A non-steroidal drug "diclofenac" is a substrate for electrochemical degradation process using graphite anode.

In the electrochemical degradation process, the elimination of organic pollutants could be enhanced using supporting electrolyte and applied voltage. After degradation of the target organic compound, some by-products are formed. Chlorinated by-products are the main products formed in the presence of sodium chloride. In the present study, an electrochemical oxidation process has been applied to diclofenac (DCF) using graphite as an anode and sodium chloride (NaCl) as a supporting electrolyte. Monitoring the removal of the by-products and elucidating them were provided using HPLC and LC-TOF/MS, respectively. A high removal% of 94% DCF was observed under the conditions: 0.5 g NaCl, 5 V, and 80 min of electrolysis, while the removal% of chemical oxygen demand (COD) was 88% under the same conditions, but 360 min of electrolysis was required. The pseudo-first-order rate constant values were quite varied based on the selected experimental conditions; the rate constants were between 0.0062 and 0.054 min-1, between 0.0024 and 0.0326 min-1 under the influence of applied voltage and sodium chloride, respectively. The maximum values of energy consumption were 0.93 and 0.55 Wh/mg using 0.1 g NaCl and 7 V, respectively. Some chlorinated by-products, C13H18Cl2NO5, C11H10Cl3NO4, and C13H13Cl5NO5, were selected and elucidated using LC-TOF/MS.

The fate of prazosin and levonorgestrel after electrochemical degradation process: Monitoring by-products using LC-TOF/MS.

Prazosin (PRZ) and levonorgestrel (LNG) are widely used as an anti-disease drugs due to their biological activity in the human body. The frequent detection of these compounds in water samples requires alternative technologies for the removal of both compounds. After electrochemical degradation of PRZ and LNG, the parent compounds could be completely removed after treatment, but the identification and characterization of by-products are necessary as well. In this study, the effects of NaCl concentration and applied voltage were investigated during the electrochemical degradation process. The results revealed that the increase of NaCl concentration and applied voltage could promote the generation of hypochlorite OCl- and then enhance the degradation of PRZ and LNG. After initial study, 6V and 0.2g NaCl were selected for further experiments (96% and 99% removal of PRZ and LNG after 40min, respectively). Energy consumption was also evaluated and calculated for PRZ and LNG at 3, 6 and 8V. Solid phase extraction (SPE) method plays an important role in enhancing the detection limit of by-products. Furthermore, characterization and identification of chlorinated and non-chlorinated by-products were conducted using an accurate liquid chromatography-time of flight/mass spectrometry LC-TOF/MS instrument. The monitoring of products during the electrochemical degradation process was performed at 6V and 0.2g NaCl in a 50mL solution. The results indicated that two chlorinated products were formed during the electrochemical process. The toxicity of by-products toward E. coli bacteria was investigated at 37°C and 20hr incubation time.

Chronic toxicity of parabens and their chlorinated by-products in Ceriodaphnia dubia.

The chronic toxicity of 12 compounds of parabens and their chlorinated by-products was investigated using 7-day Ceriodaphnia dubia test under static renewal condition in order to generate information on how to disinfect by-products of preservatives that are discharged in aquatic systems. The mortality and inhibition of reproduction tended to increase with increasing hydrophobicity and decreased with the degree of chlorination of parabens. The EC50 values for mortality, offspring number, and first brood production ranged between 0.30-3.1, 0.047-12, and 1.3-6.3 mg L(-1) , respectively. For the number of neonates, the most sensitive endpoint, the no-observed-effect concentration (NOEC) and lowest-observed-effect concentration (LOEC) values ranged from 0.63 to 10 mg L(-1) and from 1.2 to 19 mg L(-1) , respectively. Methylparaben (MP), benzylparaben (BnP), and dichlorinated BnP (Cl2 BnP) elicited a significant decrease in offspring numbers even at their lowest concentration tested; the NOEC for these compounds was determined to be less than the lowest test concentration (1.3, 0.04, and 0.63 mg L(-1) for MP, BnP, and Cl2 BnP, respectively). Propylparaben (PP), chlorinated PP, isopropylparaben (iPP), and chlorinated iPP exhibited nonmonotonic concentration-dependent response; their NOEC and LOEC values could not be determined. The multivariate approach involving principal component analysis and hierarchical cluster analysis revealed four groups that corresponded to the toxicological profiles of parabens. Our results suggested that disinfection of parabens by chlorination could reduce aquatic toxicity of original compounds. The findings obtained in our study together with the data available on paraben concentrations in aquatic systems can be used to perform preliminary risk assessment by comparing the predicted environmental concentration (PEC) with the predicted no-effect concentration (PNEC) for the marine aquatic environment. The calculated PEC/PNEC ratios ranged from 0.0012 to 0.2, with the highest value observed in MP. This suggested that there are negligible environmental risks for aquatic organisms at current use levels.

