Direct Determination of Absolute Radical Quantum Yields in Hydroxyl and Sulfate Radical-Based Treatment Processes.

The absolute radical quantum yield (Φ) is a critical parameter to evaluate the efficiency of radical-based processes in engineered water treatment. However, measuring Φ is fraught with challenges, as current quantification methods lack selectivity, specificity, and anti-interference capabilities, resulting in significant error propagation. Herein, we report a direct and reliable time-resolved technique to determine Φ at pH 7.0 for commonly used radical precursors in advanced oxidation processes. For H2O2 and peroxydisulfate (PDS), the values of Φ•OH and ΦSO4•- at 266 nm were measured to be 1.10 ± 0.01 and 1.46 ± 0.05, respectively. For peroxymonosulfate (PMS), we developed a new approach to determine Φ•OHPMS with terephthalic acid as a trap-and-trigger probe in the nonsteady state system. For the first time, the Φ•OHPMS value was measured to be 0.56 by the direct method, which is stoichiometrically equal to ΦSO4•-PMS (0.57 ± 0.02). Additionally, radical formation mechanisms were elucidated by density functional theory (DFT) calculations. The theoretical results showed that the highest occupied molecular orbitals of the radical precursors are O-O antibonding orbitals, facilitating the destabilization of the peroxy bond for radical formation. Electronic structures of these precursors were compared, aiming to rationalize the tendency of the Φ values we observed. Overall, this time-resolved technique with specific probes can be used as a reliable tool to determine Φ, serving as a scientific basis for the accurate performance evaluation of diverse radical-based treatment processes.

Degradation behaviors of Nabumetone and its metabolite during UV/monochloramine process: Experimental and theoretical study.

This study investigated degradation behaviors of a nonsteroidal anti-inflammatory drug Nabumetone (NMT) and its major metabolite 6-methoxy-2-naphthylacetic acid (MNA) in the coupling process of ultraviolet and monochloramine (UV/NH2Cl). The second-order rate constants of the contaminants reacting with reactive radicals (HO•, Cl•, Cl2•⁻, and CO3•⁻) were determined by laser flash photolysis experiments. HO• and Cl• contributed predominantly with 52.3% and 21.7% for NMT degradation and 60.8% and 22.3% for MNA degradation. The presence of chlorides retarded the degradation of NMT, while promoted the destruction of MNA, which was ascribed to the photosensitization effects of MNA under UV irradiation. Density functional theory (DFT) calculations revealed that radical adduct formation (RAF) was dominant pathway for both HO• and Cl• reacting with the contaminants, and hydrogen atom transfer (HAT) preferred to occur on side chains of NMT and MNA. NMT reacted with NO2• through single electron transfer (SET) with the second-order rate constant calculated to be 5.35 × 107 (mol/L)-1 sec-1, and the contribution of NO2• was predicted to be 13.0% of the total rate constant of NMT in pure water, which indicated that NO2• played a non-negligible role in the degradation of NMT. The acute toxicity and developmental toxicity of NMT were enhanced after UV/NH2Cl treatment, while those of MNA were alleviated. The transformation products of both NMT and MNA exhibited higher mutagenicity than their parent compounds. This study provides a deep understanding of the mechanism of radical degradation of NMT and MNA in the treatment of UV/NH2Cl.

Bimolecular versus Trimolecular Reaction Pathways for H2O2 with Hypochlorous Species and Implications for Wastewater Reclamation.

The benchmark advanced oxidation technology (AOT) that uses UV/H2O2 integrated with hypochlorous species exhibits great potential in removing micropollutants and enhancing wastewater treatability for reclamation purposes. Although efforts have been made to study the reactions of H2O2 with hypochlorous species, there exist great discrepancies in the order of reaction kinetics, the rate constants, and the molecule-level mechanisms. This results in an excessive use of hypochlorous reagents and system underperformance during treatment processes. Herein, the titled reaction was investigated systematically through complementary experimental and theoretical approaches. Stopped-flow spectroscopic measurements revealed a combination of bi- and trimolecular reaction kinetics. The bimolecular pathway dominates at low H2O2 concentrations, while the trimolecular pathway dominates at high H2O2 concentrations. Both reactions were simulated using direct dynamics trajectories, and the pathways identified in the trajectories were further validated by high-level quantum chemistry calculations. The theoretical results not only supported the spectroscopic data but also elucidated the molecule-level mechanisms and helped to address the origin of the discrepancies. In addition, the impact of the environmental matrix was evaluated by using two waters with discrete characteristics, namely municipal wastewater and ammonium-rich wastewater. Municipal wastewater had a negligible matrix effect on the reaction kinetics of H2O2 and the hypochlorous species, making it a highly suitable candidate for this integration technique. The obtained in-depth reaction mechanistic insights will enable the development of a viable and economical technology for safe water reuse.

