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.

(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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Characterization and comparison of Ti/TiO2-NT/SnO2-SbBi, Ti/SnO2-SbBi and BDD anode for the removal of persistent iodinated contrast media (ICM).

In this study, we investigated the impact of a TiO2 nanotube (NT) interlayer on the electrochemical performance and service life of Sb and Bi-doped SnO2-coatings synthesized on a titanium mesh. Ti/SnO2-SbBi electrode was synthetized by a thermal decomposition method using ionic liquid as a precursor solvent. Ti/TiO2-NT/SnO2-SbBi electrode was obtained by a two-step electrochemical anodization, followed by the same process of thermal decomposition. The synthesized electrodes were electrochemically characterized and analyzed by scanning electron microscopy and energy dispersive X-ray spectroscopy. Terephthalic acid (TA) experiments showed that Ti/SnO2-SbBi and Ti/TiO2-NT/SnO2-SbBi electrodes formed somewhat higher amounts of hydroxyl radicals (HO) compared with the mesh boron doped diamond (BDD) anode. Electrochemical oxidation experiments were performed using iodinated contrast media (ICM) as model organic contaminants persistent to oxidation. At current density of 50 A m-2, BDD clearly outperformed the synthesized mixed metal oxide (MMO) electrodes, with 2 to 3-fold higher oxidation rates observed for ICM. However, at 100 and 150 A m-2, Ti/SnO2-SbBi had similar performance to BDD, whereas Ti/TiO2-NT/SnO2-SbBi yielded even higher oxidation rates. Disappearance of the target ICM was followed by up to 80% removal of adsorbable organic iodide (AOI) for all three materials, further demonstrating iodine cleavage and thus oxidative degradation of ICM mediated by HO. The presence of a TiO2 NT interlayer yielded nearly 4-fold increase in anode stability and dislocated the oxygen evolution reaction by +0.2 V. Thus, TiO2 NT interlayer enhanced electrode stability and service life, and the electrocatalytic activity for the degradation of persistent organic contaminants.

Electrochemical removal of sulfide on porous carbon-based flow-through electrodes.

Electrochemical oxidation of hydrogen sulfide and its separation from the waste stream in the form of sulfur was studied at low-cost carbon-based porous materials, activated carbon felt (ACF) and graphite felt (GF). Both materials were capable of selective HS- oxidation to elemental sulfur in low-conductivity solutions (i.e., <1 mS cm-1), as well as in raw sewage. The HS- removal rate was ten times faster at ACF compared with GF electrode due to the higher surface area and chemisorption of HS-. To address the electrode passivation with the electrodeposited sulfur, different electrochemical recovery strategies were tested. GF could be only partially regenerated (i.e., 30% efficiency) using cathodic polarization. Also, both anodic and cathodic polarization improved the sulfide removal in the subsequent working cycle due to the introduction of new redox-active oxygen containing functional groups. Sulfur deposited at the ACF electrode could not be recovered by any of the investigated strategies. Thus, sulfur was incorporated into the carbon matrix and strongly bonded with the carbon functional groups at both GF and ACF electrodes. Although carbon-based electrodes have been widely investigated for electrochemical sulfide removal, this study demonstrates that their application is limited by low regeneration efficiency of the electrodeposited sulfur.

Removal of sulfamethoxazole by electrochemically activated sulfate: Implications of chloride addition.

Electrochemical oxidation is considered to be an attractive alternative to chemical oxidation for the treatment of polluted water. Given the of ability of boron-doped diamond (BDD) electrodes to generate hydroxyl radicals (OH), they are often selected for the degradation of persistent organic contaminants. Recently, BDD anodes have been demonstrated to form strong oxidants, sulfate radicals (SO4-), directly from sulfate ions. In this study, electrochemical activation of sulfate to SO4- at BDD anodes enhanced the removal of an antibiotic sulfamethoxazole (SMX). The rate of SMX oxidation was 6 times higher in sulfate anolyte compared to inert nitrate anolyte. Addition of chloride accelerated the disappearance of SMX in both anolytes due to electrochlorination. Yet, mineralization efficiency was decreased, particularly in Na2SO4 anolyte due to the scavenging of SO4- by Cl-. Electrogenerated SO4- yielded nitroso- and nitro-derivatives, which were not observed in the absence of sulfate. The peak intensities of chlorinated TPs were three orders of magnitude lower in Na2SO4 than in NaNO3 anolyte, suggesting that addition of sulfate may lower the formation of chlorinated organics. However, attention should be paid to the formation of inorganic byproducts, as the formation rates of toxic chlorate and in particular perchlorate were higher in Na2SO4 anolyte.

Predicting reactivity of model DOM compounds towards chlorine with mediated electrochemical oxidation.

