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1.
Chemosphere ; 355: 141855, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38570051

RESUMO

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.


Assuntos
Cloro , Poluentes Químicos da Água , Técnicas Eletroquímicas , Percloratos , Microfluídica , Água , Cloratos , Cloretos , Oxirredução , Eletrodos , Poluentes Químicos da Água/análise
2.
Wei Sheng Yan Jiu ; 53(1): 102-108, 2024 Jan.
Artigo em Chinês | MEDLINE | ID: mdl-38443180

RESUMO

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.


Assuntos
Cloratos , Percloratos , Cromatografia Líquida , Espectrometria de Massas em Tandem
3.
Environ Sci Pollut Res Int ; 31(6): 8510-8518, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38182951

RESUMO

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.


Assuntos
Cloratos , Poluentes Ambientais , Humanos , Cloratos/análise , Percloratos/análise , Chá , China
4.
Environ Sci Technol ; 57(48): 20392-20399, 2023 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-37976223

RESUMO

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.


Assuntos
Cloratos , Vanádio , Vanádio/química , Oxirredução , Água/química , Cloretos , Concentração de Íons de Hidrogênio , Catálise , Paládio/química
5.
Environ Res ; 238(Pt 2): 117185, 2023 12 01.
Artigo em Inglês | MEDLINE | ID: mdl-37742753

RESUMO

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.


Assuntos
Antibacterianos , Poluentes Químicos da Água , Cefaclor , Peróxido de Hidrogênio , Cloratos , Titânio , Percloratos , Oxirredução , Eletrodos , Poluentes Químicos da Água/análise
6.
Environ Sci Technol ; 57(32): 12063-12071, 2023 08 15.
Artigo em Inglês | MEDLINE | ID: mdl-37531609

RESUMO

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.


Assuntos
Compostos Clorados , Desinfetantes , Purificação da Água , Desinfecção , Cloratos , Cloro , Compostos Clorados/química , Óxidos/química , Desinfetantes/química
7.
J AOAC Int ; 106(6): 1505-1524, 2023 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-37462536

RESUMO

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.


Assuntos
Cloratos , Espectrometria de Massas em Tandem , Humanos , Lactente , Adulto , Cromatografia Líquida/métodos , Cloratos/análise , Percloratos/análise , Metanol , Fórmulas Infantis/análise , Água , Cromatografia Líquida de Alta Pressão
8.
Microbiology (Reading) ; 169(7)2023 07.
Artigo em Inglês | MEDLINE | ID: mdl-37450378

RESUMO

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.


Assuntos
Cloratos , Leite , Animais , Oxirredução , Leite/metabolismo , Cloratos/metabolismo , Bactérias/metabolismo
9.
Biosensors (Basel) ; 13(6)2023 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-37366994

RESUMO

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.


Assuntos
Técnicas Biossensoriais , Escherichia coli , Cloratos , Alimentos , Bactérias
10.
Environ Res ; 233: 116450, 2023 09 15.
Artigo em Inglês | MEDLINE | ID: mdl-37343761

RESUMO

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.


Assuntos
Água Potável , Poluentes Químicos da Água , Água Potável/química , Cloratos/análise , Chile , Nitratos/análise , Percloratos , Cidades , Cloretos/análise , Poluentes Químicos da Água/análise
11.
Water Res ; 240: 120100, 2023 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-37247439

RESUMO

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.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Brometos , Cloro , Água , Cloratos , Bromo , Bromatos , Fotólise , Cloretos , Poluentes Químicos da Água/análise
12.
J Agric Food Chem ; 71(13): 5345-5357, 2023 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-36946919

RESUMO

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.


Assuntos
Compostos Clorados , Desinfetantes , Prunus dulcis , Gases , Cloro/farmacologia , Contagem de Colônia Microbiana , Cloratos , Microbiologia de Alimentos , Desinfetantes/farmacologia , Óxidos/farmacologia , Compostos Clorados/farmacologia , Salmonella , Lipídeos
13.
Environ Sci Technol ; 57(8): 3311-3322, 2023 02 28.
Artigo em Inglês | MEDLINE | ID: mdl-36787277

RESUMO

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.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Animais , Oxidantes , Peróxido de Hidrogênio , Bromatos/toxicidade , Águas Residuárias , Cloratos , Poluentes Químicos da Água/análise , Peróxidos , Oxirredução , Halogênios , Mamíferos
14.
Environ Sci Technol ; 57(9): 3962-3970, 2023 03 07.
Artigo em Inglês | MEDLINE | ID: mdl-36808945

RESUMO

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.