Potential Alignment in Tandem Catalysts Enhances CO2-to-C2H4 Conversion Efficiencies.

The in-tandem catalyst holds great promise for addressing the limitation of low *CO coverage on Cu-based materials for selective C2H4 generation during CO2 electroreduction. However, the potential mismatch between the CO-formation catalyst and the favorable C-C coupling Cu catalyst represents a bottleneck in these types of electrocatalysts, resulting in low tandem efficiencies. In this study, we propose a robust solution to this problem by introducing a wide-CO generation-potential window nickel single atom catalyst (Ni SAC) supported on a Cu catalyst. The selection of Ni SAC was based on theoretical calculations, and its excellent performance was further confirmed by using in situ IR spectroscopy. The facilitated carbon dimerization in our tandem catalyst led to a ∼370 mA/cm2 partial current density of C2H4, corresponding to a faradic efficiency of ∼62%. This performance remained stable and consistent for at least ∼14 h at a high current density of 500 mA/cm2 in a flow-cell reactor, outperforming most tandem catalysts reported so far.

Implementation of laser flash photolysis for radical-induced reactions and environmental implications.

Confronted with the imperative crisis of water quality deterioration, the pursuit of state-of-the-art decontamination technologies for a sustainable future never stops. Fitting into the framework of suitability, advanced oxidation processes have been demonstrated as powerful technologies to produce highly reactive radicals for the degradation of toxic and refractory contaminants. Therefore, investigations on their radical-induced degradation have been the subject of scientistic and engineering interests for decades. To better understand the transient nature of these radical species and rapid degradation processes, laser flash photolysis (LFP) has been considered as a viable and powerful technique due to its high temporal resolution and rapid response. Although a number of studies exploited LFP for one (or one class of) specific reaction(s), reactions of many possible contaminants with radicals are largely unknown. Therefore, there is a pressing need to critically review its implementation for kinetic quantification and mechanism elucidation. Within this context, we introduce the development process and milestones of LFP with emphasis on compositions and operation principles. We then compare the specificity and suitability of different spectral modes for monitoring radicals and their decay kinetics. Radicals with high environmental relevance, namely hydroxyl radical, sulfate radical, and reactive chlorine species, are selected, and we discuss their generation, detection, and implications within the frame of LFP. Finally, we highlight remaining challenges and future perspectives. This review aims to advance our understandings of the implementation of LFP in radical-induced transient processes, and yield new insights for extrapolating this pump-probe technique to make significant strides in environmental implications.

Merits and Limitations of Radical vs. Nonradical Pathways in Persulfate-Based Advanced Oxidation Processes.

Urbanization and industrialization have exerted significant adverse effects on water quality, resulting in a growing need for reliable and eco-friendly treatment technologies. Persulfate (PS)-based advanced oxidation processes (AOPs) are emerging as viable technologies to treat challenging industrial wastewaters or remediate groundwater impacted by hazardous wastes. While the generated reactive species can degrade a variety of priority organic contaminants through radical and nonradical pathways, there is a lack of systematic and in-depth comparison of these pathways for practical implementation in different treatment scenarios. Our comparative analysis of reaction rate constants for radical vs. nonradical species indicates that radical-based AOPs may achieve high removal efficiency of organic contaminants with relatively short contact time. Nonradical AOPs feature advantages with minimal water matrix interference for complex wastewater treatments. Nonradical species (e.g., singlet oxygen, high-valent metals, and surface activated PS) preferentially react with contaminants bearing electron-donating groups, allowing enhancement of degradation efficiency of known target contaminants. For byproduct formation, analytical limitations and computational chemistry applications are also considered. Finally, we propose a holistically estimated electrical energy per order of reaction (EE/O) parameter and show significantly higher energy requirements for the nonradical pathways. Overall, these critical comparisons help prioritize basic research on PS-based AOPs and inform the merits and limitations of system-specific applications.

