with these compounds than that of SO4•- and •OH. Reasons for misidentifying 1O2 as the dominant RS for pollutant abatement by the quenching method were then analyzed based on reaction kinetics principles. The results of this study highlight that while 1O2 can be generated in significant amounts and be present at higher concentrations than SO4•- and •OH in PS-AOP systems, 1O2 is unlikely to be the dominant RS for the abatement of most pollutants during the PS-AOPs because of its weak and selective oxidation capacity, and caution should be taken when using the quenching method to evaluate the role of RS for pollutant abatement by the PS-AOPs.

Wall shear stress and its role in atherosclerosis.

Atherosclerosis (AS) is the major form of cardiovascular disease and the leading cause of morbidity and mortality in countries around the world. Atherosclerosis combines the interactions of systemic risk factors, haemodynamic factors, and biological factors, in which biomechanical and biochemical cues strongly regulate the process of atherosclerosis. The development of atherosclerosis is directly related to hemodynamic disorders and is the most important parameter in the biomechanics of atherosclerosis. The complex blood flow in arteries forms rich WSS vectorial features, including the newly proposed WSS topological skeleton to identify and classify the WSS fixed points and manifolds in complex vascular geometries. The onset of plaque usually occurs in the low WSS area, and the plaque development alters the local WSS topography. low WSS promotes atherosclerosis, while high WSS prevents atherosclerosis. Upon further progression of plaques, high WSS is associated with the formation of vulnerable plaque phenotype. Different types of shear stress can lead to focal differences in plaque composition and to spatial variations in the susceptibility to plaque rupture, atherosclerosis progression and thrombus formation. WSS can potentially gain insight into the initial lesions of AS and the vulnerable phenotype that gradually develops over time. The characteristics of WSS are studied through computational fluid dynamics (CFD) modeling. With the continuous improvement of computer performance-cost ratio, WSS as one of the effective parameters for early diagnosis of atherosclerosis has become a reality and will be worth actively promoting in clinical practice. The research on the pathogenesis of atherosclerosis based on WSS is gradually an academic consensus. This article will comprehensively review the systemic risk factors, hemodynamics and biological factors involved in the formation of atherosclerosis, and combine the application of CFD in hemodynamics, focusing on the mechanism of WSS and the complex interactions between WSS and plaque biological factors. It is expected to lay a foundation for revealing the pathophysiological mechanisms related to abnormal WSS in the progression and transformation of human atherosclerotic plaques.

Assessment of the validity of the quenching method for evaluating the role of reactive species in pollutant abatement during the persulfate-based process.

Reactive species such as sulfate radicals (SO4•-), hydroxyl radicals (•OH), and/or singlet oxygen (1O2) have often been proposed as the main reactive species for pollutant abatement during the persulfate-based process, and their relative importance is conventionally assessed by the quenching method based on an implicit fundamental assumption that the added high-concentration quenchers (e.g., tert-butanol and methanol) only scavenge their target reactive species, but do not considerably affect the other reaction mechanism of the system. To examine the validity of this assumption, this study evaluated the effects of several commonly used quenchers (tert-butanol, methanol, ethanol, isopropanol, furfuryl alcohol, and L-histidine) on the mechanism of a cobalt mediated peroxymonosulfate (Co(II)/PMS) process. The results demonstrate that besides quenching target reactive species, the added high-concentration quenchers can cause many confounding effects on the Co(II)/PMS process, e.g., accelerating PMS decomposition, interfering reactive species production, and quenching of non-target reactive species. Because of these confounding effects, the quenching method can actually lead to serious misinterpretation of the role of reactive species in pollutant abatement during the persulfate-based process. The findings of this study highlight that the underlying assumption of the quenching method is usually invalid for the persulfate-based process. Therefore, it should be cautious to apply the quenching method to investigate the mechanism of the persulfate-based process, and some debatable conclusions of prior studies obtained with the quenching method may require further verification.

Experimental and theoretical study of kinetic and mechanism of hydroxyl radical-mediated degradation of sulfamethazine.

