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In a recent study, copper was shown to act as a novel quencher for investigating the mechanism of the photooxidation and photobleaching of dissolved organic matter (DOM) by selectively quenching the one-electron oxidizing intermediates of DOM (DOM D•+ ). However, the capture of DOM D•+ by Cu is possibly partially due to strong competition from phenolic antioxidant moieties intrinsically present in DOM for DOM D•+ quenching. In this study, the extent of interaction between DOM D•+ and phenolic antioxidant moieties is quantified by measuring the inhibitory effect of Cu on DOM photooxidation and photobleaching under varying pH (5.2-10.0) conditions. The increase in pH facilitates formation of deprotonated phenolic moieties (p K a ∼ 9-10), increasing their quenching capacity of DOM D•+ . Accordingly, our results indicate that the inhibitory effect of Cu on the DOM photobleaching and the loss of electron-donating moieties of DOM significantly decreased with an increase in pH, suggesting more pronounced competition for DOM D•+ from antioxidant phenolic moieties within DOM. Considering the precursors of DOM D•+ also originate from phenolic moieties of DOM, the findings of this study provide important insights into the long-distance charge transfer reactions occurring at different phenolic moiety sites during DOM photooxidation.

Redox fluctuations within redox dynamic environments influence the redox state of natural organic matter (NOM) and its interaction with redox-active elements, such as iron. In this work, we investigate the changes in the molecular composition of NOM during redox fluctuations as well as the impact of these changes on the Fe-NOM interaction employing Suwannee River Dissolved Organic Matter (SRDOM) as a representative NOM. Characterization of SRDOM using X-ray photoelectron spectroscopy and Fourier transform infrared spectrometry showed that irreversible changes occurred following electrochemical reduction and reoxidation of SRDOM in air. Changes in the redox state of SRDOM impacted its interaction with iron with higher rates of Fe(III) reduction in the presence of reduced and reoxidized SRDOM than in the presence of the original SRDOM. The increased rate of Fe(III) reduction in the presence of reduced SRDOM was due to the formation of reduced organic moieties on SRDOM reduction. The Fe(II) oxidation rate also increased in the presence of reduced SRDOM due to the formation of redox-active moieties that were capable of oxidizing Fe(II). Overall, our study provides useful insights into the changes in SRDOM that may occur in redox dynamic environments and the associated impact of these changes on Fe transformations.

Heavy metals-laden industrial wastewater represents both a threat to ecosystems and human health and, in some instances, a potential source of valuable metals however the presence of organic ligands that bind the metals in heavy metal complexes (HMCs) renders metal removal (and, where appropriate, recovery) difficult. Electrochemical-based oxidation and reduction processes represent a potentially promising means of degrading the organic ligands and reducing their ability to retain the metals in solution. In this state-of-the-art review, we provide a comprehensive overview of the current status on use of electrochemical redox technologies for organic ligand degradation and subsequent heavy metal removal and recovery from industrial wastewaters. The principles and degradation mechanism of common organic ligands by various types of electrochemical redox technologies are discussed in this review and consideration given to recent progress in electrode materials synthesis, cell architecture, and operation of electrochemical redox systems. Furthermore, we highlight the current challenges in application of electrochemical redox technologies for treatment of HMC-containing wastewaters including (i) limited understanding of the chemical composition of industrial wastewaters, (ii) constrained mass transfer process affecting the direct/indirect electron transfer, (iii) absence of approaches to convert recovered metal into high-value-added products, and (iv) restricted semi-or full-industrial-scale application of these technologies. Potential strategies for improvement are accordingly provided to guide efforts in addressing these challenges in future research., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Electrochemical advanced oxidation processes (EAOP) have shown great potential for the abatement of complexed heavy metals, such as metal-EDTA complexes, in recent studies. While removal of metal-EDTA complexes has been extensively examined in bench-scale reactors, much less attention has been given to the efficacy of this process at larger scale. In this study, we utilize a 72 L pilot-scale continuous flow system comprised of six serpentine flow channels and 90 pairs of flow-through electrodes for the degradation of Ni-EDTA complexes and removal of Ni from solution. The influence of a range of key operating parameters including flow rate, current density and initial Ni-EDTA concentration on rate and extent of Ni-EDTA degradation and Ni removal were examined. Our results showed that at a feed flow rate of 36 L h -1 , current density of 5 mA cm -2 and initial Ni-EDTA concentration of 1 mM, the pilot-scale system achieved 74 % total Ni removal, 78 % total EDTA removal and 40 % TOC removal with energy consumption of 13.6 kWh m -3 order -1 and energy efficiency of 7.9 g kWh -1 for total Ni removal. A mechanistically-based kinetic model, which was developed in our previous bench-scale study, provides a satisfactory description of the experimental results obtained in the pilot-scale unit. Long term operation of the pilot-scale unit resulted in corrosion of PbO 2 anode along with inorganic scaling as well as organic fouling on the PbO 2 surface resulting in an obvious decline in Ni-EDTA degradation. Overall, the results of this study suggest that large scale anodic oxidation of wastewaters containing metal-organic complexes is an effective means of degrading organic ligands thereby enabling removal of the metal at the cathode. However, additional efforts are required to enhance the durability of the anode material and reduce material costs and energy consumption., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

