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UNLABELLED: A hydrometallurgical process is described for conversion of an aqueous solution of lithium chloride into an aqueous solution of lithium hydroxide via a chloride/hydroxide anion exchange reaction by solvent extraction. The organic phase comprises a quaternary ammonium chloride and a hydrophobic phenol in a diluent. The best results were observed for a mixture of the quaternary ammonium chloride Aliquat 336 and 2,6-di-tert-butylphenol (1:1 molar ratio) in the aliphatic diluent Shellsol D70. The solvent extraction process involves two steps. In the first step, the organic phase is contacted with an aqueous sodium hydroxide solution. The phenol is deprotonated, and a chloride ion is simultaneously transferred to the aqueous phase, leading to in situ formation of a quaternary ammonium phenolate in the organic phase. The organic phase, comprising the quaternary ammonium phenolate, is contacted in the second step with an aqueous lithium chloride solution. This contact converts the phenolate into the corresponding phenol by protonation with water extracted to the organic phase, followed by a transfer of hydroxide ions to the aqueous phase and chloride ions to the organic phase. As a result, the aqueous lithium chloride solution is transformed into a lithium hydroxide solution. The process has been demonstrated in continuous counter-current mode in mixer-settlers. Solid battery-grade lithium hydroxide monohydrate was obtained from the aqueous solution by crystallization or by antisolvent precipitation with isopropanol. The process consumes no chemicals other than sodium hydroxide. No waste is generated, with the exception of an aqueous sodium chloride solution. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40831-022-00629-2. ispartof: JOURNAL OF SUSTAINABLE METALLURGY vol:9 issue:1 pages:107-122 ispartof: location:Netherlands status: published

Among halogenated molecules, those containing chlorine atoms are fundamental in many areas such as pharmaceuticals, polymers, agrochemicals and natural metabolites. Despite the fact that many reactions have been developed to install chlorine on organic molecules, most of them rely on toxic and hazardous chlorinating reagents as well as harsh conditions. In an attempt to move towards more sustainable approaches, photoredox catalysis and electrocatalysis have emerged as powerful alternatives to traditional methods. In this review, we collect the most recent and significant examples of visible-light- or current-mediated chlorination published in the last five years.

Disinfection of surface waters for human consumption and use often results in reaction between the disinfectant (generally chlorine) and organic substrates present at the source. These substrates are majorly in the form of aquatic humic materials. This work was designed to assess reduced glutathione (GSH) concentration in pig liver and kidney in the presence of chlorinated aquatic humic materials (CAHMs) using biochemical parameters. GSH concentration in pig liver and kidney was investigated following standard procedures using Ellman’s reagent. Effect of chlorinated local and foreign aquatic humic products on the GSH concentration of the two tissues was studied in line with standard methodologies. GSH concentration was found to be higher in pig liver (0.874 ± 0.003µmol/g) than the kidney (0.545 ± 0.002µmol/g). All the chlorinated aquatic humic samples studied were found to deplete the GSH concentration of the two tissues, with the more toxic and concentrated purified chlorinated foreign aquatic humics having higher depletion. Certain amount of GSH was also found to be left in both tissues after conjugation with the chlorinated aquatic humic samples which perhaps could be used for subsequent conjugation and detoxification of water pollutants by the tissues. In conclusion, the liver contains more GSH than the kidney. The levels of this antioxidant in pig liver and kidney were both reduced by the aquatic humic materials used. This study may therefore reemphasize earlier suggestions that the amino acids needed for cellular synthesis of GSH could be supplemented regularly through dietary sources.

The interaction between UN and CdCl2 in the LiCl–KCl molten eutectic was studied at 1023 K. The chlorination was monitored by sampling and recording the redox potential of the medium. At 1023 K the chlorination of UN with cadmium chloride in the molten LiCl–KCl eutectic proceeds completely and results in the formation of uranium chlorides. The melts of the LiCl–KCl–UCl3 or LiCl–KCl–UCl4 compositions can be obtained by the end of experiment depending on the presence of metallic cadmium in the reaction zone. The higher the concentration of the chlorinating agent, the faster the reaction rate. At [CdCl2]/[UN] = 1.65 (10% excess) the reaction proceeds to completion in about 7.5 h. At [CdCl2]/[UN] = 7 the complete chlorination takes 2.5–3 h.

This study analysed the spatial and temporal occurrence of 29 disinfection by-products (DBPs) formed by chlorination and chloramination. Four full-scale treatment works, and distribution system locations were sampled, and the results were compared with laboratory-based simulated distribution system (SDS) tests. The DBPs monitored incorporated 4 trihalomethanes (THMs), 9 haloacetic acids (HAAs), 7 haloacetonitriles (HANs) and 9 haloacetamides (HAcAms). For the first time, SDS tests were shown to successfully simulate the levels and speciation of HANs and HAcAms in both chlorinated and chloraminated systems. While THM and HAA concentrations generally increased with water age, HAN and HAcAm concentrations fluctuated and resulted in less pronounced overall increases. To explore the impact of switching the disinfectant in distribution, free chlorine and chloramines were applied in the SDS tests, which showed that chloramination not only reduces the yields of THMs (by 34%) and HAAs (by 49%), but also HANs (by 61%) and HAcAms (by 51%), although it shifts speciation towards more brominated HAAs, HANs and HAcAms species when compared against chlorination. Overall, the aim of the study was to demonstrate that SDS tests can be recommended for the simultaneous estimation of THM, HAA, HAN and HAcAm concentrations in distribution systems and to assess the effect of potential DBP minimisation strategies, such as switching the disinfectant in distribution.

International audience; Sulfonamides have been proved to damage organisms if the contact time last over the long term. We studied the degradation kinetic of sulfapyridine in the chlorination stage of a pilot-scale water distribution system. Results show that the degradation of sulfapyridine simultaneously followed the first-order and pseudo second-order kinetics. In the beakers tests or water distribution system, the reaction rate reaches maximum values when the pH is about 7. The degradation rate of sulfapyridine would be higher with the increase of water velocity in the water distribution system. Degradation experiments in different pipe materials show that degradation efficiency is in the following order: stainless-steel pipe > ductile iron pipe > polyethylene pipe. We observed a significant increase in the content of trihalomethanes when chlorination of tap water-containing sulfapyridine were performed in both the water distribution system and beakers. The mechanism of this process was analyzed in combination with the intermediate products. In addition, density functional theory calculations were performed to assist in the identification of 6 intermediates and possible degradation pathways.

Widespread implementation of on-site water reuse systems is hindered by the limited ability to ensure the level of treatment and protection of human health during operation. In this study, we tested the ability of five commercially available online sensors (free chlorine (FC), oxidation-reduction potential (ORP), pH, turbidity, UV absorbance at 254 nm) to predict the microbial water quality in membrane bioreactors followed by chlorination using logistic regression-based and mechanism-based models. The microbial water quality was assessed in terms of removal of enteric bacteria from the wastewater, removal of enteric viruses, and regrowth of bacteria in the treated water. We found that FC and ORP alone could predict the microbial water quality well, with ORP-based models generally performing better. We further observed that prediction accuracy did not increase when data from multiple sensors were integrated. We propose a methodology to link online sensor measurements to risk-based water quality targets, providing operation setpoints protective of human health for specific combinations of wastewaters and reuse applications. For instance, we recommend a minimum ORP of 705 mV to ensure a virus log-removal of 5, and an ORP of 765 mV for a log-removal of 6. These setpoints were selected to ensure that the percentage of events where the water is predicted to meet the quality target but it does not remains below 5%. Such a systematic approach to set sensor setpoints could be used in the development of water reuse guidelines and regulations that aim to cover a range of reuse applications with differential risks to human health., Water Research X, 18, ISSN:2589-9147

