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.

Síntomas depresivos en una muestra de mujeres con hipotiroidismo subclínico y su relación con los cloratos del agua del grifo / Depressive symptoms in a sample of women with subclinical hypothyroidism and their relationship to chlorates in tap water

Introducción: en el hipotiroidismo subclínico pueden aparecer síntomas depresivos y su presencia suele facilitar la instauración de un tratamiento de reemplazo; sin embargo, estudios recientes no han encontrado una asociación entre ambos. Por otra parte, la función tiroidea puede verse afectada por disruptores endocrinos y, algunos de ellos, como los cloratos, pueden encontrarse en el agua que bebemos. Objetivos: conocer si el tipo de consumo de agua puede influir en la aparición de síntomas depresivos en pacientes con hipotiroidismo subclínico. Métodos: participaron 96 mujeres con hipotiroidismo subclínico, sin tratamiento tiroideo, de un área de salud de España. Estudiamos, entre otras variables, la presencia de síntomas depresivos, el tipo de consumo de agua (grifo/embotellada o manantial) y el nivel de cloratos en el agua del grifo. Resultados: el 41,7 % (40) de las mujeres presentaban síntomas depresivos y estos se relacionaban con el consumo de agua del grifo (p = 0,001), resultando este un predictor confiable (OR: 27,79; p = 0,007). El nivel de cloratos en el agua del grifo era de 250 µg/L, valor situado en el límite máximo permitido por la ley. Conclusiones: en mujeres con hipotiroidismo subclínico, la exposición crónica a cloratos en el agua, en niveles autorizados por la ley, podría favorecer la inhibición del transporte de yodo y la aparición de síntomas depresivos. Sería interesante comprobar esta hipótesis, así como su posible efecto sobre otros perfiles poblacionales.(AU)

Introduction: depressive symptoms may develop in subclinical hypothyroidism and their presence usually facilitates recognition and the establishment of replacement treatment; however, recent studies have found no association between the two. Besides, thyroid function can be affected by endocrine disruptors and some of them, such as chlorates, can be found in the water we drink. Objectives: to know if the type of water consumed may influence the development of depressive symptoms in patients with subclinical hypothyroidism. Methods: 96 women with subclinical hypothyroidism, without thyroid treatment, were enrolled. We studied, among other variables, the presence of depressive symptoms, type of water consumption (tap, bottled or spring) and the level of chlorates in the tap water. Results: 41.7 % (40) of women presented depressive symptoms and these were related to the consumption of tap water (p = 0.001), resulting in a reliable predictor (OR, 27.79; p = 0.007). Chlorate level in the tap water was 250 μg/L, a value within the maximum limit allowed by law. Conclusions: chronic exposure to chlorates in water, in women with subclinical hypo-thyroidism, at levels authorized by law, could favor the inhibition of iodine transport and the appearance of depressive symptoms. It would be interesting to test this hypothesis as well as its possible effect on other population profiles.(AU)

[Determination of perchlorate and chlorate in drinks by ultra-performance liquid chromatography-tandem mass spectrometry].

OBJECTIVE: To establish a method for determination of perchlorate and chlorate in drinks by ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS) based on isotopic internal standard method. METHODS: The perchlorate and chlorate residue in liquid drinks were extracted with methanol, in solid drinks with acetic acid solution, then centrifuged. The supernatant was cleaned-up with PSA/C18 cleanup tube. The separation of perchlorate and chlorate was carried out on a Acquity CSH fluorophenyl column(100 mm×2.1mm, 1.7 µm) and the detection was performed with tandem mass spectrometry with internal standard method for quantification. RESULTS: The peak area ratio of perchlorate and chlorate had a good linear relationship with their mass concentration within their respective linear ranges, with correlation coefficients(r) greater than 0.999. The limits of detection of perchlorate and chlorate were 0.2and 1 µg/L respectively and the limits of quantification were 0.5 and 3 µg/L respectively. The mean recoveries of two compounds were from 84.0% to 105.5% with relative standard deviations from 4.2% to 17.0% and 82.7% to 112.1% with relative standard deviations from 5.5% to 18.4%(n=6), respectively. The perchlorates in 11 kinds of beverage samples were 0.53-4.12 µg/L, chlorates were 3.27-61.86 µg/L. CONCLUSION: This method is simple, sensitive, accurate and reliable, which is suitable for the determination of perchlorate and chlorate in drinks.

