Influence of water matrix components on the UV/chlorine process and its reactions mechanism.

The UV/chlorine system has become an attractive alternative Advanced Oxidation Process (AOP) for the removal of recalcitrant pollutants in the last decade due to the simultaneous formation of chlorine and hydroxyl radicals. However, there is no consensus regarding the results and trends obtained in previous micropollutant removal studies by AOPs, highlighting the complexity of the UV/chlorine process and the need for further research. This study investigates the degradation of acetaminophen (ACTP) by UV/chlorine and the effects of the water matrix in the reaction kinetics. In particular, the effects of natural organic matter (NOM), alkalinity and mineral salts on the kinetics and reactive species were elucidated. The complexity of the system was revealed by the analysis of the radical generation and transformation in different water matrices, applying the kinetic modelling approach to complement the scavenger tests. The higher kinetic rates of ACTP at alkaline pH provided new insights into the chlorine reactions under UV radiation, where secondary and tertiary reactive oxygen species including ozone were proven to play the major role in degradation. On the contrary, at acidic pH, reaction kinetic modelling demonstrated that ClO• radical occurs at high concentrations in the order of 10-10 M, being therefore the main oxidant, followed by other chlorine radicals. It is noteworthy that at alkaline pH the presence of typical inorganic ions such as carbonate had little impact on ACTP degradation, contrary to the observed reduction of degradation rates at acidic pH. The expected detrimental effect of the NOM in AOPs was also evidenced, although the use of chlorine as radical source reduces the relevance of the inner filter effect in comparison to UV/H2O2.

Facing the Challenge of Poly- and Perfluoroalkyl Substances in Water: Is Electrochemical Oxidation the Answer?

Electrochemical treatment systems have the unique ability to completely mineralize poly- and perfluoroalkyl substances (PFASs) through potential-driven electron transfer reactions. In this review, we discuss the state-of-the-art on electrooxidation of PFASs in water, aiming at elucidating the impact of different operational and design parameters, as well as reported mechanisms of PFAS degradation at the anode surface. We have identified several shortcomings of the existing studies that are largely limited to small-scale laboratory batch systems and unrealistic synthetic solutions, which makes extrapolation of the obtained data to real-world applications difficult. PFASs are surfactant molecules, which display significant concentration-dependence on adsorption, electrosorption, and dissociation. Electrooxidation experiments conducted with high initial PFAS concentration and/or in high conductivity supporting electrolytes likely overestimate process performance. In addition, the formation of organohalogen byproducts, chlorate and perchlorate, was seldom considered. Nevertheless, the first step toward advancing from laboratory-scale to industrial-scale applications is recognizing both the strengths and limitations of electrochemical water treatment systems. More comprehensive and rigorous evaluation of novel electrode materials, application of scalable proof-of-concept studies, and acknowledgment of all treatment outputs (not just the positive ones) are imperative. The presence of PFASs in drinking water and in the environment is an urgent global public health issue. Developments made in material science and application of novel three-dimensional, porous electrode materials and nanostructured coatings are forging a path toward more sustainable water treatment technologies and potential chemical-free treatment of PFAS-contaminated water.

Challenges and Opportunities for Electrochemical Processes as Next-Generation Technologies for the Treatment of Contaminated Water.

Electrochemical processes have been extensively investigated for the removal of a range of organic and inorganic contaminants. The great majority of these studies were conducted using nitrate-, perchlorate-, sulfate-, and chloride-based electrolyte solutions. In actual treatment applications, organic and inorganic constituents may have substantial effects on the performance of electrochemical treatment. In particular, the outcome of electrochemical oxidation will depend on the concentration of chloride and bromide. Formation of chlorate, perchlorate, chlorinated, and brominated organics may compromise the quality of the treated effluent. A critical review of recent research identifies future opportunities and research needed to overcome major challenges that currently limit the application of electrochemical water treatment systems for industrial and municipal water and wastewater treatment. Given the increasing interest in decentralized wastewater treatment, applications of electrolytic systems for treatment of domestic wastewater, greywater, and source-separated urine are also included. To support future adoption of electrochemical treatment, new approaches are needed to minimize the formation of toxic byproducts and the loss of efficiency caused by mass transfer limitations and undesired side reactions. Prior to realizing these improvements, recognition of the situations where these limitations pose potential health risks is a necessary step in the design and operation of electrochemical treatment systems.