There is a growing demand for water treatment systems for which the quality of feedwater in and product water out are not necessarily fixed with "tunable" technologies essential in many instances to satisfy the unique requirements of particular end-users. For example, in household applications, the optimal water hardness differs for particular end uses of the supplied product (such as water for potable purposes, water for hydration, or water for coffee or tea brewing) with the inclusion of specific minerals enhancing the suitability of the product in each case. However, conventional softening technologies are not dynamically flexible or tunable and, typically, simply remove all hardness ions from the feedwater. Membrane capacitive deionization (MCDI) can potentially fill this gap with its process flexibility and tunability achieved by fine tuning different operational parameters. In this article, we demonstrate that constant-current MCDI can be operated flexibly by increasing or decreasing the current and flow rate simultaneously to achieve the same desalination performance but different productivity whilst maintaining high water recovery. This characteristic can be used to operate MCDI in an energy-efficient manner to produce treated water more slowly at times of normal demand but more rapidly at times of peak demand. We also highlight the "tunability" of MCDI enabling the control of effluent hardness over different desired ranges by correlating the rates of hardness and conductivity removal using a power function model. Using this model, it is possible to either i) soften water to the same hardness level regardless of the fluctuation in hardness of feed waters, or ii) precisely control the effluent hardness at different levels to avoid excessive or insufficient hardness removal., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Pd-based electrodes are recognized to facilitate effective electrochemical hydrodechlorination (EHDC) as a result of their superior capacity for atomic hydrogen (H*) generation. However, challenges such as electrode stability, feasibility of treating complex matrices, and high cost associated with electrode synthesis hinder the application of Pd-based electrodes for EHDC. In this work, we investigated the feasibility of degrading 2,4-dichlorophenol (2,4-DCP) by EHDC employing Pd-loaded activated carbon particles, prepared via a simple wet-impregnation method, as a flow cathode (FC) suspension. Compared to other Pd-based EHDC studies, a much lower Pd loading (0.02-0.08 mg cm -2 ) was used. Because of the excellent mass transfer in the FC system, almost 100% 2,4-DCP was hydrodechlorinated to phenol within 1 h. The FC system also showed excellent performance in treating complex water matrices (including hardness ion-containing wastewater and various other chlorinated organics such as 2,4-dichlorobenzoic acid and trichloroacetic acid) with a relatively low energy consumption (0.26-1.56 kW h m -3 mg -1 of 2,4-DCP compared to 0.32-7.61 kW h m -3 mg -1 of 2,4-DCP reported by other studies). The FC synthesized here was stable over 36 h of continuous operation, indicating its potential suitability for real-world applications. Employing experimental investigations and mathematical modeling, we further show that hydrodechlorination of 2,4-DCP occurs via interaction with H*, with no role of direct electron transfer and/or HO•-mediated processes in the removal of 2,4-DCP.

An industrially viable catalyst for heterogeneous catalytic ozonation (HCO) in water purification requires the characteristics of good dispersion of active species on its surface, efficient electron transfer for ozone decay, and maximum active species utilization. While metal-organic frameworks (MOFs) represent an attractive platform for HCO, the metal nodes in the unmodified MOFs exhibit low catalytic activity. Herein, we present a perfluorinated Fe-MOF catalyst by substituting H atoms on the metalated ligands with F atoms (termed 4F-MIL-88B) to induce structure evolution. The Lewis acidity of 4F-MIL-88B was enhanced via the formation of Fe nodes, tailoring the electron distribution on the catalyst surface. As a result of catalyst modification, the rate constant for degradation of the target compounds examined increased by ∼700% compared with that observed for the unmodified catalyst. Experimental evidence and theoretical calculations showed that the modulated polarity and the enhanced electron transfer between the catalyst and ozone molecules contributed to the adsorption and transformation of O 3 to • OH on the catalyst surface. Overall, the results of this study highlight the significance of tailoring the metalated ligands to develop highly efficient and stable MOF catalysts for HCO and provide an in-depth mechanistic understanding of their structure-function evolution, which is expected to facilitate the applications of nanomaterial-based processes in water purification.