[Depressive symptoms in a sample of women with subclinical hypothyroidism and their relationship to chlorates in tap water]. / Síntomas depresivos en una muestra de mujeres con hipotiroidismo subclínico y su relación con los cloratos del agua del grifo.

Introduction: Introduction: depressive symptoms may develop in subclinical hypothyroidism and their presence usually facilitates recognition and the establishment of replacement treatment; however, recent studies have found no association between the two. Besides, thyroid function can be affected by endocrine disruptors and some of them, such as chlorates, can be found in the water we drink. Objectives: to know if the type of water consumed may influence the development of depressive symptoms in patients with subclinical hypothyroidism. Methods: 96 women with subclinical hypothyroidism, without thyroid treatment, were enrolled. We studied, among other variables, the presence of depressive symptoms, type of water consumption (tap, bottled or spring) and the level of chlorates in the tap water. Results: 41.7 % (40) of women presented depressive symptoms and these were related to the consumption of tap water (p = 0.001), resulting in a reliable predictor (OR, 27.79; p = 0.007). Chlorate level in the tap water was 250 µg/L, a value within the maximum limit allowed by law. Conclusions: chronic exposure to chlorates in water, in women with subclinical hypothyroidism, at levels authorized by law, could favor the inhibition of iodine transport and the appearance of depressive symptoms. It would be interesting to test this hypothesis as well as its possible effect on other population profiles.

Introducción: Introducción: en el hipotiroidismo subclínico pueden aparecer síntomas depresivos y su presencia suele facilitar la instauración de un tratamiento de reemplazo; sin embargo, estudios recientes no han encontrado una asociación entre ambos. Por otra parte, la función tiroidea puede verse afectada por disruptores endocrinos y, algunos de ellos, como los cloratos, pueden encontrarse en el agua que bebemos. Objetivos: conocer si el tipo de consumo de agua puede influir en la aparición de síntomas depresivos en pacientes con hipotiroidismo subclínico. Métodos: participaron 96 mujeres con hipotiroidismo subclínico, sin tratamiento tiroideo, de un área de salud de España. Estudiamos, entre otras variables, la presencia de síntomas depresivos, el tipo de consumo de agua (grifo/embotellada o manantial) y el nivel de cloratos en el agua del grifo. Resultados: el 41,7 % (40) de las mujeres presentaban síntomas depresivos y estos se relacionaban con el consumo de agua del grifo (p = 0,001), resultando este un predictor confiable (OR: 27,79; p = 0,007). El nivel de cloratos en el agua del grifo era de 250 µg/L, valor situado en el límite máximo permitido por la ley. Conclusiones: en mujeres con hipotiroidismo subclínico, la exposición crónica a cloratos en el agua, en niveles autorizados por la ley, podría favorecer la inhibición del transporte de yodo y la aparición de síntomas depresivos. Sería interesante comprobar esta hipótesis, así como su posible efecto sobre otros perfiles poblacionales.

Chlorate and perchlorate in tea leaves from major producing regions in China and related human exposure risk.

Chlorate and perchlorate are emerging pollutants that may interfere with thyroid function. Since they are highly water soluble, chlorate and perchlorate in tea leaves cause health concerns but have scarcely been studied. In this study, chlorate and perchlorate concentrations in 216 tea samples from different regions of China were determined. Perchlorate was detected in all the samples with a median concentration of 44.1 µg kg-1, while the chlorate detection frequency was 15.7%. We observed regional differences in perchlorate contents in tea leaves, with the highest quantity found in the central region of China. Except for dark tea, the concentration of perchlorate in tea infusions decreased with the increased number of times the tea leaves were brewed. The hazard quotients (HQs) of chlorate and perchlorate in all the samples were less than 1, suggesting negligible health risks caused by these pollutants from tea consumption. To the best of our knowledge, this is the first study to investigate chlorate and perchlorate contamination in tea infusions by simulating brewing behavior.

Enhancing Aqueous Chlorate Reduction Using Vanadium Redox Cycles and pH Control.