Assuntos
Cloratos , Paládio , Oxirredução , Concentração de Íons de Hidrogênio
15.
Biodegradation ; 34(4): 301-323, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-36598629

RESUMO

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.


Assuntos
Nitratos , Poluentes Químicos da Água , Nitratos/metabolismo , Percloratos/metabolismo , Cloratos/metabolismo , Bactérias/metabolismo , Biodegradação Ambiental , Poluentes Químicos da Água/metabolismo
16.
ISME J ; 17(1): 70-83, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36202926

RESUMO

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.


Assuntos
Cloratos , Cloro , Cloro/metabolismo , Cloretos/metabolismo , Oxirredução , Bactérias/metabolismo
17.
Water Res ; 230: 119531, 2023 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-36580803

RESUMO

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.


Assuntos
Águas Residuárias , Poluentes Químicos da Água , Cloro , Cloretos , Percloratos , Cloratos , Oxirredução , Carbono
18.
J Hazard Mater ; 443(Pt B): 130363, 2023 02 05.
Artigo em Inglês | MEDLINE | ID: mdl-36444064

RESUMO

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.


Assuntos
Cloretos , Poluentes Orgânicos Persistentes , Cloratos , Cloro , Oxigênio , Águas Residuárias , Halogênios
19.
Nutrients ; 16(1)2023 Dec 27.
Artigo em Inglês | MEDLINE | ID: mdl-38201922

RESUMO

Despite strontium ranelate use in osteoporosis management being one of the promising concepts in disease treatment, there is no clear evidence that strontium organic compounds are more effective than inorganic ones. The aim of this study was to compare strontium chlorate and strontium ranelate influence on the mice bone microarchitecture. We investigated whether strontium chlorate (7.532 mmol/L) and strontium ranelate (7.78 mmol/L) solutions fed to healthy SWISS growing mice (n = 42) had an influence on the percent of bone volume (BV/TV), trabecular thickness (Tb.Th), number of trabeculae (Tb.N), and separation between each trabecula (Tb.Sp) in the chosen ROI (region of interest) in the distal metaphysis of the left femurs. The cortical bone surface was examined close to the ROI proximal scan. There was an increase in each examined parameter compared with the control group. There were no statistical differences between strontium ranelate and strontium chlorate parameters. Our study indicates that organic and inorganic strontium compounds similarly affect the bone microarchitecture and strength.


Assuntos
Cloratos , Estrôncio , Tiofenos , Animais , Camundongos , Estrôncio/farmacologia , Suplementos Nutricionais , Remodelação Óssea
20.
Molecules ; 27(23)2022 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-36500616

RESUMO

Unlike halides, where the kosmotropicity decreases from fluoride to iodide, the kosmotropic nature of halates apparently increases from chlorate to iodate, in spite of the lowering in the static ionic polarizability. In this paper, we present an experimental study that confirms the results of previous simulations. The lyotropic nature of aqueous solutions of sodium halates, i.e., NaClO3, NaBrO3, and NaIO3, is investigated through density, conductivity, viscosity, and refractive index measurements as a function of temperature and salt concentration. From the experimental data, we evaluate the activity coefficients and the salt polarizability and assess the anions' nature in terms of kosmotropicity/chaotropicity. The results clearly indicate that iodate behaves as a kosmotrope, while chlorate is a chaotrope, and bromate shows an intermediate nature. This experimental study confirms that, in the case of halates XO3-, the kosmotropic-chaotropic ranking reverses with respect to halides. We also discuss and revisit the role of the anion's polarizability in the interpretation of Hofmeister phenomena.


Assuntos
Cloratos , Água , Ânions , Cloreto de Sódio , Temperatura , Iodatos
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