There is growing interest in the fate and effects of transformation products generated from emerging pollutant classes, and new tools that help predict the products most likely to form will aid in risk assessment. Here, using a family of structurally related steroids (enones, dienones, and trienones), we evaluate the use of density functional theory to help predict products from reaction with chlorine, a common chemical disinfectant. For steroidal dienones (e.g., dienogest) and trienones (e.g., 17β-trenbolone), computational data support that reactions proceed through spontaneous C4 chlorination to yield 4-chloro derivatives for trienones and, after further reaction, 9,10-epoxide structures for dienones. For testosterone, a simple steroidal enone, in silico predictions suggest that C4 chlorination is still most likely, but slow at environmentally relevant conditions. Predictions were then assessed through laboratory chlorination reactions (0.5-5 mg Cl2/L) with product characterization via HRMS and NMR, which confirmed near exclusive 4-chloro and 9,10-epoxide products for most trienones and all dienones, respectively. Also consistent with computational expectations, testosterone was effectively unreactive at these same chlorine levels, although products consistent with in silico predictions were observed at higher concentrations (in excess of 500 mg Cl2/L). Although slight deviations from in silico predictions were observed for steroids with electron-rich substituents (e.g., C17 allyl-substituted altrenogest), this work highlights the potential for computational approaches to improve our understanding of transformation products generated from emerging pollutant classes., Environmental Science & Technology, 55 (21), ISSN:0013-936X, ISSN:1520-5851

Hospitals are regarded as ecological niches of antibiotic-resistant bacteria (ARB). ARB can spread outside the hospital environment via hospital wastewater (HWW). Therefore, HWW is often disinfected in local stations to minimize that risk. Chlorine-based treatment is the most popular method of HWW disinfection around the world, however, recent research has suggested that it can contribute to the spread of antimicrobial resistance (AMR). The aim of this study is to determine the impact of HWW disinfection on the clonal similarity of Enterobacteriaceae species and their ability to produce extended-spectrum beta-lactamases (ESBLs). The study was conducted in a hospital with a local chlorine-based disinfection station. Samples of wastewater before disinfection and samples of disinfected wastewater, collected in four research seasons, were analyzed. Bacteria potentially belonging to the Enterobacteriaceae family were isolated from HWW. The Enterobacterial Repetitive Intergenic Consensus Polymerase Chain Reaction (ERIC-PCR) method was used to generate DNA fingerprints of all bacterial isolates. The isolates were phenotypically tested for the production of ESBLs. Antibiotic resistance genes (blaSHV, blaTEM, and blaOXA, blaCTX-M-1-group, blaCTX-M-2-group, blaCTX-9-group and blaCTX-M-8/25-group) were detected by PCR in strains with confirmed phenotypic ability to produce ESBLs. The ESBL+ isolates were identified by the sequencing of 16S rDNA. In the present study, the same bacterial clones were isolated from HWW before and after disinfection and HWW was sampled in different seasons. Genetic and phenotypic variations were observed in bacterial clones. ESBL+ strains were isolated significantly more often from disinfected than from non-disinfected HWW. The blaOXA gene was significantly more prevalent in isolates from disinfected than non-disinfected HWW. Enterobacter hormaechei and Klebsiella pneumoniae were the dominant species in ESBL+ strains isolated from both sampling sites. The results of this study indicate that chlorine-based disinfection promotes the survival of ESBL-producing bacteria and/or the transmission of genetic determinants of antimicrobial resistance. As a result, chlorination increases the proportion of ESBL-producing Enterobacteriaceae in disinfected wastewater. Consequently, chlorine-based disinfection practices may pose a risk to the environment and public health by accelerating the spread of antimicrobial resistance.

International audience; Disinfecting swimming pool water is essential for preventing waterborne diseases. An unforeseen consequence of treating water with disinfectants is the formation of disinfection byproducts (DPBs) that can cause harmful effects to health through the interactions between the added disinfectant and organic matter in the water. The present work focuses on the chlorine reactivity with particles released by bathers. Such particles are collected in the filter backwash water of swimming pools and this study intends to distinguish DPBs generated from dissolved chemicals from those formed by particulate matter. Therefore, filtered and unfiltered backwash waters were collected from several swimming pools, analyzed physicochemically and chemically, and then chlorinated as is (79 mgL-1) and as diluted suspensions (36.2 and 11.9 mgL-1) at varying concentrations of chlorine (1.2 mg and 24 mgCl2L-1). Utilizing a DPD colorimetric technique and GC-ECD, respectively, the kinetics of chlorine consumption and DPBs production have been investigated. Up to 25.7 µgL-1 of chloroform was produced within 96 h at 1.2 mgCl2L-1 , followed by haloacetic acids (HAAs) and haloacetonitriles (HANs). Within 96 h, the concentration of trichloroacetic acid reached a maximum of 231.8 µgL-1 at a chlorine concentration of 231.8 µgL-1. The formations of 0.13 µmol THMs, 0.31 µmol HAAs, and 0.04 µmol HANs per mg of dissolved organic carbon (DOC) were finally determined by correlating the organic content of particles with the nature of the DBPs generated. Comparing the quantities of DBPs generated in filtered and unfiltered samples helps us conclude that ~50% of DBPs formed during the chlorination of swimming pool water are derived from particles brought by bathers.

Processing of end-of-life products (EoL) containing rare earth elements (REE) has gained increasing importance in recent years with the aim of avoiding supply risks. In addition, circular economy renders complete recirculation of technology metals mandatory. Fluorescent lamp wastes are an important source for REE recovery since they contain significant amounts, up to 55 wt%, of Y and Eu in red phosphors. For these purposes, solid-state chlorination (SSC) is an economically attractive alternative to wet acid leaching treatment, which profits from a considerable reduction of chemicals consumption and process costs. Chlorination takes place with dry HCl(g) produced from thermal decomposition of NH4Cl(s), not only converting the REE content of the Hg-free phosphor waste into water soluble REE metal chlorides, but also avoiding the implications of aqueous complex chemistry of REE. To establish an industrial process viable on a commercial scale, the SSC process has been optimized by (i) using a design of experiment (DOE) varying temperature, residence time, and gNH4Cl/gsolid ratio and (ii) improved leaching of the chlorinated metals with an organic mixture selective for REE. As a result, 95.7% of the Y and 92.2% of the Eu were selectively recovered at 295.9 °C, 67 min and a ratio of 1.27 gNH4Cl/gsolid, followed by quantitative selective leaching of the REE. Owed to its low chemicals consumption and operation costs, the current process allows for valorizing lamp waste even when raw material prices are low.

In response to the finding of chironomid larvae in tap water, South Korea’s water treatment system has stepped up water quality monitoring. However, due to the challenging nature of larval behavior, effective elimination remains difficult despite the use of various purification techniques such as coagulation, sedimentation, filtration, and disinfection. Based on it, the aim of this study is to evaluate the effectiveness of coagulation and chlorination in inactivating chironomid larvae and investigate their behavior. The coagulation experiment tested how the behavior of the larvae changed in water with a high turbidity level of ±100 mg/L and 2 mg/L Al3+ as a coagulant, compared to water with a lower turbidity level of ±30 mg/L and 1 mg/L of Al3+ as a coagulant. The larvae were exposed to various doses of chlorine (0.5–20 mg/L as Cl) in 500 mL beaker glasses. The behavioral activity of the larvae was observed at different time points for 5 days. It was found that chironomid larvae exhibit different responses to exposure to coagulant and chlorine, with coagulation causing the formation of flocs that cover the larval body as a protective measure. Conversely, exposure to chlorine causes a decrease in activity and growth, leading to the death of the larvae and subsequent melting. The results showed that the first instar larvae dead after 48 h of exposure to coagulation treatment, while the first instar larvae exposed to chlorination experienced mortality after a mere 5 min of exposure to 10–20 mg/L as Cl. The larvae can still grow and transform into pupae and adults, especially during the third and fourth instars, even after exposure to coagulant and chlorine with low dosage. These findings suggest that the floc generated during coagulation must be thoroughly cleaned, as it may contain larvae that can persist and develop further. Furthermore, the presence of larvae during the chlorination process highlights the need for alternative, more effective oxidants to be utilized in place of the conventional chlorine treatment.