Packed fixed-bed reactors are traditionally used for heterogeneous catalytic ozonation. However, a high solid-to-liquid requirement, poor ozone dissolution, ineffective utilization of catalyst surface area, and production of large amounts of catalyst waste impede application of such reactors. In this study, we designed a suspension catalytic ozonation reactor and compared the performance of this reactor with that of a traditional fixed-bed catalytic ozonation reactor employing oxalic acid (OA) as the target contaminant. Our results showed that total O 3 dissolved into the suspension reactor (117-134 mg.L -1 ) was much higher compared to that measured in the fixed-bed reactor (53 mg.L -1 ) due to a higher O 3 (g) interphase mass transfer rate in the suspension reactor. In accordance with the higher O 3 (g) interphase mass transfer, we observed a much higher proportional OA removal (32 %) compared to that achieved in the fixed-bed reactor (10%) employing an Fe-oxide catalyst supported on Al 2 O 3 (Fe-oxide@Al 2 O 3 ) in both reactors. Use of a double-layered Cu-Al hydroxide (Cu-Al LDHs) catalyst in the suspension reactor further enhanced the performance with nearly 90 % OA removal observed. Given the superior performance of the suspension reactor, we investigated the impact of operating conditions (catalyst dosage, hydraulic retention time and ozone dosage) employing Cu-Al LDHs as the catalyst. We also developed a mathematical kinetic model to describe the performance of the suspension reactor and, through use of the kinetic model, showed that O 3 (g) interphase transfer rate was the rate-limiting step in OA removal. Thus, improvement in ozone gas diffuser design is required to improve the performance of the suspension reactor. Overall, the present study demonstrated that suspension reactors were more effective than fixed-bed reactors for oxidation of surface-active organic compounds such as OA due to the higher ozone interphase mass transfer rate and effective utilization of the catalyst surface area that can be achieved. As such, further research on suspension reactor design and development of catalysts suitable for use in suspension reactors should facilitate large-scale application of catalytic ozonation processes by the wastewater treatment industry., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

A long-term field trial of membrane capacitive deionization (MCDI) was conducted in a remote community in the Northern Territory of Australia, with the aim of producing safe palatable drinking water from groundwater that contains high concentrations of salt and hardness ions and other contaminants. This trial lasted for 1.5 years, which, to our knowledge, is one of the longest reported studies of pilot-scale MCDI field trials. The 8-module MCDI pilot unit reduced salt concentration to below the Australian Drinking Water Guideline value of 600 mg/L total dissolved solids (TDS) concentration with a relatively high water recovery of 71.6 ± 8.7 %. During continuous constant current operation and electrode discharging at near zero volts, a rapid performance deterioration occurred that was primarily attributed to insufficient desorption of multivalent ions from the porous carbon electrodes. Performance could be temporarily recovered using chemical cleaning and modified operating procedures however these approaches could not fundamentally resolve the issue of insufficient electrode performance regeneration. Constant current discharging of the electrodes to a negative cell cut-off voltage was hence employed to enhance the stability and overall performance of the MCDI unit during the continuous operation. An increase in selectivity of monovalent ions over divalent ions was also attained by implementing negative voltage discharging. The energy consumption of an MCDI system with a capacity of 1000 m 3 /day was projected to be 0.40∼0.53 kWh/m 3 , which is comparable to the energy consumption of electrodialysis reversal (EDR) and brackish water reverse osmosis (BWRO) systems of the same capacity. The relatively low maintenance requirements of the MCDI system rendered it the most cost-efficient water treatment technology for deployment in remote locations. The LCOW of an MCDI system with a capacity of 1000 m 3 /day was projected to be AU$1.059/m 3 and AU$1.146/m 3 under two operational modes, respectively. Further investigation of particular water-energy trade-offs amongst MCDI performance metrics is required to facilitate broader application of this promising water treatment technology., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

