Halogenation of Anilines: Formation of Haloacetonitriles and Large-Molecule Disinfection Byproducts.

Aniline-related structures are common in anthropogenic chemicals, such as pharmaceuticals and pesticides. Compared with the widely studied phenolic compounds, anilines have received far less assessment of their disinfection byproduct (DBP) formation potential, even though anilines and phenols likely exhibit similar reactivities on their respective aromatic rings. In this study, a suite of 19 aniline compounds with varying N- and ring-substitutions were evaluated for their formation potentials of haloacetonitriles and trihalomethanes under free chlorination and free bromination conditions. Eight of the aniline compounds formed dichloroacetonitrile at yields above 0.50%; the highest yields were observed for 4-nitroaniline, 3-chloroaniline, and 4-(methylsulfonyl)aniline (1.6-2.3%). Free bromination generally resulted in greater haloacetonitrile yields with the highest yield observed for 2-ethylaniline (6.5%). The trihalomethane yields of anilines correlated with their haloacetonitrile yields. Product analysis of aniline chlorination by liquid chromatography-high-resolution mass spectrometry revealed several large-molecule DBPs, including chloroanilines, (chloro)hydroxyanilines, (chloro)benzoquinone imines, and ring-cleavage products. The product time profiles suggested that the reaction pathways include initial ring chlorination and hydroxylation, followed by the formation of benzoquinone imines that eventually led to ring cleavage. This work revealed the potential of aniline-related moieties in micropollutants as potent precursors to haloacetonitriles and other emerging large-molecule DBPs with the expected toxicity.

Closing Dichloramine Decomposition Nitrogen and Oxygen Mass Balances: Relative Importance of End-Products from the Reactive Nitrogen Species Pathway.

In drinking water chloramination, monochloramine autodecomposition occurs in the presence of excess free ammonia through dichloramine, the decay of which was implicated in N-nitrosodimethylamine (NDMA) formation by (i) dichloramine hydrolysis to nitroxyl which reacts with itself to nitrous oxide (N2O), (ii) nitroxyl reaction with dissolved oxygen (DO) to peroxynitrite or mono/dichloramine to nitrogen gas (N2), and (iii) peroxynitrite reaction with total dimethylamine (TOTDMA) to NDMA or decomposition to nitrite/nitrate. Here, the yields of nitrogen and oxygen-containing end-products were quantified at pH 9 from NHCl2 decomposition at 200, 400, or 800 µeq Cl2·L-1 with and without 10 µM-N TOTDMA under ambient DO (∼500 µM-O) and, to limit peroxynitrite formation, low DO (≤40 µM-O). Without TOTDMA, the sum of free ammonia, monochloramine, dichloramine, N2, N2O, nitrite, and nitrate indicated nitrogen recoveries ±95% confidence intervals were not significantly different under ambient (90 ± 6%) and low (93 ± 7%) DO. With TOTDMA, nitrogen recoveries were less under ambient (82 ± 5%) than low (97 ± 7%) DO. Oxygen recoveries under ambient DO were 88-97%, and the so-called unidentified product of dichloramine decomposition formed at about three-fold greater concentration under ambient compared to low DO, like NDMA, consistent with a DO limitation. Unidentified product formation stemmed from peroxynitrite decomposition products reacting with mono/dichloramine. For a 2:2:1 nitrogen/oxygen/chlorine atom ratio and its estimated molar absorptivity, unidentified product inclusion with uncertainty may close oxygen recoveries and increase nitrogen recoveries to 98% (ambient DO) and 100% (low DO).

Divergent Fate and Roles of Dissolved Organic Matter from Spatially Varied Grassland Soils in China During Long-Term Biogeochemical Processes.

Terrestrial dissolved organic matter (DOM) is critical to global carbon and nutrient cycling, climate change, and human health. However, how the spatial and compositional differences of soil DOM affect its dynamics and fate in water during the carbon cycle is largely unclear. Herein, the biodegradation of DOM from 14 spatially distributed grassland soils in China with diverse organic composition was investigated by 165 days of incubation experiments. The results showed that although the high humified fraction (high-HS) regions were featured by high humic-like fractions of 4-25 kDa molecular weight, especially the abundant condensed aromatics and tannins, they unexpectedly displayed greater DOM degradation during 45-165 days. In contrast, the unique proteinaceous and 25-100 kDa fractions enriched in the low humified fraction (low-HS) regions were drastically depleted and improved the decay of bulk DOM but only during 0-45 days. Together, DOM from the high-HS regions would cause lower CO2 outgassing to the atmosphere but higher organic loads for drinking water production in the short term than that from the low-HS regions. However, this would be reversed for the two regions during the long-term transformation processes. These findings highlight the importance of spatial and temporal variability of DOM biogeochemistry to mitigate the negative impacts of grassland soil DOM on climate, waters, and humans.