Removal of Persistent Organic Contaminants by Electrochemically Activated Sulfate.

Solutions of sulfate have often been used as background electrolytes in the electrochemical degradation of contaminants and have been generally considered inert even when high-oxidation-power anodes such as boron-doped diamond (BDD) were employed. This study examines the role of sulfate by comparing electro-oxidation rates for seven persistent organic contaminants at BDD anodes in sulfate and inert nitrate anolytes. Sulfate yielded electro-oxidation rates 10-15 times higher for all target contaminants compared to the rates of nitrate anolyte. This electrochemical activation of sulfate was also observed at concentrations as low as 1.6 mM, which is relevant for many wastewaters. Electrolysis of diatrizoate in the presence of specific radical quenchers (tert-butanol and methanol) had a similar effect on electro-oxidation rates, illustrating a possible role of the hydroxyl radical ((•)OH) in the anodic formation of sulfate radical (SO4(•-)) species. The addition of 0.55 mM persulfate increased the electro-oxidation rate of diatrizoate in nitrate from 0.94 to 9.97 h(-1), suggesting a nonradical activation of persulfate. Overall findings indicate the formation of strong sulfate-derived oxidant species at BDD anodes when polarized at high potentials. This may have positive implications in the electro-oxidation of wastewaters containing sulfate. For example, the energy required for the 10-fold removal of diatrizoate was decreased from 45.6 to 2.44 kWh m(-3) by switching from nitrate to sulfate anolyte.

Distinctive effects of graphene oxide and reduced graphene oxide on methane production kinetics and pharmaceuticals removal in anaerobic reactors.

Graphene oxide (GO) addition to anaerobic digestion has been suggested to enhance direct electron transfer. The impact of GO (0.075 g GO g-1 VS) and biologically and hydrothermally reduced GO (bio-rGO and h-rGO, respectively) on the methane production kinetics and removal of 12 pharmaceuticals was assessed in Fed-batch reactors. A decrease of 15 % in methane production was observed in the tests with GO addition compared with the control and the h-rGO. However, bio-rGO and h-rGO substantially increased the methane production rate compared to the control tests (+40 %), in the third fed-batch test. Removal of pharmaceuticals was enhanced only during the bio-reduction of GO (1st fed-batch test), whereas once the GO was bio-reduced, it followed a similar trend in the control and h-rGO tests. The addition of GO can enhance the methane production rate and, therefore, reduce the anaerobic treatment time.

Removal of the X-ray contrast media diatrizoate by electrochemical reduction and oxidation.