Overlooked Transformation of Nitrated Polycyclic Aromatic Hydrocarbons in Natural Waters: Role of Self-Photosensitization.

Photochemical transformation is an important process that involves trace organic contaminants (TrOCs) in sunlit surface waters. However, the environmental implications of their self-photosensitization pathway have been largely overlooked. Here, we selected 1-nitronaphthalene (1NN), a representative nitrated polycyclic aromatic hydrocarbon, to study the self-photosensitization process. We investigated the excited-state properties and relaxation kinetics of 1NN after sunlight absorption. The intrinsic decay rate constants of triplet (31NN*) and singlet (11NN*) excited states were estimated to be 1.5 × 106 and 2.5 × 108 s-1, respectively. Our results provided quantitative evidence for the environmental relevance of 31NN* in waters. Possible reactions of 31NN* with various water components were evaluated. With the reduction and oxidation potentials of -0.37 and 1.95 V, 31NN* can be either oxidized or reduced by dissolved organic matter isolates and surrogates. We also showed that hydroxyl (•OH) and sulfate (SO4•-) radicals can be generated via the 31NN*-induced oxidation of inorganic ions (OH- and SO42-, respectively). We further investigated the reaction kinetics of 31NN* and OH- forming •OH, an important photoinduced reactive intermediate, through complementary experimental and theoretical approaches. The rate constants for the reactions of 31NN* with OH- and 1NN with •OH were determined to be 4.22 × 107 and 3.95 ± 0.01 × 109 M-1 s-1, respectively. These findings yield new insights into self-photosensitization as a pathway for TrOC attenuation and provide more mechanistic details into their environmental fate.

Kinetic and Mechanistic Considerations of the Photosensitized Transformation of Chlorine in Chromophoric Dissolved Organic Matter Solutions under Simulated Solar Irradiation.

Chlorination is one of the most common disinfection methods for water treatments. Although the direct photolysis of free available chlorine (FAC) induced by solar irradiation has been extensively investigated, the photosensitized transformation of FAC caused by chromophoric dissolved organic matter (CDOM) has not previously been examined. Our results suggest that the photosensitized transformation of FAC can occur in sunlit CDOM-enriched solutions. Interestingly, the photosensitized decay of FAC can be fitted using a combined zero- and first-order kinetic model. The photogenerated O2•- from CDOM contributes to the zero-order kinetic component. The reductive triplet CDOM (3CDOM*) contributes to the pseudo-first-order decay kinetic component. The bimolecular reaction rate constants of the model triplet (3-methoxyacetophenone) with HOCl and OCl- were (3.6 ± 0.2) × 109 and (2.7 ± 0.3) × 109 M-1 s-1, respectively. Under simulated solar irradiation, the quantum yield coefficient of the reductive 3CDOM* toward FAC attenuation (fFAC = 840 ± 40 M-1) was 13 times greater than that of the oxidative 3CDOM* toward trimethylphenol (TMP) attenuation (fTMP = 64 ± 4 M-1). This study provides new insights into the photochemical transformation of FAC in sunlit surface waters, and the results are applicable when sunlight/FAC system is employed as an advanced oxidation process.

Mechanistic and quantitative profiling of electro-Fenton process for wastewater treatment.

Electro-Fenton (EF) process represents an energy-efficient and scalable advanced oxidation technology (AOT) for micropollutants removal in wastewaters. However, mechanistic profiling and quantitation of contribution of each subprocess (i.e., adsorption at electrode, coagulation, radical oxidation, electrode oxidation/reduction, and H2O2 oxidation) to the overall degradation are substantially unclear, resulting in difficulty in tunability and optimization for different treatment scenarios. In this study, we investigated degradation kinetics of a target micropollutant in an EF system. The contribution of all possible subprocesses was elucidated by comparing the observed degradation rate in the EF system with the sum of the kinetics in each subprocess. The results indicated that the overall degradation can be attributed to the synergistic action of the above-mentioned subprocesses. The radical oxidation accounts for 87% elimination, followed by electrode reoxidation/reduction of 7.7%. These results not only advance the fundamental understanding of synergistic effect in EF system, but also open new possibilities to optimize these techniques for better scalability. In addition, the methodology in this study could potentially boost the in-depth exploration of subprocess contribution in other Fenton-like systems.