Chlorate (ClO3-) is a toxic oxyanion pollutant from industrial wastes, agricultural applications, drinking water disinfection, and wastewater treatment. Catalytic reduction of ClO3- using palladium (Pd) nanoparticle catalysts exhibited sluggish kinetics. This work demonstrates an 18-fold activity enhancement by integrating earth-abundant vanadium (V) into the common Pd/C catalyst. X-ray photoelectron spectroscopy and electrochemical studies indicated that VV and VIV precursors are reduced to VIII in the aqueous phase (rather than immobilized on the carbon support) by Pd-activated H2. The VIII/IV redox cycle is the predominant mechanism for the ClO3- reduction. Further reduction of chlorine intermediates to Cl- could proceed via VIII/IV and VIV/V redox cycles or direct reduction by Pd/C. To capture the potentially toxic V metal from the treated solution, we adjusted the pH from 3 to 8 after the reaction, which completely immobilized VIII onto Pd/C for catalyst recycling. The enhanced performance of reductive catalysis using a Group 5 metal adds to the diversity of transition metals (e.g., Cr, Mo, Re, Fe, and Ru in Groups 6-8) for water pollutant treatment via various unique mechanisms.

Insights into antibiotic cefaclor mineralization by electro-Fenton and photoelectro-Fenton processes using a Ti/Ti4O7 anode: Performance, mechanism, and toxic chlorate/perchlorate formation.

A comparative degradation of antibiotic cefaclor (CEC) between Ti/Ti4O7 and Ti/RuO2 anodes, in terms of degradation kinetics, mineralization efficiency, and formation of toxic chlorate (ClO3-) and perchlorate (ClO4-), was performed with electrochemical-oxidation (EO), electro-Fenton (EF), and photoelectro-Fenton (PEF) processes. Besides, CEC degradation by EF with boron-doped diamond (BDD) anode was also tested. Results showed CEC decays always followed pseudo-first-order kinetics, with increasing apparent rate constants in the sequence of EO < EF < PEF. The mineralization efficiency of the processes with Ti/Ti4O7 anode was higher than that of Ti/RuO2 anode, but slightly lower than that of BDD anode. Under the optimal conditions, 94.8% mineralization was obtained in Ti/Ti4O7-PEF, which was much higher than 64.4% in Ti/RuO2-PEF. The use of Ti/RuO2 gave no generation of ClO3- or ClO4-, while the use of Ti/Ti4O7 yielded a small amount of ClO3- and trace amounts of ClO4-. Conversely, the use of BDD led to the highest generation of ClO3- and ClO4-. The reaction mechanism was studied systematically by detecting the generated H2O2 and •OH. The initial N of CEC was released as NH4+ and, in smaller proportion, as NO3-. Four short-chain carboxylic acids and nine aromatic intermediates were also detected, a possible reaction sequence for CEC mineralization was finally proposed.

Purified Chlorine Dioxide as an Alternative to Chlorine Disinfection to Minimize Chlorate Formation During Postharvest Produce Washing.

The washwater used to wash produce within postharvest washing facilities frequently contains high chlorine concentrations to prevent pathogen cross-contamination. To address concerns regarding the formation and uptake of chlorate (ClO3-) into produce, this study evaluated whether switching to chlorine dioxide (ClO2) could reduce chlorate concentrations within the produce. Because ClO2 exhibits lower disinfectant demand than chlorine, substantially lower concentrations can be applied. However, ClO3- can form through several pathways, particularly by reactions between ClO2 and the chlorine used to generate ClO2 via reaction with chlorite (ClO2-) or chlorine that forms when ClO2 reacts with produce. This study demonstrates that purging ClO2 from the chlorine and ClO2- mixture used for its generation through a trap containing ClO2- can scavenge chlorine, substantially reducing ClO3- concentrations in ClO2 stock solutions. Addition of low concentrations of ammonia to the produce washwater further reduced ClO3- formation by binding the chlorine produced by ClO2 reactions with produce as inactive chloramines without scavenging ClO2. While chlorate concentrations in lettuce, kale, and broccoli exceeded regulatory guidelines during treatment with chlorine, ClO3- concentrations were below regulatory guidelines for each of these vegetables when treated with ClO2 together with these two purification measures. Switching to purified ClO2 also reduced the concentrations of lipid-bound oleic acid chlorohydrins and protein-bound chlorotyrosines, which are exemplars of halogenated byproducts formed from disinfectant reactions with biomolecules within produce.

Quantification of Chlorate and Perchlorate in a Broad Range of Food Commodities, Including Baby Food, Nutritional Formulas, and Ingredients by LC-MS/MS: First Action AOAC 2022.06.