The peroxone process (O 3 /H 2 O 2 ) is reported to be a more effective process than the ozonation process due to an increased rate of generation of hydroxyl radicals ( • OH) and inhibition of bromate (BrO 3 - ) formation which is otherwise formed on ozonation of bromide containing waters. However, the trade-off between the H 2 O 2 dosage required for minimization of BrO 3 - formation and effective pollutant removal has not been clearly delineated. In this study, employing experimental investigations as well as chemical modelling, we show that the concentration of H 2 O 2 required to achieve maximum pollutant removal may not be the same as that required for minimization of BrO 3 - formation. At the H 2 O 2 dosage required to minimize BrO 3 - formation (<10 µg/L), only pollutants with high to moderate reactivity towards O 3 and • OH are effectively removed. For pollutants with low reactivity towards O 3 / • OH, high O 3 (O 3 :DOC>>1 g/g) and high H 2 O 2 dosages (O 3 :H 2 O 2 ∼1 (g/g)) are required for minimizing BrO 3 - formation along with effective pollutant removal which may result in a very high residual of H 2 O 2 in the effluent, causing secondary pollution. On balance, we conclude that the peroxone process is not effective for the removal of low reactivity micropollutants if minimization of BrO 3 - formation is also required., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Metal-organic complexes, especially those of ethylenediaminetetraacetic acid (EDTA) with metals such as copper (Cu) and nickel (Ni) (denoted here as Cu-EDTA and Ni-EDTA), are common contaminants in wastewaters from chemical and plating industries. In this study, a multi-electrode (ME) system using a two-chamber reactor and two pairs of electrodes is proposed for simultaneous electrochemical oxidation of a wastewater containing both Cu-EDTA and Ni-EDTA complexes as well as separation and selective recovery of Cu and Ni onto two different cathodes via electrodeposition. Our results demonstrate that the ME system successfully achieved 90% EDTA removal, 99% solid Cu recovery at the Cu recovery cathode and 56% Ni recovery (33.3% on the Ni recovery cathode and 22.6% in the solution) after a four-hour operation. The system further achieved 85.5% Ni recovery after consecutive five cycles of operation for 20 h. While Cu removal was mainly driven by the direct reduction of EDTA-complexed Cu(II) at the cathode, oxidation of EDTA within the Ni-EDTA complex at the anode was a prerequisite for Ni removal. The oxidation of metal-bound EDTA and free EDTA was driven by • OH and direct electron transfer on the PbO 2 anode surface and graphite anode, respectively. We further show that ME system performs well for all pH conditions, treatment of real wastewaters as well as wastewaters containing other metals ions (Cr and Zn) along with Cu/Ni. The separation efficiency of Cu and Ni is dependent on applied electrode potential as well as nature and concentration of binding ligand present with comparatively lower separation efficiency achieved in the presence of weaker binding capacity and/or at lower ligand concentration and lower applied electrode potential. As such, some optimization of electrode potential is required depending on the nature/concentration of ligands in the wastewaters. Overall, this study provides new insights into the design and operation of EAOP technology for effective organic abatement and metal recovery from wastewaters containing mixtures of various metal-organic complexes., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The kinetics of oxidation of micromolar concentrations of ascorbic acid (AA) catalyzed by Cu(II) in solutions representative of biological and environmental aqueous systems has been investigated in both the presence and absence of oxygen. The results reveal that the reaction between AA and Cu(II) is a relatively complex set of redox processes whereby Cu(II) initially oxidizes AA yielding the intermediate ascorbate radical (A •- ) and Cu(I). The rate constant for this reaction was determined to have a lower limit of 2.2 × 10 4 M -1 s -1 . Oxygen was found to play a critical role in mediating the Cu(II)/Cu(I) redox cycle and the oxidation reactions of AA and its oxidized forms. Among these processes, the oxidation of the ascorbate radical by molecular oxygen was identified to play a key role in the consumption of ascorbic acid, despite being a slow reaction. The rate constant for this reaction ( A • - + O 2 → DHA + O 2 • - ) was determined for the first time with a calculated value of 54 ± 8 M -1 s -1 . The kinetic model developed satisfactorily describes the Cu/AA/O 2 system over a range of conditions including different concentrations of NaCl (0.2 and 0.7 M) and pH (7.4 and 8.1). Appropriate adjustments to the rate constant for the reaction between Cu(I) and O 2 were found to account for the influence of the chloride ions and pH on the kinetics of the process. Additionally, the presence of Cu(III) as the primary oxidant resulting from the interaction between Cu(I) and H 2 O 2 in the Cu(II)/AA system was confirmed, along with the coexistence of HO • , possibly due to an equilibrium established between Cu(III) and HO • .