Due to their resistance to biological wastewater treatment, iodinated X-ray contrast media (ICM) have been detected in municipal wastewater effluents at relatively high concentrations (i.e., up to 100 µg L(-1)), with hospitals serving as their main source. To provide a new approach for reducing the concentrations of ICMs in wastewater, electrochemical reduction at three-dimensional graphite felt and graphite felt doped with palladium nanoparticles was examined as a means for deiodination of the common ICM diatrizoate. The presence of palladium nanoparticles significantly enhanced the removal of diatrizoate and enabled its complete deiodination to 3,5-diacetamidobenzoic acid. When the system was employed in the treatment of hospital wastewater, diatrizoate was reduced, but the extent of electrochemical reduction decreased as a result of competing reactions with solutes in the matrix. Following electrochemical reduction of diatrizoate to 3,5-diacetamidobenzoic acid, electrochemical oxidation with boron-doped diamond (BDD) anodes was employed. 3,5-Diacetamidobenzoic acid disappeared from solution at a rate that was similar to that of diatrizoate, but it was more readily mineralized than the parent compound. When electrochemical reduction and oxidation were coupled in a three-compartment reactor operated in a continuous mode, complete deiodination of diatrizoate was achieved at an applied cathode potential of -1.7 V vs SHE, with the released iodide ions electrodialyzed in a central compartment with 80% efficiency. The resulting BDD anode potential (i.e., +3.4-3.5 V vs SHE) enabled efficient oxidation of the products of the reductive step. The presence of other anions (e.g., chloride) was likely responsible for a decrease in I(-) separation efficiency when hospital wastewater was treated. Reductive deiodination combined with oxidative degradation provides benefits over oxidative treatment methods because it does not produce stable iodinated intermediates. Nevertheless, the process must be further optimized for the conditions encountered in hospital wastewater to improve the separation efficiency of halide ions prior to the electrooxidation step.

Impact of supporting electrolyte on electrochemical performance of borophene-functionalized graphene sponge anode and degradation of per- and polyfluoroalkyl substances (PFAS).

Graphene sponge anode functionalized with two-dimensional (2D) boron, i.e., borophene, was applied for electrochemical oxidation of C4-C8 per- and polyfluoroalkyl substances (PFASs). Borophene-doped graphene sponge outperformed boron-doped graphene sponge anode in terms of PFASs removal efficiencies and their electrochemical degradation; whereas at the boron-doped graphene sponge anode up to 35% of the removed PFASs was recovered after the current was switched off, the switch to a 2D boron enabled further degradation of the electrosorbed PFASs. Borophene-doped graphene sponge anode achieved 32-77% removal of C4-C8 PFASs in one-pass flow-through mode from a 10 mM phosphate buffer at 230 A m-2 of anodic current density. Higher molarity phosphate buffer (100 mM) resulted in lower PFASs removal efficiencies (11-60%) due to the higher resistance of the graphene sponge electrode in the presence of phosphate ions, as demonstrated by the electrochemical impedance spectroscopy (EIS) analyses. Electro-oxidation of PFASs was more efficient in landfill leachate despite its high organic loading, with up to 95% and 75% removal obtained for perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), versus 77% and 57% removal in the 10 mM phosphate buffer, respectively. Defluorination efficiencies as determined relative to the electrooxidized fraction of PFASs indicated up to 69% and 82% of defluorination of PFOS and PFOA in 10 mM phosphate buffer, which was decreased to 16 and 29% defluorination, respectively, for higher buffer molarity (100 mM) due to the worsened electrochemical performance of the sponge. In landfill leachate, relative defluorination efficiencies of PFOS and PFOA were 33% and 45%, respectively, indicating the inhibiting effect of complex organic and inorganic matrix of landfill leachate on the C-F bond breakage. This study demonstrates that electrochemical degradation of PFASs is possible to achieve in complex and brackish streams using a low-cost graphene sponge anode, without forming toxic chlorinated byproducts even in the presence of >7 g L-1 of chloride.

(Electro)catalytic oxidation of sulfide and recovery of elemental sulfur from sulfide-laden streams.

MnxOy coated over TiO2 nanotube array substrate was doped with Mo and polyaniline (PANI) and applied for electrochemical desulfurization of concentrated sulfide (HS-) solutions at basic pH, typical of biogas scrubbing solutions and industrial wastewater. Mo and PANI co-dopants significantly enhanced the anode activity towards sulfide oxidation and ensured its complete stability even in highly corrosive sulfide solutions (e.g., 200 mM HS-). This was due to the increased electrochemically active surface area, improved coating conductivity and reduced charge transfer resistance. The (electro)catalytic oxidation of HS- demonstrated robust performance with very limited impact of different operational parameters (e.g., dissolved oxygen, anode potential, HS- concentration). Due to the formation of elemental sulfur (S0) layer at the anode surface at basic pH, longer term anode usage requires its periodic removal. Chemical dissolution of S0 with toluene allows its rapid removal without affecting the anode activity, and easy recrystallization and recovery of pure sulfur.

