N-Chlorotaurine Solutions as Agents for Infusion Detoxification Therapy: Preclinical Studies.

N-chlorotaurine (NCT) is a broad-spectrum antimicrobial agent with outstanding tolerability, effective for topical and inhalation use. This paper presents the results of studies of single and repeated intravenous infusions of NCT to laboratory animals. The studies were conducted on female Wistar Han rats. The effect of NCT infusions on the general condition, behavioral reactions, main biochemical and hematological parameters, hemocoagulation system, cardiovascular system, and on the condition of the internal organs was studied. It was found that NCT infusions do not reveal deviations in the studied parameters that could indicate a toxic effect. The estimated LD50 is more than 80 mg/kg. In a subchronic experiment, a statistically significant decrease in cholesterol (by up to 11%), glucose (by up to 15%) and excess bases (up to four times) in the blood, and an increase in heart rate (by up to 31%) and frequency of defecations (by up to 35%), as well as pronounced antiplatelet effect, were found. In animals with simulated endotoxicosis, a decrease in the cytolysis and oxidative stress markers was observed. Such effects are caused by both chlorine-active compounds and taurine.The results obtained indicate broad prospects for the use of NCT solutions as an infusion detoxifying agent.

Energy-Efficient Electrosynthesis of High Value-Added Active Chlorine Coupled with H2 Generation from Direct Seawater Electrolysis through Decoupling Electrolytes.

Direct saline (seawater) electrolysis is a well-recognized system to generate active chlorine species for the chloride-mediated electrosynthesis, environmental remediation and sterilization over the past few decades. However, the large energy consumption originated from the high cell voltage of traditional direct saline electrolysis system, greatly restricts its practical application. Here, we report an acid-saline hybrid electrolysis system for energy-saving co-electrosynthesis of active chlorine and H2. We demonstrate that this system just requires a low cell voltage of 1.59 V to attain 10 mA cm-2 with a large energy consumption decrease of 27.7 % compared to direct saline electrolysis system (2.20 V). We further demonstrate that such acid-saline hybrid electrolysis system could be extended to realize energy-saving and sustainable seawater electrolysis. The acidified seawater in this system can absolutely avoid the formation of Ca/Mg-based sediments that always form in the seawater electrolysis system. We also prove that this system in the half-flow mode can realize real-time preparation of active chlorine used for sterilization and pea sprout production.

Boosting Hydroxyl Radical Yield via Synergistic Activation of Electrogenerated HOCl/H2O2 in Electro-Fenton-like Degradation of Contaminants under Chloride Conditions.

Hydroxyl radical production via catalytic activation of HOCl is a new type of Fenton-like process. However, metal-chlorocomplex formation under high chloride conditions could deactivate the catalyst and reduce the process efficiency. Herein, in situ electrogenerated HOCl was activated to •OH via a metal-free, B/N-codoped carbon nanofiber cathode for the first time to degrade contaminant under high chloride condition. The results show 98% degradation of rhodamine B (RhB) within 120 min (k = 0.036 min-1) under sulfate conditions, while complete degradation (k = 0.188 min-1) was obtained in only 30 min under chloride conditions. An enhanced degradation mechanism consists of an Adsorb & Shuttle process, wherein adsorption concentrates the pollutants at the cathode surface and they are subsequently oxidized by the large amount of •OH produced via activation of HOCl and H2O2 at the cathode. Density functional theory calculations verify the pyridinic N as the active site for the activation of HOCl and H2O2. The process efficiency was also evaluated by treating tetracycline and bisphenol A as well as high chloride-containing real secondary effluents from a pesticide manufacturing plant. High yields of •OH and HOCl allow continuous regeneration of the cathode for several cycles, limiting its fast deactivation, which is promising for real application.

Energy-efficient electrochemical treatment of paracetamol using a PbO2 anode based on pulse electrodeposition strategy: Kinetics, energy consumption and mechanism.