Hydroxyl radical (•OH)-based advanced oxidation technologies (AOTs) is an effective and clean way to remove sulfonamide antibiotics in water at ambient temperature and pressure. In this study, we systematically investigated the degradation kinetics of sulfamethazine (SMT) by •OH with a combination of experimental and theoretical approaches. The second-order rate constant (k) of SMT with •OH was experimentally determined to be 5.27 ± 0.06 × 109 M-1 s-1 at pH 4.5. We also calculated the thermodynamic and kinetic behaviors for the reactions by density functional theory (DFT) using the B3LYP/6-31G*. The results revealed that •OH addition pathways at the methylene (C4) site on the pyridine ring and the ortho sites (C12 and C14) of the amino group on the benzene ring dominate the reaction, especially C14 site on the benzene ring accounted for 43.95% of SMT degradation kinetics. The theoretical k value which was calculated by conventional transition state theory is 3.96 × 109 M-1 s-1, indicating that experimental observation (5.27 ± 0.06 × 109) is correct. These results could further help AOTs design in treating sulfonamide during wastewater treatment processes.

Kinetics and mechanism of thiamethoxam abatement by ozonation and ozone-based advanced oxidation processes.

In this study, the abatement of neonicotinoid insecticide, thiamethoxam, by single ozonation, ozone/ultraviolet (O3/UV) and electro-peroxone (EP) process was evaluated. The second-order rate constants for the reaction of thiamethoxam with O3 and hydroxyl radical (OH) at pH 7 were determined to be 15.4 M-1 s-1 and 3.9 × 109 M-1 s-1, respectively. The degradation pathways of thiamethoxam were proposed based on quantum chemical calculations and transformation products were identified using chromatographic and mass-spectrometric techniques. The acute and chronic toxicity of thiamethoxam and its major TPs to various aquatic organisms were assessed. With typical ozone doses applied in water treatment (≤5 mg/L), thiamethoxam was abated by only ∼16-32 % in two real water matrices (groundwater and surface water) during single ozonation, but by ∼100 % and >70 % during the O3/UV and EP treatment, respectively. The energy demand to abate 90 % thiamethoxam in the two water matrices was generally comparable for single ozonation and the EP process (∼0.14 ±â€¯0.03 kW h/m3), but higher for the O3/UV process (0.21-0.22 kW h/m3). These results suggest that single ozonation is unable to sufficiently abate thiamethoxam under typical conditions of water treatment. Therefore, ozone-based advanced oxidation processes are needed to enhance thiamethoxam abatement.

Experimental and theoretical insights into kinetics and mechanisms of hydroxyl and sulfate radicals-mediated degradation of sulfamethoxazole: Similarities and differences.

Hydroxyl radical (•OH)- and sulfate radical ()-based advanced oxidation technologies (AOTs) have been proven an effective method to remove antibiotics in wastewater treatment plants (WWTPs). This study aims to gain insights into kinetics and mechanisms of neutral sulfamethoxazole (SMX) degradation, a representative antibiotic, by •OH and using an experimental and theoretical approach. First, the second-order rate constants (k) of SMX with •OH and were determined to be (7.27 ± 0.43) × 109 and (2.98 ± 0.32) × 109 M-1 s-1 in UV/H2O2 and UV/persulfate (UV/PS) systems, respectively. The following theoretical calculations at the M06-2X level of theory revealed that addition of radicals to the benzene ring is the most favorable first-step reaction for both •OH and , but that exhibits higher energy barriers and selectivity than •OH due to steric hindrance. We further analyzed subsequent reactions and, interestingly, our findings closely corroborated HOMO/LUMO distributions of SMX to the oxidation pathways. Finally, the estimation of energy consumption for UV alone, •OH-, and -mediated oxidation processes was compared. These comparative results, for the first time, provide insights into the similarities and differences of degradation of SMX by •OH/ at the molecular level and can help improve antibiotics removal using radical based AOTs in WWTPs.

Mechanistic Study on the Role of Soluble Microbial Products in Sulfate Radical-Mediated Degradation of Pharmaceuticals.