Degradation of organic pollutants by the Cl-/PMS process.

The viewpoints on whether high concentrations of chloride ion (Cl-) promote or inhibit the oxidation activity of activated persulfates are still inconclusive. Furthermore, the degradation of organic pollutants by the persulfates in the presence of high Cl- concentrations without any activation medium has not yet been studied. In this work, the efficiency and mechanism of degradation of organic pollutants such as carbamazepine (CBZ), sulfadiazine (SDZ), and phenol (PN) by Cl--activated PMS (denoted as Cl-/PMS) were investigated. Results showed that Cl- could effectively activate PMS for the complete removal of CBZ, SDZ, and PN with reaction kinetic constants of 0.4516 min-1, 0.01753 min-1, and 0.06805 min-1, respectively. Parameters such as PMS dose, Cl- concentration, solution pH, and initial concentrations of organic pollutants that affect the degradation efficiencies of the Cl-/PMS process were optimized. Unlike conventional activated persulfates, it was confirmed that the free chlorine was the main active species in the Cl-/PMS process. Finally, the degradation by-products of CBZ and SDZ as well as their toxicity were detected, and a possible degradation pathway for CBZ and SDZ was proposed. Though higher toxic chlorinated by-products were generated, the Cl-/PMS process was still an efficient oxidation method for the removal of organic pollutants in aqueous solutions which contain high concentrations of Cl-.

High-valent metal-oxo species transformation and regulation by co-existing chloride: Reaction pathways and impacts on the generation of chlorinated by-products.

High-valent metal-oxo species (HMOS) have been extensively recognized in advanced oxidation processes (AOPs) owing to their high selectivity and high chemical utilization efficiency. However, the interactions between HMOS and halide ions in sewage wastewater are complicated, leading to ongoing debates on the intrinsic reactive species and impacts on remediation. Herein, we prepared three typical HMOS, including Fe(IV), Mn(V)-nitrilotriacetic acid complex (Mn(V)NTA) and Co(IV) through peroxymonosulfate (PMS) activation and comparatively studied their interactions with Cl- to reveal different reactive chlorine species (RCS) and the effects of HMOS types on RCS generation pathways. Our results show that the presence of Cl- alters the cleavage behavior of the peroxide OO bond in PMS and prohibits the generation of Fe(IV), spontaneously promoting SO4•- production and its subsequent transformation to secondary radicals like Cl• and Cl2•-. The generation and oxidation capacity of Mn(V)NTA was scarcely influenced by Cl-, while Cl- would substantially consume Co(IV) and promote HOCl generation through an oxygen-transfer reaction, evidenced by density functional theory (DFT) and deuterium oxide solvent exchange experiment. The two-electron-transfer standard redox potentials of Fe(IV), Mn(V)NTA and Co(IV) were calculated as 2.43, 2.55 and 2.85 V, respectively. Due to the different reactive species and pathways in the presence of Cl-, the amounts of chlorinated by-products followed the order of Co(II)/PMS > Fe(II)/PMS > Mn(II)NTA/PMS. Thus, this work renovates the knowledge of halide chemistry in HMOS-based systems and sheds light on the impact on the treatment of salinity-containing wastewater.

Sodium tetraborate simultaneously enhances the degradation of acetaminophen and reduces the formation potential of chlorinated by-products with heat-activated peroxymonosulfate oxidation.

In this study, sodium tetraborate (Na2B4O7) was introduced to enhance the degradation of acetaminophen (ACT) in heat-activated peroxymonosulfate (PMS) process. The elimination of ACT in Na2B4O7/heat/PMS process followed the pseudo-first order kinetics. The corresponding kobs value with 10 mM Na2B4O7 was 33.1 times higher than that in heat/PMS process. 1O2 and HO· were identified as primary reactive species via quenching experiments and electron paramagnetic resonance technology. B(OH)4-, the hydrolysis product of Na2B4O7, reacted with PMS to generate HOOB(OH)3-. 1O2 was generated by the self-decomposition of PMS using B(OH)4- as catalyst, while HO· was produced via the breakage of peroxide bond of PMS and HOOB(OH)3-under high temperature. ACT was degraded by reactive species via the pathways of -NH- bond breakage, -OH replacement, -NH2 oxidation and benzene ring cleavage. Nine transformation intermediates were detected by LC/Q-TOF/MS, and the toxicity of reaction solution decreased significantly with the elimination of ACT. Increasing Na2B4O7 dosage, PMS concentration, initial pH and reaction temperature were conducive to ACT elimination. Humic acid, Cl- and CO32- inhibited the degradation of ACT heavily, while SO42- and NO3- had the negligible effects. Moreover, B(OH)4- could react with free chlorine to the inert B(OH)3OCl- and further significantly suppress the formation of chlorinated by-products for the treatment of Cl--containing water in Na2B4O7/heat/PMS process. This study provided an effective way to enhance the oxidation capacity of heat/PMS process and suppress the formation of chlorinated by-products in chloride-containing water, and the findings had important implications for using borate buffer in the studies of PMS-based advanced oxidation processes.