The COVID-19 pandemic draws much attention to virus inactivation since the SARS-CoV-2 was detected in miscellaneous environments and the wastewater can be a potential transmitting pathway. UV irradiation, ozonation and chlorination are widely used disinfection processes in water treatment. In this review, the mechanisms and applications of three disinfection processes are introduced, and their inactivation effects on virus as well as other microorganisms are compared and discussed. The resistance of viruses to UV irradiation is generally stronger than that of bacteria. 4-log inactivation of bacteria can be easily obtained within a UV dose of 10 ​mJ/cm2. However, the doses to reach the same virus removal rate vary greatly from 10 to 140 ​mJ/cm2. The coronaviruses have even stronger UV resistance. Comparatively, ozonation and chlorination are effective methods to inactivate viruses, and the CT values of 4-log removal for most viruses concerned are lower than 1 ​mg·min/L and 10 ​mg·min/L, respectively. Protozoa, fungal spores and bacterial spores are more resistant to disinfection. Temperature, pH, organic matters, turbidity and other parameters all have influences on the disinfection. With a 10 ​°C decrease in temperature, the CT value required for certain removal rates doubles. Generally low pH promotes disinfection and high pH is against it. In drinking water and wastewater treatment process, the resistance properties of microorganisms and other influence parameters should be taken into consideration when choosing disinfection technologies.

The aim of this review was to rapidly synthesize the available evidence regarding the expected impacts of piped water chlorination, drainage, and sewerage on individuals living in low- and middle-income urban settings. A systematic search was conducted in bibliographic databases and library catalogs. Impact evaluations that included a comparator and one of the three interventions of interest, attempted to control for confounding and selection bias, and took place in urban settings in a low- or middle-income country were considered. Outcomes related to health, well-being, economic growth, and the bacterial content of water were considered. A total of 1,483 articles were identified, with 18 included after final screening. Most studies were case-control and took place in Brazil, the Pacific Islands, or south-western Asia. Fifteen studies considered sewerage, five considered chlorination, and two studies considered drainage with some studies considering multiple interventions. All primary outcomes were related to health. When implemented alone, the sewerage and chlorination interventions were largely successful. The evidence regarding the effects of chlorination, drainage, and sewerage interventions is limited and generally has a high risk of bias. When properly implemented, sewerage and chlorination are likely to have positive health impacts. However, when implemented poorly, all three interventions can have negative health impacts. HIGHLIGHTS Most studies focused on sewerage interventions.; Chlorination and sewerage interventions were successful in reducing disease burden.; Contamination sources included lack of improved WaSH, sources in the nearby environment, and household hygiene practices.; Infrastructure maintenance issues affected the interventions’ impacts.; Proper household hygiene practices should be included for effective interventions.

Analytical methods based on the Berthelot reaction were recently adapted for determining monochloramine (MCA: NH2Cl) in freshwater. The specificity of the Berthelot reaction with regard to MCA is related to the need for two exchangeable hydrogen atoms to form indophenol blue. MCA can thus be distinguished from organic N-chloramines, which have only one exchangeable hydrogen atom. Monobromamine (MBA: NH2Br) may be formed during chlorination of seawater containing ammonium ions. Quantifying MBA is quite challenging and no method has been reported for its specific determination in seawater. As MBA also has two exchangeable hydrogen atoms, its reactivity might be analogous to that of MCA, but this hypothesis has never been investigated. The aim of this study was to examine the applicability of the so-called &ldquo, indophenol method&rdquo, for the determination of the MBA in freshwater and seawater samples. The reaction between MBA and Berthelot reagents was studied in both ultrapure water and artificial seawater. The reaction products were characterized by using gas chromatography coupled to mass spectrometry (GC&ndash, MS), Fourier transform-ion cyclotron resonance mass spectrometry (FT&ndash, ICR MS), and UV&ndash, vis spectroscopy. Results showed that colorimetric methods based on the Berthelot reaction were not suitable for measuring MBA in freshwater or seawater, since NH2Br reacts with alkaline phenol derivative via electrophilic substitution to form ortho- and para-brominated phenols instead of forming indophenol.

The interaction between UN and CdCl2 in the LiCl-KCl molten eutectic was studied at 773 K.The reaction was controlled by sampling the melt, as well as by analysis of the resulting precipitate. The process was shown to proceed according to several parallel reactions. The summary reaction was determined to have two stages: a fast one and a slow one. The 19–53% UN → UCl3 conversion was obtained for the molar ratio of CdCl2/UN = 1.22–14.9. The rest of UN converts into the precipitate of complex composition (UNCl + U2N3 + U4N7 + UN2). The increase in the CdCl2/UN molar ratio from 1.22 to 14.9 resulted in the decrease in duration of the first “fast” stage of the process from 18 h to 1 h. Keywords: Spent nuclear fuel, Nitride nuclear fuel, Chlorination, Pyrochemistry, UN, UNCl, Molten salts

Bacterial multimodular polyketide synthases (PKSs) are large enzymatic assembly lines that synthesize many bioactive natural products of therapeutic relevance. While PKS catalysis is mostly based on fatty acid biosynthetic principles, polyketides can be further diversified by post-PKS enzymes. Here, we characterized a remarkably versatile trans-acyltransferase (trans-AT) PKS from Serratia that builds structurally complex macrolides via more than ten functionally distinct PKS modules. In the oocydin PKS, we identified a new oxygenation module that α-hydroxylates polyketide intermediates, a halogenating module catalyzing backbone γ-chlorination, and modular O-acetylation by a thioesterase-like domain. These results from a single biosynthetic assembly line highlight the expansive biochemical repertoire of trans-AT PKSs and provide diverse modular tools for engineered biosynthesis from a close relative of E. coli. ISSN:1433-7851 ISSN:1521-3773 ISSN:0570-0833

Due to the prevalence of the COVID-19 outbreak, as well as findings of SARS-CoV-2 RNA in wastewater and the possibility of viral transmission through wastewater, disinfection is required. As a consequence, based on prior investigations, this work initially employed the viral concentration detection technique, followed by the RT-qPCR assay, as the foundation for identifying the SARS-CoV-2 virus in wastewater. After that, the ability and efficacy of chlorine, ozone, and UV disinfection to inactivate the SARS-CoV-2 virus from wastewater were examined. Chlorine disinfection is the most extensively used disinfection technology due to its multiple advantages. With a chlorine dioxide disinfectant dose of 40 mg/L, the SARS-CoV virus is inactivated after 30 min of contact time. On the other hand, ozone is a powerful oxidizer and an effective microbicide that is employed as a disinfectant due to its positive characteristics. After 30 min of exposure to 1000 ppmv ozone, corona pseudoviruses are reduced by 99%. Another common method of disinfection is using ultraviolet radiation, which is usually 253.7 nm suitable for ultraviolet disinfection. At a dose of 1048 mJ/cm2, UVC radiation completely inactivates the SARS-CoV-2 virus. Finally, to evaluate disinfection performance and optimize disinfection strategies to prevent the spread of SARS-CoV-2, this study attempted to investigate the ability to remove and compare the effectiveness of each disinfectant to inactive the SARS-CoV-2 virus from wastewater, summarize studies, and provide future solutions due to the limited availability of integrated resources in this field and the spread of the SARS-CoV-2 virus worldwide.