BACKGROUND: Chlorate is an effective herbicide, but also a byproduct of chlorinating agents used to disinfect water, which is one of the reasons why it is regularly found in food. Perchlorate is a ubiquitous contaminant, which is naturally occurring in the environment but also released from anthropogenic sources such as the industrial use of certain natural fertilizers. Chlorate affects the hematological system, and perchlorate the thyroid. OBJECTIVE: Implement and validate a simple and robust analytical method for the accurate determination of chlorate and perchlorate in baby food, infant and adult formulas, and ingredients thereof, which is suited for its application in routine environments where a broad variety of food commodities must be analyzed simultaneously. METHOD: Typically, analytes are extracted with a mixture of water, acidified methanol, and dichloromethane. Optionally, for dairy products and byproducts, extraction can be performed with water, acidified methanol, and EDTA, followed by two steps of cleanup (freezing out and dispersive solid-phase extraction with C18 in acetonitrile). Quantitative determination is carried out by isotopic dilution liquid chromatography tandem mass spectrometry (LC-MS/MS). RESULTS: The method was single-laboratory validated in five Nestlé Quality Assurance Centers (NQACs) in a comprehensive range of representative matrixes of different categories such as baby foods, infant/adult formulas, and ingredients, with results generally in agreement with the acceptance criteria of the Standard Method Performance Requirement (SMPR®) 2021.001 defined by AOAC INTERNATIONAL, in terms of representative matrixes validated, LOQs, trueness, and precision.The data generated during validation show that the method proposed is simple, accurate and robust enough to be implemented and applied in routine environments. CONCLUSION: The data generated during validation show that the method proposed is simple, accurate and robust enough to be implemented and applied in routine environments. HIGHLIGHTS: The AOAC Expert Review Panel approved the present method as AOAC Official First Action 2022.06.

Isolation and identification of chlorate-reducing Hafnia sp. from milk.

Chlorate has become a concern in the food and beverage sector, related to chlorine sanitizers in industrial food production and water treatment. It is of particular concern to regulatory bodies due to the negative health effects of chlorate exposure. This study investigated the fate of chlorate in raw milk and isolated bacterial strains of interest responsible for chlorate breakdown. Unpasteurized milk was demonstrated to have a chlorate-reducing capacity, breaking down enriched chlorate to undetectable levels in 11 days. Further enrichment and isolation using conditions specific to chlorate-reducing bacteria successfully isolated three distinct strains of Hafnia paralvei. Chlorate-reducing bacteria were observed to grow in a chlorate-enriched medium with lactate as an electron donor. All isolated strains were demonstrated to reduce chlorate in liquid medium; however, the exact mechanism of chlorate degradation was not definitively identified in this study.

Engineering of a Bacterial Biosensor for the Detection of Chlorate in Food.

Chlorate can contaminate food due to the use of chlorinated water for processing or equipment disinfection. Chronic exposure to chlorate in food and drinking water is a potential health concern. The current methods for detecting chlorate in liquids and foods are expensive and not easily accessible to all laboratories, highlighting an urgent need for a simple and cost-effective method. The discovery of the adaptation mechanism of Escherichia coli to chlorate stress, which involves the production of the periplasmic Methionine Sulfoxide Reductase (MsrP), prompted us to use an E. coli strain with an msrP-lacZ fusion as a biosensor for detecting chlorate. Our study aimed to optimize the bacterial biosensor's sensitivity and efficiency to detect chlorate in various food samples using synthetic biology and adapted growth conditions. Our results demonstrate successful biosensor enhancement and provide proof of concept for detecting chlorate in food samples.

Perchlorate and chlorate assessment in drinking water in northern Chilean cities.