Dosing with pyrite significantly increases anammox performance: Its role in the electron transfer enhancement and the functions of the Fe-N-S cycle.

Anaerobic ammonium oxidation (anammox) represents an energy-efficient process for biological nitrogen removal from ammonium-rich wastewater. However, there are mechanistic issues unsolved regarding the low microbial electron transfer and undesired accumulation of nitrate in treated water, limiting its widespread engineering applications. We found that the addition of pyrite (1 g L-1 reactor), an earth-abundant iron-bearing sulfide mineral, to the anammox system significantly improved the nitrogen removal rate by 52% in long-term operation at a high substrate shock loading (3.86 kg N m-3 d-1). Two lines of evidence were presented to unravel the underlying mechanisms of the pyrite-induced enhancement. Physiochemical evidence indicated that an increase of cytochromes c and Fe-S protein was responsible for the accelerated electron transfer among metabolic enzymes. Multi-omics evidence showed that the depletion of nitrate was attributed to the Fe-N-S cycle driven by nitrate-dependent Fe(II) oxidation and S-based denitrification. This study deepens our understanding of the roles of electron transfer and the Fe-N-S cycle in anammox systems, providing a fundamental basis for the development of mediators in the anammox process for practical implications.

New insight to superoxide radical-mediated degradation of pentachlorophenate: Kinetic determination and theoretical calculations.

This study reported the reactivity and mechanisms of superoxide radical (O2˙-)-mediated transformation of pentachlorophenate. Our results indicated that O2˙- alone exhibits limited effects on its degradation, and bimolecular nucleophilic substitution is the dominant reaction pathway.

Making waves: Defining advanced reduction technologies from the perspective of water treatment.

Studies related to advanced reduction technologies (ARTs) have grown exponentially since the term was first coined in 2013. Despite recent interests in ARTs, the conditions and requirements for these processes have yet to be defined and clarifed. In comparision to well defined advanced oxidation technologies/processes (AOTs/AOPs) which involve the generation of hydroxyl radical as the common characteristic, ARTs function by electron donation from a variety of reducing agents and activators. Based on an extensive literature review, we propose that ARTs be defined as processes employing strong chemical reductants with E° ≤ -2.3 V vs. normal hydrogen electrode at 25 ºC. While extensive studies have revealed critical fundamental details of AOTs/AOPs mediated processes, there are still significant gaps in elucidation of the mechanistic details of reductive degradation/transformation of highly toxic compounds by ARTs. A significant number of pollutants and toxins resistant to AOTs/AOPs treatment are effectively degraded by ARTs. A great leap is needed on understanding ARTs to fully utilize their potential to efficiently remediate recalcitrant compounds of different sources and structures.

Mechanistic Understanding of Superoxide Radical-Mediated Degradation of Perfluorocarboxylic Acids.

Perfluorocarboxylic acids (PFCAs) exhibit strong persistence in sunlit surface waters and in radical-based treatment processes, where superoxide radical (O2•-) is an important and abundant reactive oxygen species. Given that the role of O2•- during the transformation of PFCAs remains largely unknown, we investigated the kinetics and mechanisms of O2•--mediated PFCAs attenuation through complementary experimental and theoretical approaches. The aqueous-phase rate constants between O2•- and C3-C8 PFCAs were measured using a newly designed in situ spectroscopic system. Mechanistically, bimolecular nucleophilic substitution (SN2) is most likely to be thermodynamically feasible, as indicated by density functional theory calculations at the CBS-QB3 level of theory. This pathway was then investigated by ab initio molecular dynamics simulation with free-energy samplings. As O2•- approaches PFCA, the C-F bond at the alpha carbon is spontaneously stretched, leading to the bond cleavage. The solvation mechanism for O2•--mediated PFCA degradation was also elucidated. Our results indicated that although the less polar solvent enhanced the nucleophilicity of O2•-, it also decreased the desolvation process of PFCAs, resulting in reduced kinetics. With these quantitative and mechanistic results, we achieved a defined picture of the O2•--initiated abatement of PFCAs in natural and engineered waters.