The purpose of this research is to study the pulse electrochemical oxidation of paracetamol (PCT) using a novel PbO2 anode based on pulse electrodeposition strategy (PbO2-PE). The pulse electrodeposition strategy used to prepare a PbO2 anode resulted in rougher surface, higher directional specificity of ß(101) and more redox couples of Pb4+/Pb2+. Additionally, the oxygen evolution potential (OEP) and charge transfer resistance were also improved. When compared to direct current electrochemical oxidation process, pulse electrolysis in had a slightly higher PCT removal efficiency and active species (·OH and active chlorine) production, while 72.04% of energy consumption was saved. The effects of operating parameters on PCT degradation efficiency and specific energy consumption were studied. The findings suggested that the pulse electrochemical oxidation of PCT followed a pseudo-first-order kinetic model, with PCT removal reaching 98.63% after 60 min of electrolysis under optimal conditions. Possible mechanisms describing reaction pathways for PCT were also proposed. Finally, combinating with the economic feasibility and safety evaluation, we could conclude that pulse electrolysis with a PbO2-PE electrode was a promising option for improving the practicability of electrochemical treatment for refractory organic wastewater.

Visible Light-Driven Conversion of Carbon-Sequestrated Seawater into Stoichiometric CO and HClO with Nitrogen-Doped BiOCl Atomic Layers.

Seawater is one of the most important CO2 sequestration media for delivering value-added chemicals/fuels and active chlorine; however, this scenario is plagued by sluggish reaction rates and poor product selectivity. Herein, we first report the synthesis of nitrogen-doped BiOCl atomic layers to directly split carbon-sequestrated natural seawater (Yellow Sea, China) into stoichiometric CO (92.8 µmol h-1 ) and HClO (83.2 µmol h-1 ) under visible light with selectivities greater than 90 %. Photoelectrons enriched on the exposed BiOCl{001} facet kinetically facilitate CO2 -to-CO reduction via surface-doped nitrogen bearing Lewis basicity. Photoholes, mainly located on the lateral facets of van der Waals gaps, promote the selective oxidation of Cl- into HClO. Sequestrated CO2 also maintains the pH of seawater at around 4.2 to prevent the alkaline earth cations from precipitating. The produced HClO can effectively kill typical bacteria in the ballast water of ocean-going cargo ships, offering a green and safe way for onsite sterilization.

Visualization of Electrochemically Accessible Sites in Flow-through Mode for Maximizing Available Active Area toward Superior Electrocatalytic Ammonia Oxidation.

Active chlorine species-mediated electrocatalytic oxidation is a promising strategy for ammonia removal in decentralized wastewater treatment. Flow-through electrodes (FTEs) provide an ideal platform for this strategy because of enhanced mass transport and sufficient electrochemically accessible sites. However, limited insight into spatial distribution of electrochemically accessible sites within FTEs inhibits the improvement of reactor efficiency and the reduction of FTE costs. Herein, a microfluidic-based electrochemical system is developed for the operando observation of microspatial reactions within pore channels, which reveals that reactions occur only in the surface layer of the electrode thickness. To further quantify the spatial distribution, finite element simulations demonstrate that over 75.0% of the current is accumulated in the 20.0% thickness of the electrode surface. Based on these findings, a gradient-coated method for the active layer was proposed and applied to a Ti/RuO2 porous electrode with an optimized pore diameter of ∼25 µm, whose electrochemically accessible surface area was 381.7 times that of the planar electrode while alleviating bubble entrapment. The optimized reactor enables complete ammonia removal with an energy consumption of 60.4 kWh kg-1 N, which was 24.2% and 39.9% less than those with pore diameters of ∼3 µm and ∼90 µm, respectively.

Effect of electrolyte composition on electrochemical oxidation: Active sulfate formation, benzotriazole degradation, and chlorinated by-products distribution.