Perchlorate and chlorate are endocrine disruptors considered emerging contaminants (ECs). Both oxyanions are commonly associated with anthropogenic contamination from fertilizers, pesticides, explosives, and disinfection byproducts. However, the soils of the Atacama Desert are the most extensive natural reservoirs of perchlorate in the world, compromising drinking water sources in northern Chile. Field campaigns were carried (2014-2018) to assess the presence of these ECs in the water supply networks of twelve Chilean cities. Additionally, the occurrence of perchlorate, chlorate and other anions typically observed in drinking water matrices of the Atacama Desert (i.e., nitrate, chloride, sulfate) was evaluated using a Spearman correlation analysis to determine predictors for perchlorate and chlorate. High concentrations of perchlorate (up to 114.48 µg L-1) and chlorate (up to 9650 µg L-1) were found in three northern cities. Spatial heterogeneities were observed in the physicochemical properties and anion concentrations of the water supply network. Spearman correlation analysis indicated that nitrate, chloride, and sulfate were not useful predictors for the presence of perchlorate and chlorate in drinking water in Chile. Hence, this study highlights the need to establish systematic monitoring, regulation, and treatment for these EC of drinking water sources in northern Chilean cities for public health protection.

Unexpected trends for the formation of chlorate and bromate during the photolysis of chlorine in bromide-containing water.

Solar photolysis of free chlorine (solar/chlorine) in bromide-containing water occurs under various scenarios, such as chlorinated reservoirs and outdoor swimming pools, and the formation of chlorate and bromate is an important issue in the system. We reported unexpected trends for the formation of chlorate and bromate in the solar/chlorine system. Excess chlorine inhibited the formation of bromate, i.e., increasing chlorine dosages from 50 to 100 µM reduced the bromate yield from 6.4 to 1.2 µM in solar/chlorine at 50 µM bromide and pH 7. The yield of bromate in solar/chlorine at 100 µM chlorine and 50 µM bromide in 240 min was 18.8% of that at 50 µM bromine only. The underlying mechanism was that HOCl can react with bromite (BrO2-) to form HOClOBrO-, whose multi-step transformation finally formed chlorate as the major product and bromate as the minor product. This reaction overwhelmed the oxidation of bromite to form bromate by reactive species, such as •OH, BrO• and ozone. On the other hand, the presence of bromide greatly enhanced the formation of chlorate. Increasing bromide concentrations from 0 to 50 µM enhanced the chlorate yields from 2.2 to 7.0 µM at 100 µM chlorine. The absorbance of bromine was higher than that of chlorine, thus the photolysis of bromine formed higher levels of bromite at higher bromide concentrations. Then, bromite rapidly reacted with HOCl to form HOClOBrO- and it further transformed to chlorate. Additionally, 1 mg L-1 NOM had a negligible effect on bromate yields in solar/chlorine at 50 µM bromide, 100 µM chlorine and pH 7. This study demonstrated a new pathway of chlorate and bromate formation in the solar/chlorine system with bromide.

Lipid Oxidation and Volatile Compounds of Almonds as Affected by Gaseous Chlorine Dioxide Treatment to Reduce Salmonella Populations.

The effects of gaseous chlorine dioxide (ClO2) treatment, applied to inactivate Salmonella, on lipid oxidation, volatile compounds, and chlorate levels of dehulled almonds were evaluated during a 3 month accelerated storage at 39 °C. At treatment levels that yielded a 2.91 log reduction of Salmonella, ClO2 promoted lipid oxidation as indicated by increased peroxide values, total acid number, conjugated dienes, and thiobarbituric acid-reactive substances. Furthermore, several chlorine-containing volatile compounds including trichloromethane, 1-chloro-2-propanol, 1,1,1-trichloro-2-propanol, and 1,3-dichloro-2-propanol were identified in ClO2-treated samples. However, all the volatile chlorine-containing compounds decreased during the 3 months of storage. Chlorate (26.4 ± 5.1 µg/g) was found on the ClO2-treated samples. The amounts of non-ethanol alcohols, aldehydes, and carboxylic acids increased following ClO2 treatments. Some volatiles such as 2,3-butanediol that were present in non-treated samples became non-detectable during post-ClO2 treatment storage. Overall, our results demonstrated that gaseous ClO2 treatment promoted lipid oxidation, generation of volatiles of lipid origin, and several chlorine-containing compounds.

Overlooked Cytotoxicity and Genotoxicity to Mammalian Cells Caused by the Oxidant Peroxymonosulfate during Wastewater Treatment Compared with the Sulfate Radical-Based Ultraviolet/Peroxymonosulfate Process.