Sunlight plays a crucial role in the transformation of dissolved organic matter (DOM) and the associated carbon cycle in aquatic environments. This study demonstrates that the presence of nanomolar concentrations of copper (Cu) significantly decreases the rate of photobleaching and the rate of loss of electron-donating moieties of three selected types of DOM (including both terrestrial and microbially derived DOM) under simulated sunlight irradiation. Employing Fourier transform ion cyclotron resonance mass spectrometry, we further confirm that Cu selectively inhibits the photooxidation of lignin- and tannin-like phenolic moieties present within the DOM, in agreement with the reported inhibitory impact of Cu on the photooxidation of phenolic compounds. On the basis of the inhibitory impact of Cu on the DOM photobleaching rate, we calculate the contribution of phenolic moieties to DOM photobleaching to be at least 29-55% in the wavelength range of 220-460 nm. The inhibition of loss of electrons from DOM during irradiation in the presence of Cu is also explained quantitatively by developing a mathematical model describing hydrogen peroxide (a proxy measure of loss of electrons from DOM) formation on DOM irradiation in the absence and presence of Cu. Overall, this study advances our understanding of DOM transformation in natural sunlit waters.

Heterogeneous catalytic ozonation (HCO) has gained increasing attention as an effective process to remove refractory organic pollutants from industrial effluents. However, widespread application of HCO is still limited due to the typically low efficacy of catalysts used and matrix passivation effects. To this end, we prepared an Al 2 O 3 -supported Fe catalyst with high reactivity via a facile urea-based heterogeneous precipitation method. Due to the nonsintering nature of the preparation method, a heterogeneous catalytic layer comprised of γ-FeOOH and α-Fe 2 O 3 is formed on the Al 2 O 3 support (termed NS-Fe-Al 2 O 3 ). On treatment of a real industrial effluent by HCO, the presence of NS-Fe-Al 2 O 3 increased the removal of organics by ∼100% compared to that achieved with a control catalyst (i.e., α-Fe 2 O 3 /Al 2 O 3 or γ-FeOOH/Al 2 O 3 ) that was prepared by a conventional impregnation and calcination method. Furthermore, our results confirmed that the novel NS-Fe-Al 2 O 3 catalyst demonstrated resistance to the inhibitory effect of high concentration of chloride and sulfate ions usually present in industrial effluent. A mathematical kinetic model was developed that adequately describes the mechanism of HCO process in the presence of NS-Fe-Al 2 O 3 . Overall, the results presented here provide valuable guidance for the synthesis of effective and robust catalysts that will facilitate the wider industrial application of HCO.

Ferryl ion ([Fe IV O] 2+ ) has often been suggested to play a role in iron-based advanced oxidation processes (AOPs) with its presence commonly determined using the unique oxidation pathway from methyl phenyl sulfoxide (PMSO) to methyl phenyl sulfone (PMSO 2 ). However, we show here that the oxidation products of PMSO, formed on reaction with hydroxyl radical, enhance PMSO 2 formation as a result of their complexation with Fe(III) leading to the changes in the reactivity of Fe(III) species in the homogeneous Fenton reaction. As such, PMSO should be used with caution to investigate the role of [Fe IV O] 2+ in iron-based AOPs with these insights suggesting the need to reassess the findings of many previous studies in which this reagent was used. The other common target compounds, phthalhydrazide and hydroxybenzoic acids, were also found to modify the rate and extent of iron cycling as a result of complexation and/or redox reactions, either by the probe compound itself and/or oxidation products formed. Overall, this study highlights that these confounding effects of the aromatic probe compounds on the reactivity of iron species should be recognized if reliable mechanistic insights into iron-based AOPs are to be obtained.