Electrochemical oxidation is an effective technique for treating persistent organic pollutants, which are hardly removed in conventional wastewater treatment plants. Sulfate and chloride salts commonly used and present in natural wastewater influence the electrochemical degradation process. In this study, the effect of electrolyte composition on the active sulfate species (SO4●⁻ and S2O82⁻) formation, benzotriazole degradation-a model organic compound, and chlorinated by-products distribution have been investigated while using a boron-doped diamond (BDD) anode. Different Na2SO4:NaNO3 and Na2SO4:NaCl ratios with constant conductivity of 10 mS/cm were used in the experiments and applied anode potential was kept constant at 4.3 V vs. Ag/AgCl. The electrogenerated SO4●⁻ and S2O82⁻ formation were faster in 10:1 and 2:1 Na2SO4:NaNO3 ratios than in the 1:0 ratio. The ●OH-mediated SO4●⁻ production has prevailed in 10:1 and 2:1 ratios. However, ●OH-mediated SO4●⁻ production has hindered the 1:0 ratio due to excess chemisorption of SO42⁻ on the BDD anode. Similarly, the faster benzotriazole degradation, mineralization, and lowest energy consumption were achieved in the 10:1 Na2SO4:NaNO3 and Na2SO4:NaCl ratio. Besides, chlorinated organic by-product concentration (AOX) was lower in the 10:1 Na2SO4:NaCl ratio but increased with the increasing chloride ratio in the electrolyte. LC-MS analysis shows that several chlorinated organic transformation products were produced in 0:1 to 2:1 ratio, which was not found in the 10:1 Na2SO4:NaCl ratio. A comparatively higher amount of ClO4⁻ was formed in the 10:1 ratio than in 2:1 to 0:1 ratio. This ClO4⁻ formation train evidence the effective ●OH generation in a sulfate-enriched condition because the ClO4⁻ formation is positively correlated to ●OH concentration. Overall results show that sulfate-enriched electrolyte compositions are beneficial for electrochemical oxidation of biorecalcitrant organic pollutants.

Acute inhalation toxicity of aerosolized electrochemically generated solution of sodium hypochlorite.

OBJECTIVE: The objective was to determine the inhalation toxicity of the electrochemically generated sodium hypochlorite solution after its single administration to laboratory animals in the form of a highly dispersed aerosol. MATERIALS AND METHODS: The study has been conducted according to the OECD Test Guideline №403 'Acute Inhalation Toxicity.' Laboratory animals were exposed to inhalation of an aerosol containing 1.7 ± 0.13 mg/m3 of active chlorine. The hematological and biochemical parameters of the blood of experimental animals have been determined, as well as specific parameters: the activity of cathepsins B and L, catalase, and α1-antitrypsin. Histological study of the lungs of animals has been carried out. RESULTS: During inhalation and 14 days after it, no death of the animals was observed; the behavior, appearance, and weight gain did not differ from the control group. There were no significant deviations in hematological parameters, except the decrease in the level of platelets. The biochemical study showed slight changes in the activity of alkaline phosphatase and aspartate aminotransferase on the 1st day after inhalation; these parameters returned to normal within 14 days of observation. Specific biochemical parameters did not show the development of oxidative stress. No specific histological pathologies of lung tissue have been found. CONCLUSIONS: Thus, the studied electrochemically generated sodium hypochlorite solution under single inhalation exposure in aerosol form practically does not cause a toxic effect. The data obtained allow classifying such solution to the 4th (or even 5th - after additional studies) class of toxicity in accordance with Globally Harmonized System of Classification and Labeling of Chemicals.

Skin barrier response to active chlorine hand disinfectant-An experimental study comparing skin barrier response to active chlorine hand disinfectant and alcohol-based hand rub on healthy skin and eczematous skin.

BACKGROUND: Alcohol-based hand rub (ABHR) is widely used for hand disinfection in the health care sector. ABHR is, however, known to cause discomfort when applied on damaged skin emphasizing the unmet need for alternative and better tolerated types of disinfectants. Active chlorine hand disinfectants (ACHDs) are potential new candidates; however, the effect on the skin barrier function compared to ABHR remains to be assessed. MATERIALS AND METHODS: In Study A, the forearm skin of healthy adults was repeatedly exposed to ACHD and ABHR. Skin barrier function was assessed by measurement of transepidermal water loss, electrical conductance, pH, and erythema at baseline and at follow-up after 2 days, and subjective discomfort was likewise assessed. Study B was performed in the same way; however, in order to induce an experimental irritant contact dermatitis, sodium lauryl sulfate patch tests were applied to forearms before exposure to ACHD and ABHR. RESULTS: In both studies, the skin barrier function was unaffected after repetitive exposure to ACHD and ABHR, and with no significant differences between the products. Subjective discomfort was reported as sporadic or very mild in relation to both products. CONCLUSION: Our results illustrate that use of ACHD does not affect the skin barrier function negatively, neither in intact skin nor in skin with experimentally induced contact dermatitis. Future studies should include real-life evaluation of skin barrier function and subjective discomfort following ACHD use in individuals with and without hand eczema.