Graphene oxide addition to anaerobic digestion of waste activated sludge: Impact on methane production and removal of emerging contaminants.

The effect of graphene oxide on the anaerobic digestion of waste activated sludge was investigated at two graphene oxide concentrations (0.025 and 0.075 g graphene oxide per g volatile solids) using biochemical methane potential tests. The occurrence of 36 pharmaceuticals was monitored in the solid and liquid phases before and after the anaerobic treatment. The addition of graphene oxide improved the removal of most pharmaceuticals detected, even those that are considered persistent to biological degradation, such as azithromycin, carbamazepine, and diclofenac. No significant differences were observed in the final specific methane production without graphene oxide and with the lowest graphene oxide concentration, yet the highest graphene oxide concentration partially inhibited methane production. The relative abundance of antibiotic resistance genes was not affected by the graphene oxide addition. Finally, significant changes in the microbial community including bacteria and archaea were detected with graphene oxide addition.

Impact of graphene oxide addition on pharmaceuticals removal in anaerobic membrane bioreactor.

The addition of conductive materials to the anaerobic digestion bioreactor was suggested to enhance microbial activity. In the present work, an anaerobic membrane bioreactor treating municipal wastewater was operated for 385 days. The impact of different graphene oxide concentrations on the removal target pharmaceuticals and microbial community dynamics was investigated. The addition of graphene oxide did not impact the reactor stability, whereas the removals of antibiotics (e.g., trimethoprim and metronidazole) were enhanced. A shift in the microbial community was detected after the addition of 50-900 mg L-1 of graphene oxide, with the proliferation hydrogenotrophic methanogens. The proliferation of syntrophic microorganisms may indicate interactions via direct interspecific electron transfer. The obtained results suggest that the addition of graphene oxide at low mg L-1 concentrations to an anaerobic membrane bioreactor may be considered to improve the removal of antibiotics from municipal wastewater.

Assessment of degradation byproducts and NDMA formation potential during UV and UV/H2O2 treatment of doxylamine in the presence of monochloramine.

UV-C radiation is the U.S. EPA recommended technology to remove N-nitrosodimethylamine (NDMA) during drinking and recycled water production. Frequently, H(2)O(2) is added to the treatment to remove other recalcitrant compounds and to prevent NDMA reformation. However, the transformation of NDMA precursors during the UV and UV/H(2)O(2) process and the consequences for NDMA formation potential are currently not well understood, in particular in the presence of monochloramine. In this study, doxylamine has been chosen as a model compound to elucidate its degradation byproducts in the UV and UV/H(2)O(2) process and correlate those with changes to the NDMA formation potential. This study shows that during UV treatment in the presence and absence of monochloramine, NDMA formation potential can be halved. However, an increase of more than 30% was observed when hydrogen peroxide was added. Ultrafast liquid chromatography coupled to quadrupole-linear ion trap mass spectrometer was used for screening and structural elucidation of degradation byproducts identifying 21 chemical structures from the original parent compound. This work shows that further oxidation of NDMA precursors does not necessarily lead to a decrease in NDMA formation potential. Degradation byproducts with increased electron density in the vicinity of the dimethylamino moiety, for example induced by hydroxylation, may have a higher yield of nucleophilic substitution and subsequent NDMA formation compared to the parent compound during chloramination. This work demonstrates the need to consider the formation of oxidation byproducts and associated implications for the control and management of NDMA formation in downstream processes and distribution when integrating oxidative treatments into a treatment train generating either drinking water or recycled water for potable reuse.

Effect of UV and UV/H2O2 in the presence of chloramines on NDMA formation potential of tramadol.