The tetradentate tripodal ligand scaffold is capable of supporting the expected geometries of the copper ion during the oxygen reduction reaction (ORR) catalysis. As such, we probed the reactivity of copper complexes with these types of ligands by electronically and structurally tweaking the tris(pyridin 2-ylmethyl)amine (tmpa) scaffold by progressively replacing the terminal pyridines with carboxylate donors. This work shows that systems with one carboxylato donor (bpg = bis(pyridin-2-ylmethyl)glycine), (bpp = (3-(bis(pyridin-2-ylmethyl)amino)propanoic acid)) are active in electrocatalyzing the homogeneous ORR under circumneutral aqueous conditions. Turnover frequencies in the range from 10 5 to 10 6 s -1 , on par with that for Cu-tmpa under identical conditions, were obtained. It is noteworthy that the Cu II /Cu I redox potentials for the Cu-bpg, Cu-bpp, and Cu-tmpa systems in phosphate-buffered water (pH 7, under Ar) are similar at -0.409, -0.375, and -0.401 V vs Ag/AgCl, respectively. This is rationalized by the influence of the Lewis acidity of the copper ions on the water coligand. Corroborating this are p K a values for [Cu(tmpa)(H 2 O)] 2+ , Cu(bpg)(H 2 O)] + , and [Cu(bpp)(H 2 O)] + of 6.6, 8.8, and 10.2, respectively. Thus, the overall charge of the solution species for all three complexes will be +1 at pH 7 and this will be an important determinant for the redox potentials and, in turn, the catalytic overpotentials, which are also similar. A cis carboxylato donor offers H-bonding possibilities for exogenous resting state water and intermediate hydroperoxo coligands. This is reflected by the higher p K a values for Cu-bpp and Cu-bpg compared with that for Cu-tmpa, with the Cu-bpp system furnishing the least strained H-bonding.

Electrochemical reduction of nitrate is a promising method for the removal of nitrate from contaminated groundwater. However, the presence of hardness cations (Ca 2+ and Mg 2+ ) in groundwaters hampers the electroreduction of nitrate as a result of the precipitation of carbonate-containing solids of these elements on the cathode surface. Thus, some pretreatment process is required to remove unwanted hardness cations. Herein, we present a proof-of-concept of a novel three-chambered flow electrode unit, constituting a flow electrode capacitive deionization (FCDI) unit and a flow cathode (FC) unit, which achieves cation removal, nitrate capture and reduction, and ammonia generation in a single cell without the need for any additional chemicals/electrolyte. The addition of the FCDI unit not only achieves removal of hardness cations but also concentrates the nitrate ions and other anions, which facilitates nitrate reduction in the subsequent FC unit. Results show that the FCDI cell voltage influences electrode stability but has a minimal impact on the overall nitrate removal performance. The concentration of coexisting anions influences the nitrate removal due to competitive sorption of anions on the electrode surface. Our results further show that stable electrochemical performance was obtained over 26 h of operation. Overall, this study provides a scalable strategy for continuous nitrate electroreduction and ammonia generation from nitrate contaminated groundwaters containing hardness ions.

Dissolved organic matter (DOM) driven-photochemical processes play an important role in the redox cycling of trace metals and attenuation of organic contaminants in estuarine and coastal ecosystems. In this study, we evaluate the effect of Cu on 4-carboxybenzophenone (CBBP) and Suwannee River natural organic matter (SRNOM)-photosensitized degradation of seven target contaminants (TCs) including phenols and amines under pH conditions and salt concentrations typical of those encountered in estuarine and coastal waters. Our results show that trace amounts of Cu(II) (25 -500 nM) induce strong inhibition of the photosensitized degradation of all TCs in solutions containing CBBP. The influence of TCs on the photo-formation of Cu(I) and the decrease in the lifetime of transformation intermediates of contaminants (TC •+ / TC • (-H) ) in the presence of Cu(I) indicated that the inhibition effect of Cu was mainly due to the reduction of TC •+ / TC • (-H) by the photo-produced Cu(I). The inhibitory effect of Cu on the photodegradation of TCs decreased with the increase in Cl - concentration since less reactive Cu(I)-Cl complexes dominate at high Cl - concentrations. The impact of Cu on the SRNOM-sensitized degradation of TCs is less pronounced compared to that observed in CBBP solution since the redox active moieties present in SRNOM competes with Cu(I) to reduce TC •+ / TC • (-H) . A detailed mathematical model is developed to describe the photodegradation of contaminants and Cu redox transformations in irradiated SRNOM and CBBP solutions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Cu and Ni complexes with ethylenediaminetetraacetic acid (Cu/Ni-EDTA), which are commonly present in metal plating industry wastewaters, pose a serious threat to both the environment and human health due to their high toxicity and low biodegradability. In this study, the treatment of solutions containing either or both Cu-EDTA and Ni-EDTA using an electrochemical process is investigated under both oxidizing and reducing electrolysis conditions. Our results indicate that Cu-EDTA is decomplexed as a result of the cathodic reduction of Cu(II) with subsequent electrodeposition of Cu(0) at the cathode when the cathode potential is more negative than the reduction potential of Cu-EDTA to Cu(0). In contrast, the very negative reduction potential of Ni-EDTA to Ni(0) renders the direct reduction of EDTA-complexed Ni(II) at the cathode unimportant. The removal of Ni during the electrolysis process mainly occurs via anodic oxidation of EDTA in Ni-EDTA, with the resulting formation of low-molecular-weight organic acids and the release of Ni 2+ , which is subsequently deposited as Ni 0 on the cathode. A kinetic model incorporating the key reactions occurring in the electrolysis process has been developed, which satisfactorily describes EDTA, Cu, Ni, and TOC removal. Overall, this study improves our understanding of the mechanism of removal of heavy metals from solution during the electrochemical advanced oxidation of metal plating wastewaters.