Copper Oxide Nanoparticle-Induced Acute Inflammatory Response and Injury in Murine Lung Is Ameliorated by Synthetic Secoisolariciresinol Diglucoside (LGM2605).

Metal-oxide nanoparticles (MO-NPs), such as the highly bioreactive copper-based nanoparticles (CuO-NPs), are widely used in manufacturing of hundreds of commercial products. Epidemiological studies correlated levels of nanoparticles in ambient air with a significant increase in lung disease. CuO-NPs, specifically, were among the most potent in a set of metal-oxides and carbons studied in parallel regarding DNA damage and cytotoxicity. Despite advances in nanotoxicology research and the characterization of their toxicity, the exact mechanism(s) of toxicity are yet to be defined. We identified chlorination toxicity as a damaging consequence of inflammation and myeloperoxidase (MPO) activation, resulting in macromolecular damage and cell damage/death. We hypothesized that the inhalation of CuO-NPs elicits an inflammatory response resulting in chlorination damage in cells and lung tissues. We further tested the protective action of LGM2605, a synthetic small molecule with known scavenging properties for reactive oxygen species (ROS), but most importantly, for active chlorine species (ACS) and an inhibitor of MPO. CuO-NPs (15 µg/bolus) were instilled intranasally in mice and the kinetics of the inflammatory response in lungs was evaluated 1, 3, and 7 days later. Evaluation of the protective action of LGM2605 was performed at 24 h post-challenge, which was selected as the peak acute inflammatory response to CuO-NP. LGM2605 was given daily via gavage to mice starting 2 days prior to the time of the insult (100 mg/kg). CuO-NPs induced a significant inflammatory influx, inflammasome-relevant cytokine release, and chlorination damage in mouse lungs, which was mitigated by the action of LGM2605. Preventive action of LGM2605 ameliorated the adverse effects of CuO-NP in lung.

Degradation of Paracetamol and Its Oxidation Products in Surface Water by Electrochemical Oxidation.

Paracetamol and its toxic transformation products have been found in surface water, wastewater, and drinking water. Effective methods to degrade these products must be found to reduce their detrimental effects on microorganisms in aquatic systems and minimize the concern on human health. Thus, this study looked into the electrochemical oxidation of paracetamol and its oxidation products on surface water, and results were compared with those of paracetamol synthetic solution oxidation. Degradation of paracetamol was conducted using a stainless steel electrode cell, a pH of 3, and direct current densities of 5.7 mA/cm2 (6 V) and 7.6 mA/cm2 (12 V). For both current densities applied, the pharmaceutical and its oxidation products observed by high-performance liquid chromatography with diode-array detection (HPLC-DAD) at 254 nm were totally degraded. Faster degradation of paracetamol was observed at a higher current density. Indeed, 95% of paracetamol was oxidized in only 15 min at the 7.6 mA/cm2 current density. In comparison to the paracetamol synthetic solution's oxidation, degradation of paracetamol was faster in the surface water than the synthetic solution, at 5.7 mA/cm2. Nevertheless, at 7.6 mA/cm2, total degradation of paracetamol in surface water was delayed up to 40 min, versus 7.5 min in the synthetic solution. Three oxidation products, observed by HPLC-DAD at 254 nm, were fully oxidized. In comparison with the paracetamol synthetic solution, degradation of the oxidation products in surface water was faster than in synthetic solutions for both current densities. Furthermore, the 7.6 mA/cm2 current density resulted in faster degradation of oxidation products. Results obtained from this work are promising for practical applications because short reaction times and low current densities are needed for degradation of paracetamol and its oxidation products. These densities can be potentially supplied by photovoltaic cells.

Field data analysis of active chlorine-containing stormwater samples.