13 Pág. Dirección Técnica de Evaluación de Variedades y Laboratorios (DTEVL), Any active substance with phytosanitary capacity intended to be marketed in Europe must pass exhaustive controls to assess its risk before being marketed and used in European agriculture. Since the implementation of Regulation (EC) No 1107/2009, agrochemical companies have been obliged to study the formation of pesticide transformation products (TPs) during the treatment of drinking water containing pesticide residues. However, there is no consensus on how to address this requirement. In this research work, the open literature collection on alloxydim was used to propose potential chlorination paths from alloxydim isomers. Furthermore, several QSAR/QSPR models have been used to fill the of knowledge gap relative to some key parameters in the physico-chemical, environmental and ecotoxicological areas of potential alloxydim TPs from chlorinated water for which little information exists. In this way, it has been possible to estimate the state of aggregation of these TPs (they exist mainly as liquids) as well as their ease of transit between the different phases, to predict their possible behaviour in the three environmental compartments (e.g., thermophysical properties point to a change in their evolution with respect to the parent alloxydim isomers) and to anticipate their potential risk to human and animal health (e.g., all of them cause developmental toxicity). These and other results highlight that the hazards of several TPs, i.e., both chlorinated and nonchlorinated from parent alloxydim or from those obtained after cleavage of the N - O bond and the subsequent reaction with chlorine, should be seriously considered. The obtained results reopen the debate on the implications of the use of QSAR/QSPR models for pesticide risk assessment in the legislative framework., This work was supported by the project Y2020/EMT-6290 (PRIES-CM) of the Comunidad de Madrid

Chemical disinfection of water provides significant public health benefits. However, disinfectants like chlorine can react with naturally occurring materials in the water to form disinfection byproducts (DBPs). Natural levels of iodine have been reported to be too low in some source waters to account for the levels of iodinated DBPs detected. Iodinated X-ray contrast media (ICM) have been identified as a potential source of iodine. The toxicological impact of ICM present in source water at the time of disinfection has not been fully investigated. Iopamidol, iohexol, iopromide, and diatrizoate are among the ICM most frequently detected in water. In this study, source water containing one of these four ICM was chlorinated; non-chlorinated ICM-containing water samples served as controls. Reactions were conducted at an ICM concentration of 5 µM and a chlorine dose of 100 µM over 72 hr. Water concentrates (20,000-fold) were prepared by XAD-resin/ethyl acetate extraction and DMSO solvent exchange. We used the MatTek® reconstituted human epithelial skin irritation model to evaluate the water concentrates and also assessed the dermal irritation and sensitization potential of these concentrates using the LLNA:BrdU ELISA in BALB/c mice. None of the water concentrates tested (2500X) resulted in a skin irritant response in the MatTek® skin irritation model. Likewise, none of the concentrates (2500X, 1250X, 625X, 312.5X, 156.25X) produced a skin irritation response in mice: erythema was minimal; the maximum increase in ear thickness was less than 25%. Importantly, none of the concentrates produced a positive threshold response for allergic skin sensitization at any concentration tested in the LLNA:BrdU ELISA. We conclude that concentrates of water disinfected in the presence of four different ICM did not cause significant skin irritation or effects consistent with skin sensitization at the concentrations tested., The authors thank Mr. Carey Copeland, Ms. Debbie Andrews, Mr. Tony McDonald, and Mr. Yusupha M. Sey for expert technical support. C.P. acknowledges support of Marie Curie IOF grant agreement 274379 funded by the European Union 7th R&D Framework Programme (FP7/2007-2013) and grant RYC2020-028901-I funded by MCIN/AEI/10.13039/501100011033 and “ESF investing in your future” . Drs. C. Weitekamp and YH Kim are acknowledged for their thoughtful and critical review of this manuscript.

В данной статье даны результаты реакций ацилирования и хлорирования анилида хиназолон-4-ил-2-тиокарбоновой кислоты. При ацилировании образуется хиназолон-4-ил-2-тио-N-ациланилиды, а при хлорировании синтезируется 2--хлор--фенилиминометилхиназолон-4., This article gives the reactions acylation and chlorination of quinazolon-4-yl-2thiocarboxylic acid anilide. Acylation produces quinazolon-4-yl-2-thio-Nacylanilides, while chlorination produces 2--chloro-phenyliminomethylquinazolone-4.

Patients with rheumatoid arthritis (RA) show autoantibodies against post-translational protein modifications (PTMs), such as anti-citrullinated protein antibodies. However, the range of recognized PTMs is unknown. Here, we addressed four PTMs: chlorination, non-enzymatic glycation, nitration, and homocysteinylation, identified as targets of atypical RA autoantibodies in studies whose protocols we have followed. The modified antigens included collagen type II, an extract of synovial proteins and a selection of peptides. We interpreted the results according to the optical density (OD) obtained in an enzyme-linked immunosorbent assay ( ELISA) with the modified antigen and the corrected OD obtained after subtracting the reactivity against the unmodified antigen. The results showed evidence of specific antibodies against glycated collagen type II, as the corrected ODs were higher in the 182 patients with RA than in the 164 healthy controls (p = 0.0003). However, the relevance of these antibodies was doubtful because the magnitude of the specific signal was small (median OD = 0.072 vs. 0.027, respectively). There were no specific antibodies against any of the other three PTMs. Therefore, our results showed that the four PTMs are not inducing a significant autoantibody response in patients with RA. These results indicated that the repertoire of PTM autoantigens in RA is restricted.

Acetaminophen (ACE), a highly consumed pharmaceutical, was degraded in aqueous matrices by reactive chlorine species (RCS) electrogenerated using Ti/IrO2 electrodes. Although this pollutant has been extensively treated by electrochemical techniques, little information is known about its degradation in fresh urine by electrogenerated RCS, and the understanding of its transformations using analyses of atomic charge. In this work, these two topics were discussed. Initially, the effect of current (10-40 mA) and supporting electrolyte (considering typical ions present in surface water and urine (Cl and SO-42-)) on the electrochemical system was evaluated. Then, the kinetics and primary transformations products involved in the elimination of ACE were described. It was found that, in distilled water, the process at 40 mA in NaCl presence led to 100 % of ACE degradation (10 min, 0.056 Ah L-1). Theoretical analyses of atomic charge for ACE indicated that the amide group is the most susceptible to attacks by RCS such as HOCl. On the other hand, degradation of acetaminophen in synthetic fresh urine was slower (21% of degradation after 60 min of treatment) than in distilled water. This was attributed to the other substances in the urine matrix, which induce competition for the degrading RCS.

Results of an examination of the organocatalytic enantioselective α-chlorination of 2-phenylpropanal are described. Synthetic investigation including the screening of primary and secondary aminocatalysts, many different reaction conditions, and other α-branched aldehydes show that especially primary aminocatalysts can catalyze the formation of the α-chloro branched aldehydes in good yields, but only with moderate enantioselectivities. In order to try to understand the challenge in obtaining high enantioselectivity for the aminocatalytic α-chlorination of α-branched aldehydes a series of experimental investigations were performed employing 2-phenylpropanal as a model system. These investigations have been coupled with computational investigations, which provided important insight into the moderate enantioselectivity of this chlorination reaction. Analysis of the reaction showed, that the lack of control over the selectivity of formation of the (E)- and (Z)-enamine intermediate, and the clustering of reaction barriers of possible reaction pathways help to rationalize difficulties in producing high enantioselectivity.

Naegleria. fowleri, a protozoa belonging to the free-living amoeba group, is the causative agent of a central nervous system affecting disease that is fatal in more than the 95% of the reported cases. This parasite can be found in warm water bodies such as lakes, rivers or inadequately disinfected swimming pools. On the other hand, chlorination and UV light treatment are two of the most extensively used disinfection methods in recreational water facilities. In this study the effect of chlorination and UV light on N. fowleri trophozoites was studied in a close water circuit with the aim to assess the efficacy of this disinfection methods in large pools. The obtained results showed that the chlorination was able to decrease the number of viable cells despite the elimination was not totally achieved. Nonetheless, the combination of the UV light with the chlorination allowed the complete removal of the N. fowleri trophozoites from the water in experimental testing conditions.

Compressor blades made of TC4 that are serviced in marine environments suffer from severe active corrosion under the synergetic effect of NaCl and H2O(g). A SiO2-Al2O3 glass composite coating was applied on TC4 substrate for protection by first air spraying slurry and subsequent a suitable sintering process. The corrosion behavior of the SiO2-Al2O3 glass composite coating and uncoated alloy in marine environment under the simultaneous effect of NaCl(s) and H2O(g) at 650 °C were investigated. The results indicated that the SiO2-Al2O3 glass composite coating presented good corrosion behavior and provided protection for the alloy; the superior corrosion resistance is mainly attributed to the favorable effect of the SiO2-Al2O3 glass composite coating on inhibiting self-sustainable oxychlorination. The detrimental effect of Ti on self-sustainable oxychlorination mechanism in marine environment are discussed.

Antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) are emerging contaminants leading to severe worldwide health problems. Chlorination, a widely used procedure, was extensively explored as one of the main methods to remove ARB and ARGs in recent years. In this study, to enrich the analyses of chlorination, several comprehensive effects of the chlorine disinfection system on ARB and their conjugative transfer ability were explored. The results presented that the low dose of chlorine (3-log inactivation rate) triggered cell membrane changes, with little influence on the bacteria in terms of their antibiotic resistance. However, their capacity for conjugative transfer sharply decreased. Minor consumption of chloramphenicol was achieved with the chlorine dose applied in the disinfection system. Monochloroacetonitrile (MCAN) had limited effects on the frequency of conjugative transfer, indicating that the existence of MCAN would not aggravate the dissemination of ARGs by conjugative transfer. The overall impacts of the chlorine disinfection system with different containments on antibiotic resistance need further investigation.

Biological activated carbon (BAC) filtration is usually considered to be able to decrease formation potentials (FPs) of disinfection by-products (DBPs) in drinking water treatment plant (DWTP). However, BAC filters with long running time may release microbial metabolites to effluents and therefore increase FPs of nitrogenous DBPs with high toxicity. To verify this hypothesis, this study continuously tracked BAC filters in a DWTP for one year, and assessed effects of old (running time 8–9 years) and new (running time 0–13 months) BAC filters on FPs of 15 regulated and unregulated DBPs. Results revealed that dissolved organic carbon (DOC) removal was slightly higher in the new BAC than the old one. All fluorescent components of dissolved organic matter evidently declined after new BAC filtration, but fulvic acid-like and soluble microbial product-like substances increased after old BAC filtration, which could be caused by microbial leakage. Correspondingly, new BAC filter generally removed more DBP FPs than the old one. 46.5% HAA7 FPs from chlorination and 44.3% THM4 FPs from chloramination were removed by new BAC filter. However, some DBP FPs, especially HAN FPs, were poorly removed or even increased by the old BAC filter. Proteobacteria could be a main contributor for DBP precursor removal in BAC filters. Herminiimonas, most abundant genera in new BAC filter, may explain its better DOC and UV254 removal performance and lower DBP FPs, while Bradyrhizobium, most abundant genera in old BAC filter, might produce more extracellular polymeric substances and therefore increased N-DBP FPs in old BAC effluent. This study provided insight into variations of DBP FPs and microbial communities in the new and old BAC filters, and will be helpful for the optimization of DWTP design and operation for public health.

Human estrogens prescribed for hormone replacement therapy (HRT) are known to be potent carcinogens. To find safer estrogens, several chlorinated estrogens were synthesized and their carcinogenic potential were determined. A pellet containing either 2-chloro-17β-estradiol (2-ClE2) or 4-chloro-17β-estradiol (4-ClE2) was implanted subcutaneously for 52 weeks into August Copenhagen Irish (ACI) rats, a preferred animal model for human breast cancer. 17β-Estradiol (E2) frequently induced mammary tumors while both 2-ClE2 and 4-ClE2 did not. Their 17α-ethinyl forms, thought to be orally active estrogens, were also synthesized. Neither 2-chloro-17α-ethinylestradiol (2-ClEE2) nor 4-chloro-17α-ethinylestradiol (4-ClEE2) induced tumors. The less carcinogenic effects were supported by histological examination of mammary glands of ACI rats treated with the chlorinated estrogens. A chlorine atom positioned at the 2- or 4-position of E2 may prevent the metabolic activation, resulting in reducing the carcinogenicity. 2-ClE2 and 4-ClE2 administered subcutaneously and 2-ClEE2 and 4-ClEE2 given orally to ovariectomized rats all showed uterotrophic potency, albeit slightly weaker than that of E2. Our results indicate that less carcinogenic chlorinated estrogens retaining estrogenic potential could be safer alternatives to the carcinogenic estrogens now in use for HRT.

Polycyclic aromatic hydrocarbons (PAHs) that contain both five‐ and seven‐membered rings are rare, and those where these rings are annulated to each other and build azulene units have, to date, mainly been generated in minute amounts on surfaces. Herein, a rational approach to synthesize soluble contorted PAHs containing two embedded azulene units in the bulk is presented. By stepwise detachment of tert‐butyl groups, a series of three azulene embedded PAHs with different degrees of contortion has been made to study the impact of curvature on aromaticity and conjugation. Furthermore, the azulene PAHs showed high fluorescence quantum yields in the NIR regime., Deep Blue! Soluble contorted PAHs with two embedded azulene moieties with different degrees of curvature are synthesized and spectroscopically compared.

Halocarbons have tremendous significance for the chemical industry. Arylchlorides and arylbromides are typically prepared via Friedel-Crafts reaction, using oxidative halogenation or employing halogen transfer agents, such as N-chloro- and N-bromosuccineimide. Herein, we show that K-PHI, a photocatalyst of the carbon nitride family, can easily photooxidize halide anions (Cl−, Br−) in aqueous media to promote oxidative halogenation of electron rich aromatic compounds. The technique is convenient, safe and gives the haloaromatic products with excellent yields from non-harmful starting reagents in the most sustainable fashion. We show that a solution of NaCl, mimicking seawater, can be used as a reagent for photochlorination.

In this study, the chloro-substituted hydroxyxanthones were prepared by cyclodehydration of acid derivatives and substituted phenol in the presence of Eaton reagent, followed by halogenations step to electrophilic substitution of chlorine in a moderate yield. The in vitro anticancer activity study on various cell lines revealed that the chloro functional group increases the anticancer activity of the hydroxyxanthone derivatives. The molecular docking study showed that there was a binding interaction between chloro-hydroxyxanthone and the amino acid residues such as Asp810, Cys809, Ile789, His790, and Leu644 of protein tyrosine kinase receptor (1T46.pdb).

Chlorination of coastal (CS) and deep ocean (DO) seawater was accompanied by a prominent decrease (of up to 70%) of the intensity of its emission which was measured using a 315 nm excitation wavelength. Deconvolution of the emission spectra of CS and DO seawater showed that these spectra comprised three Gauss-shaped bands. The intensities of two of these bands decreased rapidly as the halogenation proceeded. For both DO and CS seawater, two stages of changes of their fluorescence were observed. The first stage in which the relative changes of the fluorescence intensity (ΔF/F) were between zero to 0.30 and 0.40 was not accompanied by the release of individual disinfection byproduct (DBP) species. For ΔF/F values above the corresponding thresholds, the relative changes of fluorescence intensity were well correlated with the concentrations of individual DBP species such as trihalomethanes and haloacetonitriles. R2 values for CHBr3, CHBr2Cl and CHBrCl2 formed in DO seawater were 0.83, 0.80 and 0.68, respectively while for CS seawater, the corresponding R2 values were 0.91, 0.93 and 0.92. The presented data demonstrate that the intrinsic chemistry of DBP formation and dissolved organic matter (DOM) halogenation in seawater can be well quantified based on the examination of changes of its fluorescence. This approach can also be employed for practical monitoring of changes of properties of marine DOM and generation of DBPs in desalination, marine aquaculture and other processes.