Membrane capacitive deionization (MCDI) is a water desalination technology that involves the removal of charged ions from water under an electric field. While constant-current MCDI coupled with stopped-flow during ion discharge is expected to exhibit high water recovery and good performance stability, previous studies have typically been undertaken using NaCl solutions only with limited investigation of MCDI performance using multi-electrolyte solutions. In the present work, the desalination performance of MCDI was evaluated using feed solutions with different levels of hardness. The increase of hardness resulted in the degradation of desalination performance with the desalination time (Δt d ), total removed charge, water recovery (WR) and productivity decreasing by 20.5%, 21.8%, 3.8% and 3.2%, respectively. A more serious degradation of WR and productivity would be caused if Δt d decreases further. Analysis of the voltage profiles and effluent ion concentrations reveal that the insufficient desorption of divalent ions at constant-current discharge to 0 V was the principal reason for the degradation of performance. The Δt d and WR can be improved by discharging the cell using a lower current but the productivity decreased by 15.7% on decreasing the discharging current from 161 to 107 mA. Discharging the cell to a negative potential was shown to be a better option with the Δt d , total removed charge, WR and productivity increasing by 27.4%, 23.9%, 3.6% and 5.3%, respectively, when the cell was discharged to a minimum voltage of - 0.3 V. Use of such a method should be feasible for operation of full scale MCDI plants and would be expected to lead to better regeneration of the electrode, improved desalination performance and, potentially, a significant reduction in the need for use of clean-in-place procedures., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Heteroleptic copper complexes of an asymmetrical pincer ligand containing a central anionic sulfonamide donor (pyridine-2-yl-sulfonyl)(quinolin-8-yl)-amide (psq), which contains a central anionic sulfonamido donor have been prepared. Meridional κ 3 - N , N ″, N‴ binding with the co-ligands acetate, chloride, or acetonitrile (MeCN), trans to the central sulfonamido N -donor, is revealed by the X-ray crystal structures of [Cu(OAc)(psq)(H 2 O)], [CuCl(psq)] 2 , and [Cu(psq)(MeCN)](PF 6 ). Either overall distorted square pyramidal or octahedral geometries of the copper atom are satisfied by coordinated water in the case of the acetate complex or interactions with periphery sulfonamido oxygen atoms on adjacent molecules in the dimeric chloride and 1D polymeric acetonitrile complexes. The cyclic voltammogram (CV) of [Cu(OAc)(psq)(H 2 O)] shows a quasi-reversible Cu II /Cu I reduction at -0.930 V ( vs Fc + /Fc 0 , MeCN), and an irreversible Cu II /Cu I reduction for [Cu(psq)(MeCN)](PF 6 ) is seen at -0.838 V. This signal is split into two quasi-reversible redox processes on the addition of 2,2,2-trifluoroethanol (TFE). This suggests that TFE pushes a solution equilibrium toward a dimeric acetate complex analogous to [CuCl(psq)] 2 , which shows two quasi-reversible waves at -0.666 V and -0.904 V vs Fc + /Fc 0 consistent with its dimeric solid-state structure. A comparison of the CVs of [Cu(OAc)(psq)(H 2 O)] under either a N 2 or an O 2 atmosphere revealed that this complex catalyzes turnover electro-reduction of O 2 to H 2 O 2 and H 2 O. The rate of reaction increases on addition of a weak organic acid, and a coulombic efficiency of 48% for H 2 O 2 was determined by iodometric titration. We propose that a Cu I complex formed on electroreduction binds O 2 to yield an intermediate superoxide complex. On electron and proton transfer to this species, a bifurcated route back to the O 2 -activating Cu I complex is feasible with either release of H 2 O 2 or O-O cleavage resulting in the liberation of H 2 O. The Cu I complex is regenerated by subsequent reduction and protonation to close the cycle.