Many municipalities in Canada and all over the world use chloramination for drinking water secondary disinfection to avoid DBPs formation from conventional chlorination. However, the long-lasting monochloramine (NH2Cl) disinfectant can pose a significant risk to aquatic life through its introduction into municipal storm sewer systems and thus fresh water sources by residential, commercial, and industrial water uses. To establish general total active chlorine (TAC) concentrations in discharges from storm sewers, the TAC concentration was measured in stormwater samples in Edmonton, Alberta, Canada, during the summers of 2015 and 2016 under both dry and wet weather conditions. The field-sampling results showed TAC concentration variations from 0.02 to 0.77 mg/L in summer 2015, which exceeds the discharge effluent limit of 0.02 mg/L. As compared to 2015, the TAC concentrations were significantly lower during the summer 2016 (0-0.24 mg/L), for which it is believed that the higher precipitation during summer 2016 reduced outdoor tap water uses. Since many other cities also use chloramines as disinfectants for drinking water disinfection, the TAC analysis from Edmonton may prove useful for other regions as well. Other physicochemical and biological characteristics of stormwater and storm sewer biofilm samples were also analyzed, and no significant difference was found during these two years. Higher density of AOB and NOB detected in the storm sewer biofilm of residential areas - as compared with other areas - generally correlated to high concentrations of ammonium and nitrite in this region in both of the two years, and they may have contributed to the TAC decay in the storm sewers. The NH2Cl decay laboratory experiments illustrate that dissolved organic carbon (DOC) concentration is the dominant factor in determining the NH2Cl decay rate in stormwater samples. The high DOC concentrations detected from a downstream industrial sampling location may contribute to a high stormwater NH2Cl decay rate in this area.

Gamma-irradiation produces active chlorine species (ACS) in physiological solutions: Secoisolariciresinol diglucoside (SDG) scavenges ACS - A novel mechanism of DNA radioprotection.

BACKGROUND: Secoisolariciresinol diglucoside (SDG), the main lignan in whole grain flaxseed, is a potent antioxidant and free radical scavenger with known radioprotective properties. However, the exact mechanism of SDG radioprotection is not well understood. The current study identified a novel mechanism of DNA radioprotection by SDG in physiological solutions by scavenging active chlorine species (ACS) and reducing chlorinated nucleobases. METHODS: The ACS scavenging activity of SDG was determined using two highly specific fluoroprobes: hypochlorite-specific 3'-(p-aminophenyl) fluorescein (APF) and hydroxyl radical-sensitive 3'-(p-hydroxyphenyl) fluorescein (HPF). Dopamine, an SDG structural analog, was used for proton (1)H NMR studies to trap primary ACS radicals. Taurine N-chlorination was determined to demonstrate radiation-induced generation of hypochlorite, a secondary ACS. DNA protection was assessed by determining the extent of DNA fragmentation and plasmid DNA relaxation following exposure to ClO(-) and radiation. Purine base chlorination by ClO(-) and γ-radiation was determined by using 2-aminopurine (2-AP), a fluorescent analog of 6-aminopurine. RESULTS: Chloride anions (Cl(-)) consumed >90% of hydroxyl radicals in physiological solutions produced by γ-radiation resulting in ACS formation, which was detected by (1)H NMR. Importantly, SDG scavenged hypochlorite- and γ-radiation-induced ACS. In addition, SDG blunted ACS-induced fragmentation of calf thymus DNA and plasmid DNA relaxation. SDG treatment before or after ACS exposure decreased the ClO(-) or γ-radiation-induced chlorination of 2-AP. Exposure to γ-radiation resulted in increased taurine chlorination, indicative of ClO(-) generation. NMR studies revealed formation of primary ACS radicals (chlorine atoms (Cl) and dichloro radical anions (Cl2¯)), which were trapped by SDG and its structural analog dopamine. CONCLUSION: We demonstrate that γ-radiation induces the generation of ACS in physiological solutions. SDG treatment scavenged ACS and prevented ACS-induced DNA damage and chlorination of 2-aminopurine. This study identified a novel and unique mechanism of SDG radioprotection, through ACS scavenging, and supports the potential usefulness of SDG as a radioprotector and mitigator for radiation exposure as part of cancer therapy or accidental exposure.

Evaluation of the formation of oxidants and by-products using Pt/Ti, RuO2/Ti, and IrO2/Ti electrodes in the electrochemical process.