The reactions of Pr2O3 and Pr6O11 with Cl2(g) were studied thermodynamically and experimentally, and proposed in the systems Pr2O3/Cl2(g) and Pr6O11/Cl2(g). A kinetic analysis was performed on Pr6O11 chlorination, which differs from with other light rare earth oxide chlorinations. The praseodymium oxychlorides obtained by full chlorination of Pr6O11 at 425 C and 800 C are different, being well characterized by X-ray diffraction, scanning electron microscopy, magnetic susceptibility measurements and X-ray photoelectron spectroscopy. The crystal structures of the oxychlorides were refined with theRietveld method. The comparison between the theoretical magnetic moment of Pr3þ and the estimated magnetic moment in the praseodymium oxychloride obtained at 425 C revealed the presence of Pr3þ and Pr4þ, whereas no significant difference was observed between the theoretical and the experimental values of Pr3þ obtained for the praseodymium oxychloride prepared at 800 C. These observations are consistent with the analyses in the X-ray photoelectron spectra for both oxychlorides. Finally, a general formula of PrO1þxCl is proposed for the oxychlorides synthesized at T < 800 C. Fil: Pomiro, Fernando. Comisión Nacional de Energía Atómica. Gerencia Complejo Tecnológico Pilcaniyeu; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Gaviría, Juan Pablo. Comisión Nacional de Energía Atómica. Gerencia Complejo Tecnológico Pilcaniyeu; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Fouga, Gastón Galo. Comisión Nacional de Energía Atómica. Gerencia Complejo Tecnológico Pilcaniyeu; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Vega, Leonardo Daniel. Comisión Nacional de Energía Atómica. Gerencia Complejo Tecnológico Pilcaniyeu; Argentina Fil: Bohe, Ana Ester. Comisión Nacional de Energía Atómica. Gerencia Complejo Tecnológico Pilcaniyeu; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

Water purification is a crucial process in the operation of a municipality. Ensuring that water treatment plants are meeting regulatory requirements is a vital, but complicated and costly process. Because water treatment plant influent and effluent rates are demand driven, and vary both diurnally and seasonally, controlling flow rates for the disinfection stage can be challenging both operationally and economically. Thus, performing large-scale field experiments to verify water quality regulatory criteria such as modal transport time of conservative tracers in a chlorine disinfection contact tank under extreme operating conditions can range from difficult and costly to impossible. In this paper, a computational fluid dynamics (CFD) approach is used to verify the compliance of a water reclamation plant disinfection stage with respect to modal time. CFD allows a large parameter space to be tested without the need to build large physical models or taking functioning systems in a treatment plant offline. This can save facilities large amounts of time and money when designing, optimizing, and developing plants or checking compliance. This paper introduces a hybrid approach of computational analysis of a water reclamation plant's chlorine contact tank in Southern California. The method uses a hybrid approach which combines three-dimensional CFD with hydraulic grade line analysis of the open water surface. Verification cases were compared to experimental measurements at a functioning, full-scale plant with modal contact time differences below 15%. The method was then used to predict residence time distributions (RTDs) for cases which could not be artificially induced at the plant, but represented peak flow conditions that could be expected. PRACTITIONER POINTS: The hybrid 3-dimensional CFD method allows low cost simulation of the disinfection stage. By using head loss calculations to properly define the water level at each section, a steady-state single phase flow simulation can be run in 3D without the need to scale down geometries. This allows for more accurate transport results and parameter studies.

Crevice corrosion behavior of Alloy 690 in high-temperature aerated chloride solution was studied using a self-designed crevice device. The SEM, EDS, XRD, and XPS analyses results indicated that the oxide films outside the crevice consisted of Ni-Cr oxides containing a small amount of hydroxides, and the oxide films on crevice mouth consisted of a (Ni,Fe)(Fe,Cr)2O4 spinel oxides outer layer and a Cr(OH)3 inner layer, and the oxide films inside the crevice consisted of a α-CrOOH outer layer and a Cr(OH)3 inner layer. When crevice corrosion occurred, the hydrolysis of Cr3+ led to the formation of Cr(OH)3 inside the crevice, and caused the pH value of crevice solution to decrease, and Cl− migrated from outside the crevice into inside the crevice due to electrical neutrality principle and accumulation. When the water chemistry inside the crevice reached the critical value of active dissolution of metal, the active dissolution of metal inside the crevice occurred. In addition, (Ni,Fe)(Fe,Cr)2O4 spinel oxides on the crevice mouth were formed by the deposition of metal ions migrated from inside the crevice. The mechanism of crevice corrosion and the formation mechanism of oxide films at different regions were also discussed.

The development of any commercial product should also be aimed at reducing the risk associated with it, according to the safe-by-design concept; that is, risk assessment should always be at the center of the design, and the impact on human and environmental health should be assessed and eliminated during the product development phase and not afterwards. Unfortunately, even today, most operators in any production sector implement the philosophy of “risk management” or rather of managing the problem when it occurs, using spot interventions instead of changing the approach. This argument is also valid in the production of solar filters, which have reached a satisfactory degree of efficiency in the face of a substantial underestimation of the risks associated with their possible environmental fate. In fact, solar filters have been found in bathing waters and their environmental fate may depend on various factors such as the pH of the water, the presence of organic material, metal ions and light, and, above all, the chemical agents used in the disinfection of the water itself. Thus, during disinfection processes, the generation of dozens of products with a lower molecular weight and generally of an aromatic nature has been tested, where some of them did not receive an exact structural definition and a precise evaluation of their precise toxicological profile. Therefore, it is interesting to draw a complete picture of organic sunscreens and of the byproducts obtained under different conditions and their related ecotoxicological profile.

Klebsiella pneumoniae is a pathogenic agent able to form biofilms on water storage tanks and pipe walls. This opportunistic pathogen can generate a thick layer as one of its essential virulence factors, enabling the bacteria to survive disinfection processes and thus develop drug resistance. Understanding the metabolic differences between biofilm and planktonic cells of the K. pneumoniae response to NaClO is key to developing strategies to control its spread. In this study, we performed an NMR metabolic profile analysis to compare the response to a sublethal concentration of sodium hypochlorite of biofilm and planktonic cells of K. pneumoniae cultured inside silicone tubing. Metabolic profiles revealed changes in the metabolism of planktonic cells after a contact time of 10 min with 7 mg L−1 of sodium hypochlorite. A decrease in the production of metabolites such as lactate, acetate, ethanol, and succinate in this cell type was observed, thus indicating a disruption of glucose intake. In contrast, the biofilms displayed a high metabolic heterogeneity, and the treatment did not affect their metabolic signature.

Iodine is a naturally-occurring halogen in natural waters generally present in concentrations between 0.5 and 100 mu g L-1. During oxidative drinking water treatment, iodine-containing disinfection by-products (I-DBPs) can be formed. The formation of I-DBPs was mostly associated to taste and odor issues in the produced tap water but has become a potential health problem more recently due to the generally more toxic character of I-DBPs compared to their chlorinated and brominated analogues., This paper is a systematic and critical review on the reactivity of iodide and on the most common intermediate reactive iodine species HOI. The first step of oxidation of I- to HOI is rapid for most oxidants (apparent second-order rate constant, k(app) > 10(3) M(-1)s(-1) at pH 7). The reactivity of hypoiodous acid with inorganic and organic compounds appears to be intermediate between chlorine and bromine. The life times of HOI during oxidative treatment determines the extent of the formation of I-DBPs. Based on this assessment, chloramine, chlorine dioxide and permanganate are of the highest concern when treating iodide-containing waters. The conditions for the formation of iodo-organic compounds are also critically reviewed., From an evaluation of I-DBPs in more than 650 drinking waters, it can be concluded that one third show low levels of I-THMs ( 10 mu g L-1. The most frequently detected I-THM is CHCl2I followed by CHBrClI. More polar I-DBPs, iodoacetic acid in particular, have been reviewed as well., Finally, the transformation of iodide to iodate, a safe iodine-derived end-product, has been proposed to mitigate the formation of I-DBPs in drinking water processes. For this purpose a pre-oxidation step with either ozone or ferrate(VI) to completely oxidize iodide to iodate is an efficient process. Activated carbon has also been shown to be efficient in reducing I-DBPs during drinking water oxidation.