A combined radical and non-radical oxidation processes for efficient degradation of Acid Orange 7 in the homogeneous Cu(II)/PMS system: important role of chloride.

Trace copper ion (Cu(II)) in water and wastewater can trigger peroxymonosulfate (PMS) activation to oxidize organic compounds, but it only works under alkaline conditions. In this work, we found that the presence of chloride could significantly accelerate the oxidation of Acid Orange 7 (AO7) by the Cu(II)/PMS process at a wide pH range (4.0-9.0). The observed pseudo-first-order rate constant k for AO7 oxidation was linearly correlated with the increased Cl- concentration (0-300 mM). An increase in mineralization rate was observed in the presence of Cl-, while the overall mineralization was quite low. Decomposition of PMS facilitated when Cl- concentration or pH value increased. Based on the scavenger experiments and electron paramagnetic resonance (EPR) measurement, the mechanism of Cu(II)-catalyzed PMS oxidation process in the presence of Cl- was proposed as both the radical and non-radical pathway, and 1O2 was the reactive oxygen species in the Cu(II)/PMS system. Finally, a possible degradation pathway of AO7 was elucidated. The feasibility of in situ utilizing high salinity and trace cupric species to accelerate the degradation of organic pollutants by the Cu(II)/PMS process in water and wastewater was demonstrated. However, the identification of undesired chlorinated by-products reminds us of cautiousness in assessing the application of Cu(II)/PMS system under chloride-rich environment. The findings of this work provide a simple and efficient approach to apply PMS in the remediation of refractory organic contaminants in the presence of trace cupric species under a high salinity environment with a wide range of pH.

Impact of chloride ions on activated persulfates based advanced oxidation process (AOPs): A mini review.

Chloride ion (Cl-) is ever-present in aquatic environments. Different Cl- concentration have been reported in industrial water (760 mM), surface water (<21 mM), seawater (540 mM) and groundwater (<21 mM) which could potentially accumulate into large concentrations in the sea. This mini-review examines more than 200 studies and found that Cl- ions can react with strong oxidants (SO4•-, •OH, and HSO5-) generated from persulfate activation, inducing the formation of chlorine radicals, that can either (1) directly react with organics or (2) generate chlorine radicals that can participate in the conversion of the organic substrate. Although the impact of chloride radicals have been identified as either negligible, positive, or negative (inhibitive) at different Cl- concentrations, only a few studies have considered the possible generation of chlorinated by-products. Another essential detail that is often neglected is the mutagenicity and toxicity of these products, as only a few studies have reported on the biotoxicity, AOX (adsorbable organic halogen) and the degree of mineralization of Cl- containing persulfate activated AOPs (Advanced Oxidation Process). Future studies need to consider the chemical analysis of the degradation products as well as the mutagenicity, toxicity and the biological effects pre and post-oxidation process. This evaluation will address several key issues including the properties, occurrence, and toxicity of the chlorinated products, which can significantly benefit its application in a large-scale environmental application.

Effective blockage of chloride ion quenching and chlorinated by-product generation in photocatalytic wastewater treatment.

Photocatalytic degradation of pollutants in high salinity wastewater usually shows extremely low activities and produces highly toxic by-products, often related to the presence of excess chloride ion (Cl-). Herein, we report for the first time that involvement of Cl- (quenching active species and generating chlorinated by-products) could be effectively blocked during photocatalytic processes. Based on a comprehensive investigation of its mechanism, we found that Cl- could quench superoxide radicals (O2-) through a cyclic indirect quenching model with holes (h+) and hydroxyl radicals (OH) quenching as "initiators". Thus, scavenging h+ and OH could successfully block the chain reactions between Cl- and O2-, and photocatalytic degradation of methyl orange (a refractory dye, with O2- as dominant attacking species) could be enhanced by nearly 50 times, even when Cl- content was up to 10 wt%. More importantly, both HPLC-MS analyses and DFT calculation validated that, by blocking its quenching effect, Cl- could be successfully excluded from the pollutant degradation processes, thus preventing the generation of toxic chlorinated by-products. This work provides new insights into control of chlorinated by-products and proposes feasible strategies to extend photocatalytic technology in high salinity wastewater.