Natural Disinfection-like Process Unveiled in Soil Microenvironments by Enzyme-Catalyzed Chlorination.

Substantial natural chlorination processes are a growing concern in diverse terrestrial ecosystems, occurring through abiotic redox reactions or biological enzymatic reactions. Among these, exoenzymatically mediated chlorination is suggested to be an important pathway for producing organochlorines and converting chloride ions (Cl-) to reactive chlorine species (RCS) in the presence of reactive oxygen species like hydrogen peroxide (H2O2). However, the role of natural enzymatic chlorination in antibacterial activity occurring in soil microenvironments remains unexplored. Here, we conceptualized that heme-containing chloroperoxidase (CPO)-catalyzed chlorination functions as a naturally occurring disinfection process in soils. Combining antimicrobial experiments and microfluidic chip-based fluorescence imaging, we showed that the enzymatic chlorination process exhibited significantly enhanced antibacterial activity against Escherichia coli and Bacillus subtilis compared to H2O2. This enhancement was primarily attributed to in situ-formed RCS. Based on semiquantitative imaging of RCS distribution using a fluorescence probe, the effective distance of this antibacterial effect was estimated to be approximately 2 mm. Ultrahigh-resolution mass spectrometry analysis showed over 97% similarity between chlorine-containing formulas from CPO-catalyzed chlorination and abiotic chlorination (by sodium hypochlorite) of model dissolved organic matter, indicating a natural source of disinfection byproduct analogues. Our findings unveil a novel natural disinfection process in soils mediated by indigenous enzymes, which effectively links chlorine-carbon interactions and reactive species dynamics.

Harnessing bromide ions to boost peroxymonosulfate for reactive yellow 145 dye degradation.

Bromide (Br-) was found in the fresh waters at concentrations from 0.1 to 1 mg/L and can be used to activate peroxymonosulfate (PMS) as a widely used chemical oxidation agent. In the present study, the reaction between PMS and Br- ions (PMS/Br- process) for the effective degradation of reactive yellow 145 (RY-145) dye was investigated by changing operational parameters vis solution pH, dosage of Br- ions and PMS, RY-145 concentration, and reaction time. Based on the results, the simultaneous presence of PMS and Br- ions in the solution led to efficient degradation of RY-145 with a synergistic index of 11.89. The degradation efficiency of RY-145 was decreased in severe basic pH and the presence of CO32- ions as a coexisting anion. Likewise, 4 mg/L of humic acid (HA), used as a classic scavenger, led to a 26.53% decrease in the RY-145 degradation efficiency. The free bromine (HOBr/OBr-), superoxide radical (●O2-), and singlet oxygen (1O2) was the dominant oxidation agents in RY-145 degradation, which confirmed the nonradical degradation pathway. In addition, PMS/Br- process showed excellent ability in mineralizing RY-145 in different aqueous solutions (total organic carbon (TOC) decreased 86.39% in deionized water and 78.23% in tap water). Although pollutants such as azo dyes can be effectively removed in the PMS/Br- process, the formation of byproducts should be strategically controlled and special attention should be paid when the PMS-based advance oxidation process is applied to treat Br- containing solutions.

Climate change and future water demand: Implications for chlorine and trihalomethanes management in water distribution systems.

The global change in surface water quality calls for increased preparedness of drinking water utilities. The increasing frequency of extreme climatic events combined with global warming can impact source and treated water characteristics such as temperature and natural organic matter. On the other hand, water saving policies in response to water and energy crisis in some countries can aggravate the situation by increasing the water residence time in the drinking water distribution system (DWDS). This study investigates the individual and combined effect of increased dissolved organic carbon (DOC), increased temperature, and reduced water demand on fate and transport of chlorine and trihalomethanes (THMs) within a full-scale DWDS in Canada. Chlorine and THM prediction models were calibrated with laboratory experiments and implemented in EPANET-MATLAB toolkit for prediction in the DWDS under different combinations of DOC, temperature, and demand. The duration of low chlorine residuals (<0.2 mg/L) and high THM (>80 µg/L) periods within a day in each scenario was reported using a reliability index. Low-reliability zones prone to microbial regrowth or high THM exposure were then delineated geographically on the city DWDS. Results revealed that water demand reduction primarily affects chlorine availability, with less concern for THM formation. The reduction in nodal chlorine reliability was gradual with rising temperature and DOC of the treated water and reducing water demand. Nodal THM reliability remained unchanged until certain thresholds were reached, i.e., temperature >25 °C for waters with DOC <1.52 mg/L, and DOC >2.2 mg/L for waters with temperature = 17 °C. At these critical thresholds, an abrupt network-wide THM exceedance of 80 µg/L occurred. Under higher DOC and temperature levels in future, employing the proposed approach revealed that increasing the applied chlorine dosage (which is a conventional method used to ensure sufficient chlorine coverage) results in elevated exposure toTHMs and is not recommended. This approach aids water utilities in assessing the effectiveness of different intervention measures to solve water quality problems, identify site-specific thresholds leading to major decreases in system reliability, and integrate climate adaptation into water safety management.