The aim of this study was to evaluate the formation of oxidants and by-products by using different electrode materials, such as Pt/Ti, RuO2/Ti, and IrO2/Ti, in the electrochemical process. The harmful by-products ClO3- and ClO4- were formed during the electrolysis of a Cl- electrolyte solution, as well as active chlorine, which is the most common water disinfectant. With regard to drinking water treatment, the most efficient electrode was defined as that leading to a higher formation of active chlorine and a lower formation of hazardous by-products. Overall, it was found that the Pt/Ti electrode should not be used for drinking water treatment applications, while the IrO2/Ti and RuO2/Ti electrodes are ideal for use.

Physicochemical properties of cassava starch oxidized by sodium hypochlorite.

In this work, cassava starch was modified by treatment with sodium hypochlorite (NaClO) at different concentrations (0.8, 2.0 and 5.0 % of active chlorine) and selected physicochemical properties of the oxidized starches were investigated. The native and modified samples were evaluated considering moisture, carboxyl content, apparent viscosity, susceptibility to syneresis, mid-infrared spectroscopy and crystallinity index. The treatment with NaClO resulted in alterations in carboxyl content of the oxidized starches that increased with increasing concentration of the oxidant. Oxidized starches also showed higher susceptibility to syneresis, as assessed by the release of liquid during freezing and thawing. Apparent viscosity analysis showed decrease in peak viscosity of the oxidized starches. X-ray diffractograms showed that the oxidation influenced the extent of cassava starch relative crystallinity found to lie between 34.4 % (native) and 39.9 % (2.0 % active chlorine). The infrared spectra are sensitive to structural changes on starch macromolecules and presented characteristic peaks as C-O-C of the six carbon glucose ring absorbs at 1,150-1,085 cm(-1) and due to axial deformation these bands changed with the crystal structure of the starch samples.

Modified activated carbon material-assisted electrochemical disinfection effectively inactivate antibiotic-resistant bacteria.

ABSTRACTThe production and widespread transmission of antibiotic-resistant bacteria (ARB) pose an emerging threat to global public health. Electrochemical disinfection (ED) is an environmentally friendly disinfection technology widely utilized to inactivate ARB. This study explored the effect of modified activated carbon material (MACM) assisted ED on multi-ARB inactivation and the regeneration ability. The established ED technique was proven to be effective in inactivating multi-resistant ARB. Specifically, a 5-log ARB removal was achieved within 30 min treatment of MACM-assisted ED at 2.5 V. Additionally, no ARB regrowth was observed, indicating a permanent inactivation of ARB. The high level of reactive chlorine induced by MACM electrolysis was stressful to the ARB. Reactive chlorine led to overproduction of reactive oxygen species and damage of cell membranes in cells, accelerating the inactivation of ARB. Conclusively, the MACM-assisted ED method demonstrated efficient performance for ARB inactivation, implying this method is a promising alternative to traditional disinfection methods in countering ARB transmission.

Effects of intensive chlorine disinfection on nitrogen and phosphorus removal in WWTPs.

The increased use of disinfection since the pandemic has led to increased effective chlorine concentration in municipal wastewater. Whereas, the specific impacts of active chlorine on nitrogen and phosphorus removal, the mediating communities, and the related metabolic activities in wastewater treatment plants (WWTPs) lack systematic investigation. We systematically analyzed the influences of chlorine disinfection on nitrogen and phosphorus removal activities using activated sludge from five full-scale WWTPs. Results showed that at an active chlorine concentration of 1.0 mg/g-SS, the nitrogen and phosphorus removal systems were not significantly affected. Major effects were observed at 5.0 mg/g-SS, where the nitrogen and phosphorus removal efficiency decreased by 38.9 % and 44.1 %, respectively. At an active chlorine concentration of 10.0 mg/g-SS, the nitrification, denitrification, phosphorus release and uptake activities decreased by 15.1 %, 69.5-95.9 %, 49.6 % and 100 %, respectively. The proportion of dead cells increased by 6.1 folds. Reverse transcriptional quantitative polymerase chain reaction (RT-qPCR) analysis showed remarkable inhibitions on transcriptions of the nitrite oxidoreductase gene (nxrB), the nitrite reductase genes (nirS and nirK), and the nitrite reductase genes (narG). The nitrogen and phosphorus removal activities completely disappeared with an active chlorine concentration of 25.0 mg/g-SS. Results also showed distinct sensitivities of different functional bacteria in the activated sludge. Even different species within the same functional group differ in their susceptibility. This study provides a reference for the understanding of the threshold active chlorine concentration values which may potentially affect biological nitrogen and phosphorus removal in full-scale WWTPs, which are expected to be beneficial for decision-making in WWTPs to counteract the potential impacts of increased active chlorine concentrations in the influent wastewater.