The role of soluble microbial products (SMP), the most important component of effluent organic matter from municipal wastewater treatment plants, in sulfate radical (SO4•-)-based advanced oxidation technologies (AOTs) remains substantially unclear. In this study, we first utilized a suite of macro- and microanalytical techniques to characterize the SMP from a membrane bioreactor for its fundamental molecular, spectroscopic, and reactivity properties. The degradation kinetics of three representative pharmaceuticals (i.e., naproxen, gemfibrozil, and sulfadiazine) in the presence of SMP was significantly reduced as compared to in its absence. Possible mechanisms for the interference by SMP in degrading these target compounds (TCs) were investigated. The low percentage of bound TCs to SMP ruled out the cage effect. The measurement of steady-state 1O2 concentration indicated that formation of 1O2 upon UV irradiation on SMP was not primarily responsible for the degradation of TCs. However, the comparative and quenching results reveal that SMP absorbs UV light acting as an inner filter toward the TCs, and meanwhile scavenges SO4•- with a high second-order rate constant of 2.48 × 108 MC-1 s-1.

Kinetic and mechanistic aspects of hydroxyl radical‒mediated degradation of naproxen and reaction intermediates.

Hydroxyl radical (•OH) based advanced oxidation technologies (AOTs) are effective for removing non‒steroidal anti-inflammatory drugs (NSAIDs) during water treatment. In this study, we systematically investigated the degradation kinetics of naproxen (NAP), a representative NSAID, with a combination of experimental and theoretical approaches. The second-order rate constant (k) of •OH oxidation of NAP was measured to be (4.32 ±â€¯0.04) × 109 M-1 s-1, which was in a reasonable agreement with transition state theory calculated k value (1.08 × 109 M-1 s-1) at SMD/M05-2X/6-311++G**//M05-2X/6-31+G** level of theory. The calculated result revealed that the dominant reaction intermediate is 2‒(5‒hydroxy‒6‒methoxynaphthalen‒2‒yl)propanoic acid (HMNPA) formed via radical adduct formation pathway, in which •OH addition onto the ortho site of the methoxy-substituted benzene ring is the most favorable pathway for the NAP oxidation. We further investigated the subsequent •OH oxidation of HMNPA via a kinetic modelling technique. The k value of the reaction of HMNPA and •OH was determined to be 2.22 × 109 M-1 s-1, exhibiting a similar reactivity to the parent NAP. This is the first study on the kinetic and mechanistic aspects of NAP and its reaction intermediates. The current results are valuable in future study evaluating and extending the application of •OH based AOTs to degrade NAP and other NSAIDs of concern in water treatment plants.

UV direct photolysis of sulfamethoxazole and ibuprofen: An experimental and modelling study.

Photodegradation characteristics of pharmaceuticals and personal care products (PPCPs) during UV irradiation are of practical and scientific importance in selecting operational parameters during water treatment processes. In this study, the molar extinction coefficient (ε), quantum yield (φ), and degradation kinetics of neutral/anionic forms of sulfamethoxazole (SMX) and ibuprofen (IBU) were compared by varying solution pH. The degradation kinetics of the target compounds were observed to reversely correlate to the energy gap between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) values of the target compounds. Then, a kinetic model for predicting the direct photolytic rates at different solution pH was established based on ε and φ of neutral/anionic species. The root mean squared errors for the modeled values suggest that the model exhibits good predictive power. Finally, in order to evaluate the electrical energy consumption during the UV direct photolysis process, the electrical energy per order (EE/O) was assessed. The experimental and modelling results are important to elucidate the mechanism of degradation of target PPCPs under UV irradiation and allow for the selection of optimal conditions in water treatment processes.

Mechanistic insight into degradation of endocrine disrupting chemical by hydroxyl radical: An experimental and theoretical approach.

Advanced oxidation processes (AOPs) based on formation of free radicals at ambient temperature and pressure are effective for treating endocrine disrupting chemicals (EDCs) in waters. In this study, we systematically investigated the degradation kinetics of bisphenol A (BPA), a representative EDC by hydroxyl radical (OH) with a combination of experimental and theoretical approaches. The second-order rate constant (k) of BPA with OH was experimentally determined to be 7.2 ± 0.34 × 109 M-1 s-1 at pH 7.55. We also calculated the thermodynamic and kinetic behaviors for the bimolecular reactions by density functional theory (DFT) using the M05-2X method with 6-311++G** basis set and solvation model based on density (SMD). The results revealed that H-abstraction on the phenol group is the most favorable pathway for OH. The theoretical k value corrected by the Collins-Kimball approach was determined to be 1.03 × 1010 M-1 s-1, which is in reasonable agreement with the experimental observation. These results are of fundamental and practical importance in understanding the chemical interactions between OH and BPA, and aid further AOPs design in treating EDCs during wastewater treatment processes.