This study evaluates the effect of UV-C and UV-C/H(2)O(2) in the presence of chloramines on the N-nitrosodimethylamine formation potential (NDMA FP) of tramadol as a model precursor. The experiments were performed at high initial concentrations of TMDL (i.e., 20 mg/L) in order to elucidate the structures of TMDL byproducts. Twenty-four byproducts were identified in UV-C, UV-C/monochloramine, and UV/H(2)O(2)/monochloramine oxidation of tramadol using MS(3) capabilities of a hybrid quadrupole-linear ion trap mass spectrometer, combined with online hydrogen/deuterium (H/D) exchange experiments. Oxidative cleavage of methoxy and methoxybenzene moiety, O-demethylation, hydroxylation, and cyclohexane ring-opening were identified as major reaction mechanisms of tramadol in UV oxidation. Addition of monochloramine decreased the degradation rates of tramadol and its byproducts and yielded several monochlorinated derivatives. The oxidation rates were significantly enhanced in the presence of H(2)O(2), and byproducts of oxidative benzene ring-opening were detected. The majority of the identified byproducts are likely to have a higher NDMA FP than the parent compound due to a reduced steric hindrance and/or insertion of electron-donating hydroxyl groups in the N,N-dimethylamine side chain. This was confirmed by the results of NDMA FP tests, which showed that the formation of NDMA was enhanced up to four times depending on the process conditions in UV alone and in UV and UV/H(2)O(2) in the presence of monochloramine. Prolonged oxidation by hydroxyl radicals in UV/H(2)O(2)/monochloramine process mineralized some of the byproducts and slightly reduced the NDMA FP at the end of the treatment. The obtained degradation pathway of tramadol allowed the correlation of changes in NDMA FP during oxidation with its major oxidative transformation reactions. This manuscript demonstrates the significance of oxidation byproducts as NDMA precursors and emphasizes the need for their consideration when evaluating the evolution of NDMA FP during oxidative treatment.

Electrochemical degradation of per- and polyfluoroalkyl substances (PFAS) using low-cost graphene sponge electrodes.

Boron-doped, graphene sponge anode was synthesized and applied for the electrochemical oxidation of C4-C8 per- and polyfluoroalkyl substances (PFASs). Removal efficiencies, obtained in low conductivity electrolyte (1 mS cm-1) and one-pass flow-through mode, were in the range 16.7-67% at 230 A m-2 of anodic current density, and with the energy consumption of 10.1 ± 0.7 kWh m-3. Their removal was attributed to electrosorption (7.4-35%), and electrooxidation (9.3-32%). Defluorination efficiencies of C4-C8 perfluoroalkyl sulfonates and acids were 8-24% due to a fraction of PFAS being electrosorbed only at the anode surface. Yet, the recovery of fluoride was 74-87% relative to the electrooxidized fraction, suggesting that once the degradation of the PFAS is initiated, the C-F bond cleavage is very efficient. The nearly stoichiometric sulfate recoveries obtained for perfluoroalkyl sulfonates (91%-98%) relative to the electrooxidized fraction demonstrated an efficient cleavage of the sulfonate head-group. Adsorbable organic fluoride (AOF) analysis showed that the remaining partially defluorinated byproducts are electrosorbed at the graphene sponge anode during current application and are released into the solution after the current is switched off. This proof-of-concept study demonstrated that the developed graphene sponge anode is capable of C-F bond cleavage and defluorination of PFAS. Given that the graphene sponge anode is electrochemically inert towards chloride and does not form any chlorate and perchlorate even in brackish solutions, the developed material may unlock the electrochemical degradation of PFAS complex wastewaters and brines.

Electrochemical degradation of antibiotics using flow-through graphene sponge electrodes.