Complete abatement of the antibiotic ciprofloxacin from water using a visible-light-active nanostructured photoanode.

The wide use of the fluoroquinolone antibiotic ciprofloxacin (CIP), combined with its limited removal in wastewater treatment plants, results in a dangerous accumulation in natural water. Here, the complete degradation of CIP by photoelectrocatalysis (PEC), using an FTO/ZnO/TiO2/Ag2Se photoanode that is responsive to blue light, has been investigated. A slow antibiotic concentration decay was found in 0.050 M Na2SO4 under the oxidizing action of holes and OH photogenerated at the anode surface. The degradation was strongly enhanced in 0.070 M NaCl due to mediated oxidation by electrogenerated active chlorine. The latter process became faster at pH 7.0, with total abatement of CIP at concentrations below 2.5 mg L-1 operating at a bias potential of +0.8 V. The performance was enhanced when increasing the anodic potential and decreasing the initial drug content. The use of solar radiation from a simulator was also beneficial, owing to the greater lamp power. In contrast, the electrochemical oxidation in the dark yielded a poor removal, thus confirming the critical role of oxidants formed under light irradiation. The generation of holes and OH was confirmed from tests with specific scavengers like ammonium oxalate and tert-butanol, respectively. The prolonged usage of the photoanode affected its performance due to poisoning of its active centers by degradation by-products, although a good PEC reproducibility was obtained upon surface cleaning.

Oxidation of organics in water by active chlorine performed in microfluidic electrochemical reactors: a new way to improve the performances of the process.

Wastewater polluted by organics can be treated by using electro-generated active chlorine, even if this promising route presents some important drawbacks such as the production of chlorinated by-products. Here, for the first time, this process was studied in a microfluidic electrochemical reactor with a very small inter-electrode distance (145 µm) using a water solution of NaCl and phenol and a BDD anode. The potential production of chloroacetic acids, chlorophenols, carboxylic acids, chlorate and perchlorate was carefully evaluated. It was shown, for the first time, up to our knowledge, that the use of the microfluidic device allows to perform the treatment under a continuous mode and to achieve higher current efficiencies and a lower generation of some important by-products such as chlorate and perchlorate. As an example, the use of the microfluidic apparatus equipped with an Ag cathode allowed to achieve a high removal of total organic carbon (about 76%) coupled with a current efficiency of 17% and the production of a small amount of chlorate (about 30 ppm) and no perchlorate. The effect of many parameters (namely, flow rate, current density and nature of cathode) was also investigated.

Boosting seawater denitrification in an electrochemical flow cell.

Nitrogen compounds in current seawater treatment processes typically are converted to nitrate, threatening seawater quality and marine ecology. Electrochemical denitrification is a promising technique, but its efficiency is severely limited by the presence of excess chloride ions. In this work, a flow-through cell went through an on-demand chlorine-mediated electrochemical-chemical tandem reaction process was designed for efficient seawater denitrification. Equipped with ultrathin cobalt-based nanosheets as the cathode catalyst and commercial IrO2-RuO2/Ti as the anode, the newly designed flow-through cell achieved nitrate removal efficiency that was about 50 times greater than the batch cell and nearly 100 % N2 selectivity. Moreover, nitrite and ammonia can also be removed with over 93 % efficiency in total nitrogen (TN) removal. Furthermore, the concentration of active chlorine in the effluent could be adjusted within two orders of magnitude, enabling on-demand release of active chlorine. Finally, this flow-through cell reduced the TN of actual mariculture tailwater (40.1 mg N L-1 nitrate) to only 5.7 mg N L-1, meeting the discharge standard for aquaculture tailwater of Fujian, China. This work demonstrates the paradigm of deep denitrification from ultra-concentrated chlorine ion wastewater using an on-demand active chlorine-mediated electrochemical-chemical tandem reaction process.