Removal of organic compounds from cooling tower blowdown by electrochemical oxidation: Role of electrodes and operational parameters.

The reuse of cooling tower blowdown (CTBD) in the cooling tower itself requires CTBD deionization and a pre-treatment before deionization to remove organic compounds (OCs) that induce membrane fouling. This study assesses the potential of electrochemical oxidation (EO) with a boron-doped diamond (BDD) and a Ti/RuO2 mixed-metal oxide (MMO) anode for CTBD pre-treatment. Also, the influence of the applied current density (j), initial pH, hydrodynamic conditions, and supporting electrolyte on the process performance was evaluated. Results show that COD and TOC removal were 85 and 51%, respectively, with the BDD-anode; however, they were 50 and 12% with MMO-anode at a j-value of 8.7 mA cm-2 and neutral pH. An increased j-value increased the COD and TOC removal; however, different pHs, hydrodynamic conditions, and the addition of supporting electrolytes had a minor impact on the removal with both anodes. Liquid chromatography-organic carbon detection analysis showed that the OC in CTBD mainly consisted of humic substances (HS). EO with the BDD-anode resulted in 35% HS mineralization, while the rest of the HS were partially oxidized into low molecular weight compounds and building blocks. However, HS mineralization was limited with the MMO-anode. The mineralization and oxidation were accompanied by the formation of organic and inorganic chlorinated species. These species increased the toxicity to Vibrio fischeri 20-fold compared to the initially low-toxic CTBD. Thus, EO with a BDD-anode is a promising pre-treatment technology for the removal of OCs before CTBD deionization, but measures to minimize the chlorinated species formation are required before its application.

The beneficial effect of cathodic hydrogen peroxide generation on mitigating chlorinated by-product formation during water treatment by an electro-peroxone process.

The formation of chlorinated by-products is a major concern associated with electrochemical water treatment processes. This study investigated the formation of chlorinated by-products during surface water treatment by a newly developed electrochemical advanced oxidation process (EAOP), the electro-peroxone (E-peroxone) process, which couples ozonation with in situ electro-generation of hydrogen peroxide (H2O2) from cathodic oxygen reduction. Due to the enhanced ozone (O3) conversion to hydroxyl radicals (•OH) by electro-generated H2O2, the E-peroxone process considerably accelerated the abatement of ozone-refractory micropollutants such as clofibric acid and chloramphenicol in the selected surface water compared to conventional ozonation. In addition, the cathodically generated H2O2 effectively quenched hypochlorous acid (HOCl) derived from the anodic oxidation of chloride in the surface water. Therefore, the formation of trichloromethane (TCM) and chloroacetic acids (CAAs) from the reactions of HOCl with dissolved organic matter (DOM) was insignificant during the E-peroxone process, and similar levels of TCM and CAAs were generally observed in the conventional ozonation and E-peroxone treated water. In contrast, considerable amounts of HOCl could be generated from the anodic oxidation of chloride and then accumulated in the surface water during conventional electrolysis process, which resulted in significantly higher concentrations of TCM and CAAs in the electrolysis treated water. The results of this study suggest that the E-peroxone process can overcome the major limitation of conventional electrochemical processes and provide an effective and safe EAOP alternative for micropollutant abatement during water treatment.

Deciphering the degradation/chlorination mechanisms of maleic acid in the Fe(II)/peroxymonosulfate process: An often overlooked effect of chloride.

In recent years, a significant effort has been devoted into investigating the effects of chloride on the degradation kinetics of aromatic pollutants. The impact of chloride on the decomposition of short-chain carboxylic acid intermediates from aromatics degradation has often been overlooked. In this study the roles of chloride in the oxidation of maleic acid (MA) in the Fe(II)/peroxymonosulfate (PMS) process was investigated. Degradation efficiency, reaction intermediates, adsorbable organic halogen (AOX) accumulation and mineralization were examined. The chloride ion (Cl-) was found to have an overall negative impact on MA degradation and mineralization in the Fe(II)/PMS system. The presence of Cl- led to the formation of chlorinated by-products and a high production of AOX. The mineralization of MA was decreased with increasing Cl- concentrations. Kinetic modeling demonstrated the impact of various radicals largely depended on the concentration of Cl-. The significance of Cl2•- or Cl2 for MA destruction was enhanced with increasing Cl- content, and overwhelmed that of SO4•- when the Cl- concentration was over 5 mM. In the absence of Cl-, SO4•- was the primary radical responsible for MA oxidation. A possible degradation pathway is proposed (cis-trans isomerization, decarboxylation and halogenations processes). These results may help to understand the full oxidation pathways of refractory aromatic compounds and the mechanism of chlorinated by-products formation in industrial saline wastewater treatment.

