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.
View Article and Find Full Text PDFHeavy 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.
View Article and Find Full Text PDFPd-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.
View Article and Find Full Text PDFElectrochemical 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.
View Article and Find Full Text PDFThere 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.
View Article and Find Full Text PDFAn 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.
View Article and Find Full Text PDFA 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.
View Article and Find Full Text PDFPacked 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.
View Article and Find Full Text PDFThe peroxone process (O/HO) 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) formation which is otherwise formed on ozonation of bromide containing waters. However, the trade-off between the HO dosage required for minimization of BrO 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 HO required to achieve maximum pollutant removal may not be the same as that required for minimization of BrO formation.
View Article and Find Full Text PDFMetal-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.
View Article and Find Full Text PDFThe 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.
View Article and Find Full Text PDFEnviron Sci Technol
December 2023
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.
View Article and Find Full Text PDFThe 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.
View Article and Find Full Text PDFElectrochemical reduction of nitrate is a promising method for the removal of nitrate from contaminated groundwater. However, the presence of hardness cations (Ca and Mg) 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.
View Article and Find Full Text PDFCu 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).
View Article and Find Full Text PDFHeteroleptic 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 -,″, binding with the co-ligands acetate, chloride, or acetonitrile (MeCN), to the central sulfonamido -donor, is revealed by the X-ray crystal structures of [Cu(OAc)(psq)(HO)], [CuCl(psq)], and [Cu(psq)(MeCN)](PF). 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.
View Article and Find Full Text PDFThe 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.
View Article and Find Full Text PDFMembrane 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.
View Article and Find Full Text PDFDissolved 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.
View Article and Find Full Text PDFBackground: Flooding can cause long-term, significant impacts on mental health in affected populations. We explored help-seeking behaviour of households affected by flooding.
Methods: A cross-sectional analysis was conducted on National Study of Flooding and Health data on households flooded in England in winter 2013/14.
Rapid climate and socioeconomic changes are transforming Arctic human-earth systems. An integral part of these systems is mobility, which encompasses the transport of humans and goods into, out of, and between Arctic regions. Impacts of climate and socioeconomic drivers on Arctic mobility are heterogenous.
View Article and Find Full Text PDFCatalyst 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 FeO/AlO•SiO 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 FeO/AlO•SiO catalyst for organic contaminant removal deteriorated over time due to formation of a dense and thin carbonaceous layer on the FeO catalyst surface.
View Article and Find Full Text PDFThe 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.
View Article and Find Full Text PDFIron complexes of tetra-amido macrocyclic ligands (Fe-TAML) are recognized to be effective catalysts for the degradation of a wide range of organic contaminants in homogeneous conditions with the high valent Fe(IV) and Fe(V) species generated on activation of the Fe-TAML complex by hydrogen peroxide (HO) recognized to be powerful oxidants. Electrochemical activation of Fe-TAML would appear an attractive alternative to HO activation, especially if the Fe-TAML complex could be attached to the anode, as this would enable formation of high valent iron species at the anode and, importantly, retention of the valuable Fe-TAML complex within the reaction system. In this work, we affix Fe-TAML to the surface of carbon black particles and apply this "suspension anode" process to oxidize selected target compounds via generation of high valent iron species.
View Article and Find Full Text PDFFerryl ion ([FeO]) 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). However, we show here that the oxidation products of PMSO, formed on reaction with hydroxyl radical, enhance PMSO 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 [FeO] in iron-based AOPs with these insights suggesting the need to reassess the findings of many previous studies in which this reagent was used.
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