Highlights: • Overview on oxidative treatment processes for different industrial applications • Compilation of disinfection by-product types/concentrations in marine water uses • Estimation of global DBP inputs into marine water from different industries • Comparison of anthropogenic bromoform production to emissions from natural sources Abstract: Oxidative treatment of seawater in coastal and shipboard installations is applied to control biofouling and/or minimize the input of noxious or invasive species into the marine environment. This treatment allows a safe and efficient operation of industrial installations and helps to protect human health from infectious diseases and to maintain the biodiversity in the marine environment. On the downside, the application of chemical oxidants generates undesired organic compounds, so-called disinfection by-products (DBPs), which are discharged into the marine environment. This article provides an overview on sources and quantities of DBP inputs, which could serve as basis for hazard analysis for the marine environment, human health and the atmosphere. During oxidation of marine water, mainly brominated DBPs are generated with bromoform (CHBr3) being the major DBP. CHBr3 has been used as an indicator to compare inputs from different sources. Total global annual volumes of treated seawater inputs resulting from cooling processes of coastal power stations, from desalination plants and from ballast water treatment in ships are estimated to be 470 – 800 × 109 m3, 46 × 109 m3 and 3.5 × 109 m3, respectively. Overall, the total estimated anthropogenic bromoform production and discharge adds up to 13.5 – 21.8 × 106 kg/a (kg per year) with contributions of 11.8 – 20.1 × 106 kg/a from cooling water treatment, 0.89 × 106 kg/a from desalination and 0.86 × 106 kg/a from ballast water treatment. This equals approximately 2 – 6 % of the natural bromoform emissions from marine water, which is estimated to be 385 – 870 × 106 kg/a.

Flavonoids, a large group of secondary plant phenolic metabolites, are important natural antioxidants and regulators of cellular redox balance. The present study addressed evaluation of the electronic properties of some flavonoids belonging to different classes such as quercetin (flavonols), catechin (flavanols), and naringenin (flavanones) and their interactions with oxidants in model systems of DPPH reduction, flavonoid autoxidation, and chlorination. According to our ab initio calculations, the high net negative excess charges of the C rings and the small positive excess charges of the B rings of quercetin, catechin, and naringenin make these parts of flavonoid molecules attractive for electrophilic attack. The 3'-OH group of the B ring of quercetin has the highest excess negative charge and the lowest energy of hydrogen atom abstraction for the flavonoids studied. The apparent reaction rate constants (s-1, 20 °C) and the activation energies (kJ/mol) of DPPH reduction were 0.34 ± 0.06 and 23.0 ± 2.5 in the case of quercetin, 0.09 ± 0.02 and 32.5 ± 2.5 in the case of catechin, respectively. The stoichiometry of the DPPH-flavonoid reaction was 1:1. The activation energies (kJ/mol) of quercetin and catechin autoxidations were 50.8 ± 6.1 and 58.1 ± 7.2, respectively. Naringenin was not oxidized by the DPPH radical and air oxygen (autoxidation) and the flavonoids studied effectively prevented HOCl-induced hemolysis due to direct scavenging of hypochlorous acid (flavonoid chlorination). The best antioxidant quercetin had the highest value of HOMO energy, a planar structure and optimal electron orbital delocalization on all the phenolic rings due to the C2=C3 double bond in the C ring (absent in catechin and naringenin).

9 pages, 5 figures, 2 table, Polychlorinated biphenyls (PCBs) are compounds of significant interest due to high toxicity, persistence, long-range atmospheric transport, and bioaccumulation. These compounds can interact with components present in the environment, including dissolved organic matter (DOM) in soils and waters, thereby modifying its availability and movement. In this study, DOM was fractionated by ultrafiltration and characterized according to its hydrophobicity and hydrophilicity, then the interaction of a series of PCBs and different DOM fractions was evaluated. The DOM was collected from the surface waters of three sectors located along a river in the southern part of America. These sectors are subject to different anthropic activities, thus the DOM of sector 1, with the least anthropic influence, was mainly hydrophobic and with a high content of aromatic structures. In contrast, the DOM collected from sectors 2 and 3, where anthropic activity is highest, was slightly hydrophobic and hydrophilic, respectively. The DOM of these two sectors was mainly composed of low molecular weight macromolecules. These results revealed that more hydrophobic PCBs (i.e., 101, 118, 138, and 180) have a greater affinity to DOM with a higher molecular weight (i.e., >1 kDa). In turn, PCBs with lesser chlorination and hydrophobicity presented a greater affinity to DOM with a lower molecular weight. In conclusion, our study shows that the high molecular weight DOM is responsible for mobilizing PCBs with a high degree of chlorination, This study was funded through project grant No. 11110223, awarded by the Chilean National Fund for Scientific and Technological Development (FONDECYT, Spanish acronym), awarded to Tatiana Garrido

Bacterial inactivation efficiency of chlorine varies with organisms and environmental conditions. The comparability of different samples/studies, especially comparing indigenous bacterial communities with pure cultures, is impeded by inconsistent experimental conditions and analytical methods used in various studies. We tested a novel 96-well plate FCM experimental and automated analytical approach, where bacterial communities and pure cultures were suspended in the same natural water matrix prior to chlorination directly in the plate. We demonstrated the ability to rapidly monitor the efficiency of 32 different combinations of chlorine concentration and time (i.e. chlorine exposure) on bacterial pure cultures and indigenous aquatic communities, which enabled correct comparison of the data from different samples under the exact same experimental conditions. In this study, the 96-well plate automated FCM approach enabled large sets (896) of independent chlorination experiments to be carried out in a short time period. To our knowledge, this is the largest dataset of chlorination experiments which consumed least time (within 18 h after sampling) until now. Staining with SYBR Green I (SG) and SG combined with propidium iodide (SGPI) was used to assess cellular damage during chlorination. The results showed that with the same chlorine exposure, a higher chlorine concentration with a shorter contact time is favorable for inactivation of bacteria. Our research provides a promising framework to compare disinfection characteristics of various microorganism and can be further developed to diagnose effect of antimicrobial products.

Orientador: Gisela de Aragão Umbuzeiro Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Tecnologia Resumo: Cerca de 70% dos corantes utilizados em indústrias têxteis são corantes do tipo azo, que se caracterizam pelo grupo -N=N- ligado a sistemas aromáticos, sendo que a função azo inclui os principais tipos de corantes. A eliminação da cor no efluente é um grande desafio para o setor têxtil, já que, aproximadamente, 15% da produção mundial de corantes são descartados para o meio ambiente durante sua produção, processamento e aplicação. O corante comercial Disperse Red 1 utilizado neste trabalho é composto por seis corantes diferentes e surfactante, porém o corante principal em sua composição é o Disperse Red 1 (N-Ethyl-N-(2-hydroxyethyl)-4-(4- nitrophenylazo) aniline; CAS number 2872-52-8) com 60% em massa. O corante comercial foi submetido ao processo de cloração com gás cloro, simulando as condições utilizadas em Estações de Tratamento de Efluentes. A toxicidade do corante comercial CI Disperse Red 1 e do subproduto clorado foi avaliada em testes agudos com Ceriodapnhia dubia, Ceriodaphnia silvestrii, Daphnia similis, Daphnia magna, Hydra attenuata, e em testes crônicos com Pseudokirchneriella subcapitata, Ceriodapnhia dubia, e Hydra attenuata. A mutagenicidade foi avaliada com ensaio Salmonella/microssoma com as linhagens TA98, TA100 e YG1041. D. similis foi o organismo mais sensível ao corante comercial; e H. attenuata foi mais sensível ao subproduto clorado. A CE50 obtida para D. similis para o corante comercial é similar ao corante puro, mostrando que a toxicidade do corante comercial é devido ao Disperse Red 1. O subproduto clorado foi menos tóxico do que o corante para todos os organismos testados, com exceção de H. attenuata. Porém, o subproduto clorado foi mais mutagênico do que o corante para todas as linhagens testadas. Mais estudos são necessários para compreender os mecanismos envolvidos na toxicidade destes corantes, considerando sua alta toxicidade para organismos aquáticos, a fim de fornecer informações para a elaboração de corantes ambientalmente corretos. Os resultados obtidos neste trabalho podem fornecer informações úteis para a derivação de critérios para qualidade da água para esse corante Abstract: About 70% of dyes used in textiles industries are of type azo. These days 15% of the dye world production is discharged into the environment during its production, processing and application. Effluent that contains dyes must have their color removed in order to be in compliance with environmental regulations, but sometimes the treatment can lead to more toxic compounds. The commercial azo dye Disperse Red 1 used in this study is composed of six different dye constituents and surfactant; however the main dye of the commercial product is the Disperse Red 1 (N-Ethyl-N-(2-hydroxyethyl)-4-(4-nitrophenylazo) aniline; CAS number 2872-52-8). Commercial dye samples were treated with chlorine gas, in order to simulate the conditions used in effluent treatment plant. The ecotoxicity of the commercial dye and chlorinated byproduct was evaluated in acute tests with Ceriodaphnia dubia, Ceriodaphnia silvestrii, Daphnia similis, Daphnia magna, and Hydra attenuata as well as in chronic toxicity tests with Pseudokirchneriella subcapitata, Ceriodapnhia dubia and Hydra attenuata. Mutagenicity was evaluated using Salmonella/microsome assay with TA98, TA100 and YG1041 strains. The commercial dye Disperse Red 1 was similarly toxic to P. subcapitata, C. dubia and D. similis, even with different endpoints. The chlorinated byproduct was less toxic to all organisms tested than the dye, except for H. attenuata. The toxicity of the commercial dye is due to Disperse Red 1 itself and the surfactant does not seem to contribute to the toxicity, at least to D. similis. The chlorinated byproduct was more mutagenic than the commercial dye. More studies are necessary to address the mechanisms involved in the toxicity of this azo dye considering its high toxicity to aquatic organisms in order to provide information for the design of more environmental friendly dye products. The results obtained in this work can provide useful information for the derivation of water quality criteria for this dye Mestrado Tecnologia e Inovação Mestre em Tecnologia