Effects of chloride on PMS-based pollutant degradation: A substantial discrepancy between dyes and their common decomposition intermediate (phthalic acid).

A considerable effort has been devoted to elucidating the roles of chloride in oxidative degradation and chlorination of dyes. However, few investigations are available on kinetic analysis and transformation pathways of secondary degradation byproducts of dyes in saline wastewater treatment. Here the impact of chlorine on the degradation rate of phthalic acid, a typical dye degradation intermediate, by the Co2+/peroxymonosulfate (PMS) process was examined. Degradation efficiency, intermediate products, AOX (adsorbable organic halogen) formation and mineralization were considered. An overall negative impact was observed within the concentration of Cl- up to 100 mM, differing from the dual effect of chloride on dye degradation process as previously observed. The presence of high levels of Cl- led to a low production of AOX and a reduction of the formation of chlorinated by-products. The mineralization was also restrained when the Cl- concentration was increased. Degradation pathways for these processes are proposed. These findings provide valuable information about the degradation pathways of dyes and about the formation mechanism of chlorinated by-products in industrial saline wastewater treatment.

Direct electrochemical oxidation of ammonia on graphite as a treatment option for stored source-separated urine.

Electrolysis can be a viable technology for ammonia removal from source-separated urine. Compared to biological nitrogen removal, electrolysis is more robust and is highly amenable to automation, which makes it especially attractive for on-site reactors. In electrolytic wastewater treatment, ammonia is usually removed by indirect oxidation through active chlorine which is produced in-situ at elevated anode potentials. However, the evolution of chlorine can lead to the formation of chlorate, perchlorate, chlorinated organic by-products and chloramines that are toxic. This study focuses on using direct ammonia oxidation on graphite at low anode potentials in order to overcome the formation of toxic by-products. With the aid of cyclic voltammetry, we demonstrated that graphite is active for direct ammonia oxidation without concomitant chlorine formation if the anode potential is between 1.1 and 1.6 V vs. SHE (standard hydrogen electrode). A comparison of potentiostatic bulk electrolysis experiments in synthetic stored urine with and without chloride confirmed that ammonia was removed exclusively by continuous direct oxidation. Direct oxidation required high pH values (pH > 9) because free ammonia was the actual reactant. In real stored urine (pH = 9.0), an ammonia removal rate of 2.9 ± 0.3 gN·m(-2)·d(-1) was achieved and the specific energy demand was 42 Wh·gN(-1) at an anode potential of 1.31 V vs. SHE. The measurements of chlorate and perchlorate as well as selected chlorinated organic by-products confirmed that no chlorinated by-products were formed in real urine. Electrode corrosion through graphite exfoliation was prevented and the surface was not poisoned by intermediate oxidation products. We conclude that direct ammonia oxidation on graphite electrodes is a treatment option for source-separated urine with three major advantages: The formation of chlorinated by-products is prevented, less energy is consumed than in indirect ammonia oxidation and readily available and cheap graphite can be used as the electrode material.

Removal of caffeine from aqueous solution by indirect electrochemical oxidation using a graphite-PVC composite electrode: A role of hypochlorite ion as an oxidising agent.

The electrochemical oxidation of caffeine, a widely over-the-counter stimulant drug, has been investigated in effluent wastewater and deionized water (DIW) using graphite-poly vinyl chloride (PVC) composite electrode as anode. Effects of initial concentration of caffeine, chloride ion (Cl(-)) loading, presence of hydrogen peroxide (H2O2), sample volume, type of sample and applied voltage were determined to test and to validate a kinetic model for the oxidation of caffeine by the electrochemical oxidation process. The results revealed that the electrochemical oxidation rates of caffeine followed pseudo first-order kinetics, with rate constant values ranged from 0.006 to 0.23 min(-1) depending on the operating parameters. The removal efficiency of caffeine increases with applied voltage very significantly, suggesting a very important role of mediated oxidation process. However, the consumption energy was considered during electrochemical oxidation process. In chloride media, removal of caffeine is faster and more efficiently, although occurrence of more intermediates takes place. The study found that the adding H2O2 to the NaCl solution will inhibit slightly the electrochemical oxidation rate in comparison with only NaCl in solution. Liquid chromatography-time of flight-mass spectrometry (LC-TOF-MS) technique was applied to the identification of the by-products generated during electrochemical oxidation, which allowed to construct the proposed structure of by-products.