Chlorine demand of a water sample depends on the characteristics of dissolved organic matter (DOM). It is an important parameter for water utilities used to assess oxidant and/or disinfectant consumption of source waters during treatment and distribution. In this study, model compounds namely resorcinol, tannic acid, vanillin, cysteine, tyrosine, and tryptophan were used to represent the reactive moieties of complex DOM mixtures. The reactivity of these compounds was evaluated in terms of Cl2 demand and electron donating capacity (EDC). The EDC was determined by mediated electrochemical oxidation (MEO) which involves the use of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) as an electron shuttle. The Cl2 demand of readily oxidizable compounds (resorcinol, tannic acid, vanillin, and cysteine) was found to correlate well with EDC (R2 = 0.98). The EDC values (mol e-/mol C) of the model compounds are as follows: 1.18 (cysteine) > 0.77 (resorcinol) > 0.59 (vanillin) > 0.52 (tannic acid) > 0.36 (tryptophan) > 0.19 (tyrosine). To determine the effect of pre-oxidation on EDC, ozone was added (0.1 mol O3/mol C) into each model compound solution. Ozonation caused a general decrease in EDC (10-40%), chlorine demand (10-30%), and UV absorbance (10-40%), except for tyrosine which showed both increased UV275 and EDC. Before and after ozonation, 24 h disinfection byproduct (DBP) formation potential tests (Cl2 residual = 1.5 mg/L) were conducted to evaluate the use of EDC for DBP formation prediction. The results indicate that there was no significant correlation between the EDC of the model compounds and the formation potentials of adsorbable organic chlorine, trichloromethane, and trichloroacetic acid. This suggests that while EDC correlates with Cl2 demand, chlorine consumption may not directly translate to DBP formation because oxidation reactions may dominate over substitution reactions. Overall, this study provides useful insights on the reactions of ABTS+ and HOCl with model DOM compounds, and highlights the potential application of MEO for rapid determination of Cl2 demand of a water sample.

Predicting scale formation during electrodialytic nutrient recovery.

Electro-concentration of nutrients from waste streams is a promising technology to enable resource recovery, but has several operational concerns. One key concern is the formation of inorganic scale on the concentrate side of cation exchange membranes when recovering nutrients from wastewaters containing calcium, magnesium, phosphorous and carbonate, commonly present in anaerobic digester rejection water. Electrodialytic nutrient recovery was trialed on anaerobic digester rejection water in a laboratory scale electro-concentration unit without treatment (A), following struvite recovery (B), and following struvite recovery as well as concentrate controlled at pH 5 for scaling control (C). Treatment A resulted in large amount of scale, while treatment B significantly reduced the amount of scale formation with reduction in magnesium phosphates, and treatment C reduced the amount of scale further by limiting the formation of calcium carbonates. Treatment C resulted in an 87 ± 7% by weight reduction in scale compared to treatment A. A mechanistic model for the inorganic processes was validated using a previously published general precipitation model based on saturation index. The model attributed the reduction in struvite scale to the removal of phosphate during the struvite pre-treatment, and the reduction in calcium carbonate scale to pH control resulting in the stripping of carbonate as carbon dioxide gas. This indicates that multiple strategies may be required to control precipitation, and that mechanistic models can assist in developing a combined approach.

Sulfate-mediated electrooxidation of X-ray contrast media on boron-doped diamond anode.

Recently, electrochemical activation of sulfate ions to sulfate radical species and nonradically activated persulfate has been demonstrated at boron-doped diamond (BDD) anode, which enhanced the electrooxidation kinetics of several persistent contaminants. In this study, we investigated the transformation pathways of two X-ray contrast media (ICM), diatrizoate and iopromide, in electrooxidation at BDD anode using sulfate and inert nitrate anolyte. Sulfate anolyte yielded a seven-fold increase in apparent rate constants for ICM oxidation compared to inert nitrate anolyte, and a two-fold increase for the removal of organic carbon. Higher iodine release was observed in electrooxidation of diatrizoate compared to iopromide. In the case of diatrizoate, around 80% of deiodination efficiency was achieved in both anolytes. Deiodination efficiency of iopromide was somewhat lower in nitrate anolyte (≤75%) and significantly reduced in sulfate anolyte (≤46%) due to a larger steric hindrance of alkyl side chains. Moreover, a considerable lag phase of iopromide deiodination was observed in sulfate anolyte, indicating that initial oxidation reactions took place almost exclusively at the alkyl side chains. Several transformation products (TPs) of ICM were identified in electrooxidation in sulfate anolyte, and only three TPs in the case of nitrate anolyte. The main mechanistic steps in the oxidation of iopromide were H-abstraction and bond cleavage in the alkyl side chains. Diatrizoate was mainly transformed through oxidative cleavage of iodine substituent and inter-molecular cyclization. Two hydroxylamine derivatives of iopromide and a nitro-derivative of diatrizoate were observed in sulfate anolyte. These products have not been reported previously for hydroxyl radical-mediated oxidation of ICM. Given that electron-transfer mechanism is more typical for sulfate than for hydroxyl radicals, formation of hydroxylamine and nitro-derivatives of ICM was assigned to one-electron charge transfer to sulfate radical species and formation of N-centered radicals.