Reactivity and reaction mechanisms of sulfate radicals with lindane: An experimental and theoretical study.

Advanced oxidation technologies (AOTs) have been intensely used to eliminate various organic pollutants in engineering waters. In this context, we investigated the kinetics and mechanisms of the sulfate radical (SO4-)-mediated degradation of lindane in UV/peroxydisulfate system, and compared results with previous studies on SO4--based AOTs for destruction of lindane. The second order rate constant (k) value between SO4- and lindane was determined to be (8.95 ± 0.29) × 106 M-1 s-1via competition kinetics using p-cyanobenzoic acid as reference compound, which is close to the theoretically calculated value of 4.41 × 107 M-1 s-1, that was performed at SMD/M05-2X/6-311++G**//M05-2X/6-31+G** level of theory using density functional theory (DFT) approach. H-atom abstraction pathway was calculated to be thermodynamically favorable and kinetically dominant. In the combined experimental and theoretical study, we aim for a better understanding on the degradation kinetics and mechanisms of lindane, serving as a starting point for more attention to SO4--mediated degradation kinetics of cycloaliphatic compounds in future.

Kinetics and mechanistic aspects of removal of heavy metal through gas-liquid sulfide precipitation: A computational and experimental study.

The production of fine particles from extremely high supersaturation has challenged the application of sulfide precipitation in treating heavy metal wastewater due to the difficulty of solid-liquid separation. To this end, a gas-liquid sulfide precipitation reactor for the removal of Cu2+ was designed by controlling the mass transfer and supersaturation levels during sulfidation processes. Particularly, a computational fluid dynamics (CFD) model of the reactor, integrating sulfidation reaction kinetics with two-phase flow hydrodynamics, was first built, followed by examining the effects of H2S(g) bubble diameter and flow rate. Based on the CFD simulation, the rate-limiting step of the gas-liquid sulfide precipitation reaction is the gas-liquid mass transfer process. Either reducing H2S(g) bubble diameter or increasing H2S(g) flow rate can result in the control of reaction rate and supersaturation level in the system. In order to validate the CFD simulations, we measured Cu2+ concentrations during the sulfidation process with the batch experiments. The agreement between computational and experimental results indicated that our mechanistic model can provide a protocol for the design and optimization of the reaction system, allowing one to visualize the time-dependent reaction process and evaluate the performance of a reactor.

Determination and Environmental Implications of Aqueous-Phase Rate Constants in Radical Reactions.

Interests in the kinetics of radical-induced reactions in aqueous solution have grown remarkably due to their water engineering significance (e.g., advanced oxidation processes). Although compilations of the rate constants (k) for various radicals have been documented, surprisingly a systematic review has yet to be reported on the development of reliable methods for determining k values. A knowledge gap exists to critically evaluate and screen the various methods to measure them. In this review, we summarize the direct and indirect methods under steady-state and non-steady-state conditions, followed by critical evaluations on their advantages and disadvantages. The radicals of ·OH, [Formula: see text] , [Formula: see text] , and Cl· were chosen based on their significant aquatic environmental relevance. MS excel spreadsheets that demonstrate the determination processes were provided allowing one to reproduce the data and/or to analyze the unprocessed raw data as a "template". We formulated a standard operation procedure for the k determination, although there is simply no "versatile" method fitting for all radical reactions. Finally, existing challenges and future research focus are discussed. This is the first review covering methodological approaches and considerations, aiming to provide a holistic and fundamental basis to choose an appropriate method for determining the k values for bimolecular reactions between target compounds and radicals in the aqueous phase.

Elucidating sulfate radical-mediated disinfection profiles and mechanisms of Escherichia coli and Enterococcus faecalis in municipal wastewater.