Byproduct formation (chlorate, bromate, organic halogen, etc.) during sulfate radical (SO4•-)-based processes like ultraviolet/peroxymonosulfate (UV/PMS) has aroused widespread concern. However, hypohalous acid (HOCl and HOBr) can form via two-electron transfer directly from PMS, thus leading to the formation of organic halogenated byproducts as well. This study found both PMS alone and UV/PMS can increase the toxicity to mammalian cells of wastewater, while the UV/H2O2 decreased the toxicity. Cytotoxicity of two wastewater samples increased from 5.6-8.3 to 15.7-29.9 mg-phenol/L, and genotoxicity increased from 2.8-3.1 to 5.8-12.8 µg 4-NQO/L after PMS treatment because of organic halogen formation. Organic halogen formation from bromide rather than chloride was found to dominate the toxicity increase. The SO4•--based process UV/PMS led to the formation of both organic halogen and inorganic bromate and chlorate. However, because of the very low concentration (<20 µg/L) and relatively low toxicity of bromate and chlorate, contributions of inorganic byproducts to toxicity increase were negligible. PMS would not form chlorate and bromate, but it generated a higher concentration of total organic halogen, thus leading to a more toxic treated wastewater than UV/PMS. UV/PMS formed less organic halogen and toxicity because of the destruction of byproducts by UV irradiation and the removal of byproduct precursors. Currently, many studies focused on the byproducts bromate and chlorate during SO4•--based oxidation processes. This work revealed that the oxidant PMS even needs more attention because it caused higher toxicity due to more organic halogen formation.

Preparation and Synergy of Supported Ru0 and Pd0 for Rapid Chlorate Reduction at pH 7.

Chlorate (ClO3-) is a common water pollutant due to its gigantic scale of production, wide applications in agriculture and industry, and formation as a toxic byproduct in various water treatment processes. This work reports on the facile preparation, mechanistic elucidation, and kinetic evaluation of a bimetallic catalyst for highly active ClO3- reduction into Cl-. Under 1 atm H2 and 20 °C, PdII and RuIII were sequentially adsorbed and reduced on a powdered activated carbon support, affording Ru0-Pd0/C from scratch within only 20 min. The Pd0 particles significantly accelerated the reductive immobilization of RuIII as >55% dispersed Ru0 outside Pd0. At pH 7, Ru-Pd/C shows a substantially higher activity of ClO3- reduction (initial turnover frequency >13.9 min-1 on Ru0; rate constant at 4050 L h-1 gmetal-1) than reported catalysts (e.g., Rh/C, Ir/C, Mo-Pd/C) and the monometallic Ru/C. In particular, Ru-Pd/C accomplished the reduction of concentrated 100 mM ClO3- (turnover number > 11,970), whereas Ru/C was quickly deactivated. In the bimetallic synergy, Ru0 rapidly reduces ClO3- while Pd0 scavenges the Ru-passivating ClO2- and restores Ru0. This work demonstrates a simple and effective design for heterogeneous catalysts tailored for emerging water treatment needs.

Impacts of co-contaminants and dilution on perchlorate biodegradation using various carbon sources.

This research investigates the biodegradation of perchlorate in the presence of the co-contaminants nitrate and chlorate using soluble and slow-release carbon sources. In addition, the impact of bio-augmentation and dilution, which results in lower total dissolved salts (TDS) and contaminant levels, is examined. Laboratory microcosms were conducted using actual groundwater and soils from a contaminated aquifer. The results revealed that both soluble and slow-release carbon sources support biodegradation of contaminants in the sequence nitrate > chlorate > perchlorate. Degradation rates, including and excluding lag times, revealed that the overall impact of the presence of co-contaminants depends on degradation kinetics and the relative concentrations of the contaminants. When the lag time caused by the presence of the co-contaminants is considered, the degradation rates for chlorate and perchlorate were two to three times slower. The results also show that dilution causes lower initial contaminant concentrations, and consequently, slower degradation rates, which is not desirable. On the other hand, the dilution resulting from the injection of amendments to support remediation promotes desirably lower salinity levels. However, the salinity associated with the presence of sulfate does not inhibit biodegradation. The naturally occurring bacteria were able to support the degradation of all contaminants. Bio-augmentation was effective only in diluted microcosms. Proteobacteria and Firmicutes were the dominant phyla identified in the microcosms.

Chlorine redox chemistry is widespread in microbiology.