Graphene sponge electrodes doped with atomic boron and nitrogen were employed for electrochemical degradation of antibiotics sulfamethoxazole, trimethoprim, ofloxacin, and erythromycin. The removal of antibiotics that displayed strong π-π interactions (i.e., ofloxacin) with reduced graphene oxide (RGO) coating was less limited by the mass transfer and removal efficiencies > 80% were observed for the investigated range of electrolyte flowrates. At the highest applied flowrate (700 LMH), increase in the anodic current significantly worsened the removal of trimethoprim and erythromycin due to the detrimental impact of the evolving gas bubbles. Increase in current at 700 LMH led to a stepwise increase in the removal efficiency of sulfamethoxazole due to its enhanced electrosorption. Electrochemical degradation was achieved via ozone, hydrogen peroxide and hydroxyl radical (•OH). Extraction of the employed graphene sponges confirmed the degradation of the strongly adsorbing antibiotics. Identified electrochemical transformation products of erythromycin confirmed the participation of •OH, through N-demethylation of the dimethylamine group. In real tap water, removal efficiencies were lower for all target antibiotics. Lower electric conductivity of tap water and thus increased thickness of the electric double layer likely limited their interaction with the graphene sponge surface, in addition to the presence of low amounts of organic matter.

Enhanced methane production kinetics by graphene oxide in fed-batch tests.

The study aims to prove that the addition of graphene oxide (GO) improves anaerobic digestion (AD) kinetic performance. Classical batch tests were modified to a fed-batch strategy at four GO levels while using two substrates (glucose and microcrystalline cellulose (MCC)). First-order and modified Gompertz models were respectively applied to evaluate the kinetic performance. The results showed significantly (p < 0.05) improved kinetic from the third refeeding step for both substrates. 20 mg GO per g of volatile solids (VS) led to an increase of up to 210% for the first-order rate constant (k) and up to 120% for maximum biochemical methane potential (BMP) rate (RMAX) compared to control for glucose and MCC, respectively. The findings of this work suggest the implementation of GO in continuously operated systems to accelerate the AD process.

Ammonia recovery from anaerobic digester centrate using onsite pilot scale bipolar membrane electrodialysis coupled to membrane stripping.

Ammonia recovery from centrate of an anaerobic digester was investigated using an onsite bipolar-electrodialysis (BP-ED) pilot scale plant coupled to two liquid/liquid membrane contactor (LLMC) modules. To investigate the process performance and robustness, the pilot plant was operated at varying current densities, load ratio (current to nitrogen loading), and in continuous and intermittent current (Donnan) mode. A higher load ratio led to higher total ammonium nitrogen (TAN, sum of ammonia and ammonium) removal efficiency, whereas the increase in the applied current did not have a significant impact the TAN removal efficiency. Continuous current application resulted in the higher TAN removal compared with the Donnan dialysis mode. The lowest specific energy consumption of 6.3 kWh kgN-1 was recorded in the Donnan mode, with the load ratio of 1.4, at 200 L h-1 flowrate and current density of 75 A m-2. Lower energy demand observed in the Donnan mode was likely due to the lower scaling and fouling of the ion exchange membranes. Nevertheless, scaling and fouling limited the operation of the BP-ED stack in all operational modes, which had to be interrupted by the daily cleaning procedures. The LLMC module enabled a highly selective recovery of ammonia as ammonium sulfate ((NH4)2SO4), with the concentration of ammonia ranging from 19 to 33 gN L-1. However, the analysis of per- and polyfluoroalkyl substances (PFASs) in the obtained (NH4)2SO4 product revealed the presence of 212-253 ng L-1 of 6:2 fluorotelomer sulfonate (FTS), a common substitute of legacy PFAS. Given the very low concentrations of 6:2 FTS (i.e., < 2 ng L-1) encountered in the concentrated stream, 6:2 FTS was likely released from the Teflon-based components in the sulfuric acid dosage line. Thus, careful selection of the pilot plant tubing, pumps and other components is required to avoid any risks associated with the PFAS presence and ensure safe use of the final product as fertilizer.

Dehalogenation of iodinated X-ray contrast media in a bioelectrochemical system.