Practical applications of disinfection technologies for engineered waters require an in‒depth understanding of disinfection profiles and mechanisms of pathogenic bacteria in a complex matrix. This study investigated the inactivation of E. coli and E. faecalis by SO4•-, an emerging advanced disinfectant, in ultrapure water (UPW) and wastewater effluent (WE). Based on the bacterial inactivation kinetics in UPW in a zerovalent iron/peroxydisulfate system, the second order rate constants (k) for SO4•- reacting with E. coli and E. faecalis were measured to be (1.39 ± 0.1) × 109 M-1 s-1 and (6.71 ± 0.1) × 109 M-1 s-1, respectively. The morphological images of both bacteria by the scanning electron microscope indicated that SO4•- initiates oxidative reactions on the wall/membranes, causing their irreversible damage, ultimately affecting membrane permeability and physiological functions. To profile the inactivation kinetics of two strains of bacteria in WE matrix, a mechanistic process‒based model with the obtained k values was developed. Sensitivity and uncertainty analyses indicated that the key parameters for the model predictions were the concentrations of halide ions (i.e., Br- and Cl-) in WE and their k values reacting with SO4•- accounting for >80% of uncertainty or variance expected in predicted bacterial inactivation. This model allows precise estimation of required disinfectant dose even in complex water matrices, shedding lights on the extension of application of SO4•-‒based technology in wastewater treatments.

An experimental and theoretical study on the degradation of clonidine by hydroxyl and sulfate radicals.

Emerging contaminants such as pharmaceuticals that cannot be completely removed by traditional biological treatments are ubiquitously present in water bodies with detected concentrations ranging from ng L-1 to mg L-1. Advanced oxidation technologies (AOTs) are promising, efficient, and environmentally friendly for the removal of these pharmaceuticals. In this study, we investigated the degradation kinetics of a model pharmaceutical, clonidine (CLD), via hydroxyl radical (OH) in UV/H2O2 and sulfate radical (SO4•-) in UV/peroxydisulfate (PS) systems for the first time. The second-order rate constants (k) of protonated cationic CLD with OH and SO4•- were measured to be (2.15 ±â€¯0.07) × 109 M-1 s-1 and (1.12 ±â€¯0.03) × 109 M-1 s-1, respectively. We also calculated the pKa value of CLD and thermodynamic behaviors for reactions of CLD/HCLD+ with OH and SO4•- at M05-2X/6-311++G**//M05-2X/6-31+G** level with SMD solvation model. The pKa value was calculated to be 8.14, confirming the literature value. H atom abstraction pathway was the most favorable pathway for both OH and SO4•-, while single electron transfer pathway was thermodynamically feasible only for SO4•- for CLD but not for HCLD+. In addition, the reactivities of both tautomeric forms of CLD (i.e., amino and imino CLD) with both radicals were also investigated. This study contributed to a better understanding on the degradation mechanisms of CLD and proposed the possibilities of the elimination of pharmaceuticals by applying AOTs during wastewater treatment processes.

Experimental and theoretical insight into hydroxyl and sulfate radicals-mediated degradation of carbamazepine.

Carbamazepine (CBZ), a widely detected pharmaceutical in wastewaters, cannot currently be treated by conventional activated sludge technologies, as it is highly resistant to biodegradation. In this study, the degradation kinetics and reaction mechanisms of CBZ by hydroxyl radical (OH) and sulfate radical ()-based advanced oxidation processes (AOPs) were investigated with a combined experimental/theoretical approach. We first measured the UV absorption spectrum of CBZ and compared it to the theoretical spectrum. The agreement of two spectra reveals an extended π-conjugation system on CBZ molecular structure. The second-order rate constants of OH and with CBZ, measured by competition kinetics method, were (4.63 ±â€¯0.01) × 109 M-1 s-1 and (8.27 ±â€¯0.01) × 108 M-1 s-1, respectively at pH 3. The energetics of the initial steps of CBZ reaction with OH and were also calculated by density functional theory (DFT) at SMD/M05-2X/6-311++G**//M05-2X/6-31 + G**level. Our results reveal that radical addition is the dominant pathway for both OH and . Further, compared to the positive ΔGR0 value for the single electron transfer (SET) reaction pathway between CBZ and OH, the ΔGR0 value for SET reaction between CBZ and is negative, showing that this reaction route is thermodynamically favorable. Our results demonstrated the remarkable advantages of AOPs for the removal of refractory organic contaminants during wastewater treatment processes. The elucidation of the pathways for the reaction of OH and with CBZ are beneficial to predict byproducts formation and assess associated ecotoxicity, providing an evaluation mean for the feasibility of AOPs application.