Chlorine is abundant in cells and biomolecules, yet the biology of chlorine oxidation and reduction is poorly understood. Some bacteria encode the enzyme chlorite dismutase (Cld), which detoxifies chlorite (ClO2-) by converting it to chloride (Cl-) and molecular oxygen (O2). Cld is highly specific for chlorite and aside from low hydrogen peroxide activity has no known alternative substrate. Here, we reasoned that because chlorite is an intermediate oxidation state of chlorine, Cld can be used as a biomarker for oxidized chlorine species. Cld was abundant in metagenomes from various terrestrial habitats. About 5% of bacterial and archaeal genera contain a microorganism encoding Cld in its genome, and within some genera Cld is highly conserved. Cld has been subjected to extensive horizontal gene transfer. Genes found to have a genetic association with Cld include known genes for responding to reactive chlorine species and uncharacterized genes for transporters, regulatory elements, and putative oxidoreductases that present targets for future research. Cld was repeatedly co-located in genomes with genes for enzymes that can inadvertently reduce perchlorate (ClO4-) or chlorate (ClO3-), indicating that in situ (per)chlorate reduction does not only occur through specialized anaerobic respiratory metabolisms. The presence of Cld in genomes of obligate aerobes without such enzymes suggested that chlorite, like hypochlorous acid (HOCl), might be formed by oxidative processes within natural habitats. In summary, the comparative genomics of Cld has provided an atlas for a deeper understanding of chlorine oxidation and reduction reactions that are an underrecognized feature of biology.

Generation, toxicity, and reduction of chlorinated byproducts: Overcome bottlenecks of electrochemical advanced oxidation technology to treat high chloride wastewater.

Electrochemical advanced oxidation process (EAOP) is recommended for high-strength refractory organics wastewater treatment, but the accompanying chlorinated byproduct generation becomes a bottleneck that limits the application of this technology to actual wastewater. In this study, we applied EAOP (0.4-40 mA cm-2) to treat ultrafiltration effluent of an actual landfill leachate, and quantitatively assessed the toxicities of the dominant chlorinated byproducts in EAOP-treated effluent. Considering both toxic effect and dose, it followed the order: active chlorine > chlorate > perchlorate > organochlorines. The toxic active chlorine could spontaneously decompose by settling. And secondary bioreactor originally serving for denitrification could be used to reduce perchlorate and chlorate. The effects of residual active chlorine and extra carbon addition on simultaneous denitrification, perchlorate, and chlorate reduction were investigated. It seemed that 20 mg of active chlorine was an acceptable level to bioactivity, and sufficient electron donors favored the removal of chlorate and perchlorate. Pseudomonas was identified as an active chlorine tolerant chlorate-reducing bacteria. And Thauera was responsible for perchlorate reduction under the conditions of sufficient carbon source supply. Our results confirmed that the perchlorate and chlorate concentrations in the effluent below their health advisory levels were achievable, solving the issue of toxic chlorinated byproduct generation during EAOP. This study provided a solution to realistic application of EAOP to treat high chloride wastewater.

Activation of chloride by oxygen vacancies-enriched TiO2 photoanode for efficient photoelectrochemical treatment of persistent organic pollutants and simultaneous H2 generation.

Photoelectrochemical (PEC) activation of chloride ions (Cl-) to degrade persistent organic pollutants (POPs) is a promising strategy for the treatment of industrial saline organic wastewater. However, the wide application of this technology is greatly restricted due to the general photoanode activation of Cl- with poor capability, the propensity to produce toxic by-products chlorates, and the narrow pH range. Herein, oxygen vacancies-enriched titanium dioxide (Ov-TiO2) photoanode is explored to strongly activate Cl- to drive the deep mineralization of POPs wastewater in a wide pH range (2-12) with simultaneous production of H2. More importantly, nearly no toxic by-product of chlorates was produced during such PEC-Cl system. The degradation efficiency of 4-CP and H2 generation rate by Ov-TiO2 were 99.9% within 60 min and 198.2 µmol h-1 cm-2, respectively, which are far superior to that on the TiO2 (33.1% within 60 min, 27.5 µmol h-1 cm-2) working electrode. DFT calculation and capture experiments revealed that Ov-TiO2 with abundant oxygen vacancies is conducive to the activation of Cl- to produce more reactive chlorine species, evidenced by its high production of free chlorine (48.7 mg L-1 vs 7.5 mg L-1 of TiO2). The as-designed PEC-Cl system in this work is expected to realize the purification of industrial saline organic wastewater coupling with green energy H2 evolution.