Iodinated X-ray contrast media (ICM) are only to a limited extent removed from conventional wastewater treatment plants, due to their high recalcitrance. This work reports on the cathodic dehalogenation of the ICM iopromide in a bioelectrochemical system (BES), fed with acetate at the anode and iopromide at the cathode. When the granular graphite cathode potential was decreased from -500 to -850 mV vs standard hydrogen electrode (SHE), the iopromide removal and the iodide release rates increased from 0 to 4.62 ± 0.01 mmol m(-3) TCC d(-1) and 0 to 13.4 ± 0.16 mmol m(-3) TCC d(-1) (Total Cathodic Compartment, TCC) respectively. Correspondingly, the power consumption increased from 0.4 ± 1 to 20.5 ± 3.3 W m(-3) TCC. The Coulombic efficiency of the iopromide dehalogenation at the cathode was less than 1%, while the Coulombic efficiency of the acetate oxidation at the anode was lower than 50% at various granular graphite cathode potentials. The results suggest that iopromide could be completely dehalogenated in BESs when the granular graphite cathode potential was controlled at -800 mV vs SHE or lower. This finding was further confirmed using mass spectrometry to identify the dehalogenated intermediates and products of iopromide in BESs. Kinetic analysis indicates that iopromide dehalogenation in batch experiments can be described by a first-order model at various cathode potentials. This work demonstrates that the BESs have a potential for efficient dehalogenation of ICM from wastewater or environmental streams.

Removal of persistent organic contaminants from wastewater using a hybrid electrochemical-granular activated carbon (GAC) system.

A three-dimensional (3D) electrochemical flow-through reactor equipped with GAC packed bed, polarized by the electric field, was evaluated for the removal of persistent organic contaminants from real sewage effluent. The performance of the reactor was investigated for 27 consecutive runs at two anodic current densities, i.e., low current density (LCD) of 15 A m-2, and high current density (HCD) of 100 A m-2. In the HCD experiments, the adsorption ability of saturated GAC was increased, mainly due to the increase in the mesoporosity of GAC. A synergy between electrosorption/adsorption on GAC and electrooxidation was observed in terms of the removal of all target pollutants. DEET presented the highest synergy, ranging from 40% to 57%, followed by iopromide (22-46%), carbamazepine (15-34%) and diatrizoate (4-30%). The addition of GAC decreased the concentrations of toxic chlorate and perchlorate by 2-fold and 10-fold, respectively, due to their electrosorption on GAC. Also, 3D electrochemical system yielded lower concentrations of adsorbable organic iodide (AOI) and adsorbable organic chlorine (AOCl). Thus, addition of low amounts of GAC in electrochemical systems may be a low-cost and simple way of minimizing the formation and final effluent concentrations of toxic halogenated byproducts.

Graphene-based sponges for electrochemical degradation of persistent organic contaminants.

Graphene-based sponges doped with atomic nitrogen and boron were applied for the electrochemical degradation of persistent organic contaminants in one-pass, flow-through mode, and in a low-conductivity supporting electrolyte. The B-doped anode and N-doped cathode was capable of >90% contaminant removal at the geometric anodic current density of 173 A m-2. The electrochemical degradation of contaminants was achieved via the direct electron transfer, the anodically formed O3, and by the OH• radicals formed by the decomposition of H2O2 produced at the cathode. The identified transformation products of iopromide show that the anodic cleavage of all three C-I bonds at the aromatic ring was preferential over scissions at the alkyl side chains, suggesting a determining role of the π- π interactions with the graphene surface. In the presence of 20 mM sodium chloride (NaCl), the current efficiency for chlorine production was <0.04%, and there was no chlorate and perchlorate formation, demonstrating a very low electrocatalytic activity of the graphene-based sponge anode towards chloride. Graphene-based sponges were produced using a low-cost, bottom-up method that allows easy introduction of dopants and functionalization of the reduced graphene oxide coating, and thus tailoring of the material for the removal of specific contaminants.