The performance of membrane capacitive deionization (MCDI) desalination was investigated at bench, pilot, and field scales for the removal of uranium from groundwater. It was found that up to 98.9% of the uranium can be removed using MCDI from a groundwater source containing 50 μg/L uranium, with the majority (94.5%) being retained on the anode. Uranium was found to physiochemically adsorb to the electrode without the application of a potential by displacing chloride ions, with 16.6% uranium removal at the bench scale via this non-electrochemical process. This displacement of chloride did not occur during the MCDI adsorption phase with the adsorption of all ions remaining constant during a time series analysis on the pilot unit. For the scenarios tested on the pilot unit, the flowrate of the product water ranged from 0.15 to 0.23 m 3 /h, electrode energy consumption from 0.28 to 0.51 kW h/m 3 , and water recovery from 69 to 86%. A portion (13-53% on the pilot unit) of the uranium was found to remain on the electrodes after the brine discharge phase with conventional cleaning techniques unable to release this retained uranium. MCDI was found to be a suitable means to remove uranium from groundwater systems though with the need to manage the accumulation of uranium on the electrodes over time.

Catalyst deactivation is an ongoing concern for industrial application of catalytic ozonation processes. In this study, we systematically investigated the performance of a catalytic ozonation process employing Fe 2 O 3 /Al 2 O 3 •SiO 2 catalyst for the treatment of coal chemical industry (CCI) wastewater using pilot-scale and laboratory-scale systems. Our results show that the activity of the Fe 2 O 3 /Al 2 O 3 •SiO 2 catalyst for organic contaminant removal deteriorated over time due to formation of a dense and thin carbonaceous layer on the Fe 2 O 3 catalyst surface. EPR and fluorescence imaging analysis confirm that the passivation layer essentially inhibited the O 3 -catalyst interaction thereby minimizing formation of surficial • OH and associated oxidation of organic contaminants on the catalyst surface. Calcination was demonstrated to be effective in restoring the activity of the catalyst since the carbonaceous layer could be efficiently combusted during calcination to re-establish the surficial • OH-mediated oxidation process. The combustion of the carbonaceous layer and restoration of the Fe layer on the surface on calcination was confirmed based on SEM-EDX, FTIR and thermogravimetric analysis. Cost analysis indicates that regeneration using calcination is economically viable compared to catalyst replacement. The results of this study are expected to pave the way for developing appropriate regeneration techniques for deactivated catalysts and optimising the catalyst synthesis procedure., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

The formula assignment of the Fourier transform ion cyclotron resonance mass spectrometry coupled with positive-ion electrospray ionization [ESI(+)-FT-ICR MS] is challenging because of the extensive occurrence of adducts. However, there is a paucity of automated formula assignment methods for ESI(+)-FT-ICR MS spectra. The novel automated formula assignment algorithm for ESI(+)-FT-ICR MS spectra developed herein has been applied to elucidate the composition of dissolved organic matter (DOM) in groundwater during air-induced ferrous [Fe(II)] oxidation. The ESI(+)-FT-ICR MS spectra of groundwater DOM were profoundly impacted by [M + Na] + adducts and, to a lesser extent, [M + K] + adducts. Oxygen-poor and N-containing compounds were frequently detected when the FT-ICR MS was operated in the ESI(+) mode, while the components with higher carbon oxidation states were preferentially ionized in the negative-ion electrospray ionization [ESI(-)] mode. Values for the difference between double-bond equivalents and the number of oxygen atoms from -13 to 13 are proposed for the formula assignment of the ESI(+)-FT-ICR MS spectra of aquatic DOM. Furthermore, for the first time, the Fe(II)-mediated formation of highly toxic organic iodine species was reported in groundwater rich in Fe(II), iodide, and DOM. The results of this study not only shed light on the further algorithm development for comprehensive characterization of DOM by ESI(-)-FT-ICR MS and ESI(+)-FT-ICR MS but also highlight the importance of appropriate treatment of specific groundwater prior to use.