C(sp3 )-Cl bonds are present in numerous biologically active small molecules, and an ideal route for their preparation is by the chlorination of a C(sp3 )-H bond. However, most current methods for the chlorination of C(sp3 )-H bonds are insufficiently site selective and tolerant of functional groups to be applicable to the late-stage functionalization of complex molecules. We report a method for the highly selective chlorination of tertiary and benzylic C(sp3 )-H bonds to produce the corresponding chlorides, generally in high yields. The reaction occurs with a mixture of an azidoiodinane, which generates a selective H-atom abstractor under mild conditions, and a readily-accessible and inexpensive copper(II) chloride complex, which efficiently transfers a chlorine atom. The reaction's exceptional functional group tolerance is demonstrated by the chlorination of >30 diversely functionalized substrates and the late-stage chlorination of a dozen derivatives of natural products and active pharmaceutical ingredients.

The present dissertation deals with catalytic and stoichiometric organohalogen chemistry. The first part of this thesis includes mechanistic studies and different synthetic applications of the organocatalytic alpha chlorination of aldehydes. The application of novel polyinterhalides as practical reagents in organic synthesis is investigated in the second part. The thesis concludes with studies towards the total synthesis of the two meroterpenes hypatulin A and B.

Concentrations of several toxic disinfection by-products (DBP), notably haloacetonitriles (e.g., trichloroacetonitrile, TCAN) and haloketones (e.g., di- and trichloropropanone, DCPN and TCPN, respectively) are affected by chlorination conditions and the inherent instability of these DBPs. In this study, effects of temperature, chlorine dose and reaction time on the formation of TCAN, DCPN and TCPN were interpreted using the approach of differential absorbance spectroscopy. Experimental data obtained for a wide range of water quality conditions demonstrate that in some cases the concentrations of some of the unstable DBPs increased rather than decreased at low temperatures and realistically long contact times. Despite the presence of pronounced changes of the kinetics of generation and degradation of these DBPs at varying temperatures and chlorine doses, their concentrations were strongly correlated with the concurrent changes of spectroscopic properties of DOM quantified via differential absorbance measurements at 272 nm (ΔA272). The maximum values of TCAN, DCPN and TCPN concentrations observed for the chlorination of eight different surface waters occur at the relative decreases of absorbance at 272 nm (defined as RΔA272) values of ca. 0.32 (±0.03), 0.24 (±0.05), and 0.42 (±0.03), respectively. The activation energies of degradation reactions of unstable DBPs were examined and the results indicate that TCAN and TCPN are caused by their hydrolysis with OH− while the degradation of DCPN is mainly caused by halogenation reaction with HOCl. These results in this study may be important for controlling the formation of unstable DBPs and further optimization of drinking water treatment.

We herein report an unprecedented strategy for the asymmetric α‐chlorination of β‐keto esters with hypervalent iodine‐based Cl‐transfer reagents using simple Cinchona alkaloid catalysts. Our investigations support an α‐chlorination mechanism where the Cinchona species serves as a nucleophilic catalyst by reacting with the chlorinating agent to generate a chiral electrophilic Cl‐transfer reagent in situ. Using at least 20 mol‐% of the alkaloid catalyst allows for good yields and enantioselectivities for a variety of different β‐keto esters under operationally simple conditions., Simple Cinchona alkaloids serve as nucleophilic organocatalysts to facilitate the enantioselective α‐chlorination of β‐keto esters by using hypervalent iodine‐based Cl‐transfer reagentsJohn Wiley & Sons, Ltd.

Pollution of natural water and even source water with pharmaceuticals is problematic worldwide and raises concern about the possibility of disinfection byproduct (DBP) formation during subsequent water treatment. In this study, the formation of DBPs, especially dichloroacetamide (DCAcAm), was investigated during chlorination and chloramination of tetracyclines, which are a class of broad-spectrum antibiotics. DBPs including DCAcAm were formed during chlorination and chloramination of tetracycline (TC). Although the concentrations and theoretical cytotoxicity of the DBPs formed from TC were affected by the contact time, disinfectant dose, and pH, DCAcAm was the main contributor determining the yields and cytotoxicity of the measured DBPs. The DCAcAm yields from four tetracycline antibiotics ranged from 0.43% to 54.26% for chlorination. For chloramination, the DCAcAm yields reached 44.57%, and the nitrogen in DCAcAm mainly came from tetracycline antibiotics rather than chloramines. ClO2 pre-oxidation and UV photolysis decreased DCAcAm formation during chlorination and chloramination of TC. The high yields observed in this study suggest that tetracycline antibiotics are possible precursors of DCAcAm., Graphical abstract Image 1, Highlights • Tetracycline antibiotics had high DCAcAm yields during chlor(am)ination. • DCAcAm was the major contributor to the DBP cytotoxicity from chloramination of TC. • Nitrogen in DCAcAm mainly came from tetracyclines during chloramination. • ClO2 pre-oxidation decreased DCAcAm formation during chlor(am)ination of TC.

This work studies the chlorination and monochloramination reaction kinetics of two phenazone-type drugs (phenazone – Phe and propyphenazone – PrPhe) and three metabolites of phenazone-type drugs (4-formylaminoantipyrine – FAA, 4-aminoantipyrine - AA and 4-acetoamidoantipyrine - AAA). Kinetics were faster with chlorine (apparent second-order constants between 100 and 66,500 times higher) than with monochloramine. For FAA and AAA, no significant reaction was observed during monochloramination. Further, apparent rate constants decreased as the pH increased from pH 5.7 to 8.3, except during chlorination of AA. The transformation products (TPs) formed were also elucidated by liquid chromatography-high resolution mass spectrometry. The main transformation pathway for Phe and PrPhe consisted of halogenations, hydroxylations and dealkylations, while AAA and FAA were firstly transformed to AA, then followed by pyrazole ring opening and hydroxylations. The extend of the reaction was also tested in real water samples, where, in general, slower reaction kinetics were obtained during monochloramination, while the chlorination reaction showed similar half-lives to ultrapure water. Finally, acute and chronic toxicity of the TPs were estimated using two quantitative structure-activity relationship (QSAR) software (ECOSAR and TEST), showing that some TPs could be more toxic than their precursor compounds This research was funded by Xunta de Galicia (ED431C2017/36), Spanish Agencia Estatal de Investigación (ref. CTM2017-84763-C3-R-2) and FEDER/ERDF funds. This research has been co-financed by the European Regional Development Fund through the Interreg V-A Spain-Portugal Programme (POCTEP) 2014–2020 (ref. 0725_NOR_WATER_1_P). It only reflects the author's view, thus Programme authorities are not liable for any use that may be made of the information contained therein. SI