Overlooked Iodo-Disinfection Byproduct Formation When Cooking Pasta with Iodized Table Salt.

Iodized table salt provides iodide that is essential for health. However, during cooking, we found that chloramine residuals in tap water can react with iodide in table salt and organic matter in pasta to form iodinated disinfection byproducts (I-DBPs). While naturally occurring iodide in source waters is known to react with chloramine and dissolved organic carbon (e.g., humic acid) during the treatment of drinking water, this is the first study to investigate I-DBP formation from cooking real food with iodized table salt and chloraminated tap water. Matrix effects from the pasta posed an analytical challenge, necessitating the development of a new method for sensitive and reproducible measurements. The optimized method utilized sample cleanup with Captiva EMR-Lipid sorbent, extraction with ethyl acetate, standard addition calibration, and analysis using gas chromatography (GC)-mass spectrometry (MS)/MS. Using this method, seven I-DBPs, including six iodo-trihalomethanes (I-THMs) and iodoacetonitrile, were detected when iodized table salt was used to cook pasta, while no I-DBPs were formed with Kosher or Himalayan salts. Total I-THM levels of 11.1 ng/g in pasta combined with cooking water were measured, with triiodomethane and chlorodiiodomethane dominant, at 6.7 and 1.3 ng/g, respectively. Calculated cytotoxicity and genotoxicity of I-THMs for the pasta with cooking water were 126- and 18-fold, respectively, compared to the corresponding chloraminated tap water. However, when the cooked pasta was separated (strained) from the pasta water, chlorodiiodomethane was the dominant I-THM, and lower levels of total I-THMs (retaining 30% of the I-THMs) and calculated toxicity were observed. This study highlights an overlooked source of exposure to toxic I-DBPs. At the same time, the formation of I-DBPs can be avoided by boiling the pasta without a lid and adding iodized salt after cooking.

Production of Dichloroacetonitrile from Derivatives of Isoxaflutole Herbicide during Water Treatment.

The herbicide isoxaflutole has the potential to contaminate drinking water directly, as well as upon hydrolyzing to its active form diketonitrile. Diketonitrile also may impact water quality by acting as a precursor for dichloroacetonitrile (DCAN), which is an unregulated but highly toxic disinfection byproduct (DBP). In this study, we investigated the reaction of diketonitrile with free chlorine and chloramine to form DCAN. We found that diketonitrile reacts with free chlorine within seconds but reacts with chloramine on the time scale of hours to days. In the presence of both oxidants, DCAN was generated at yields up to 100%. Diketonitrile reacted fastest with chlorine at circumneutral pH, which was consistent with base-catalyzed halogenation involving the enolate form of diketonitrile present at alkaline pH and electrophilic hypochlorous acid, which decreases in abundance above its pKa (7.5). In contrast, we found that diketonitrile reacts faster with chloramine as pH values decreased, consistent with an attack on the enolate by electrophilic protonated monochloramine that increases in abundance at acidic pH approaching its pKa (1.6). Our results indicate that increasing isoxaflutole use, particularly in light of the recent release of genetically modified isoxaflutole-tolerant crops, could result in greater occurrences of a high-yield DCAN precursor during disinfection.

Reactions of Monobromamine and Dibromamine with Phenolic Compounds and Organic Matter: Kinetics and Formation of Bromophenols and Bromoform.

Monobromamine (NH2Br) and dibromamine (NHBr2) produced from reactions of hypobromous acid (HOBr) with ammonia can react with phenolic structures of natural organic matter (NOM) to produce disinfection byproducts such as bromoform (CHBr3). The reactivity of NH2Br was controlled by the reaction of the bromoammonium ion (NH3Br+) with phenolate species, with specific rate constants ranging from 6.32 × 102 for 2,4,6-tribromophenol to 1.22 × 108 M-1 s-1 for phenol. Reactions of NHBr2 with phenol and bromophenols were negligible compared to its self-decomposition; rate constants could be determined only with resorcinol for pH > 7. At pH 8.1-8.2, no formation of CHBr3 was observed from the reaction of NH2Br with phenol while the reaction of NH2Br with resorcinol produced a significant concentration of CHBr3. In contrast to NH2Br, a significant amount of CHBr3 produced with an excess of NHBr2 over phenol was explained by the reactions of HOBr produced from NHBr2 decomposition. A comprehensive kinetic model including the formation and decomposition of bromamines and the reactivity of HOBr and NH2Br with phenolic compounds was developed at pH 8.0-8.3. Furthermore, the kinetic model was used to evaluate the significance of the NH2Br and NHBr2 reactions with the phenolic structures of two NOM isolates.

Changes in the structural characteristics of EfOM during coagulation by aluminum chloride and the effect on the formation of disinfection byproducts.

The effects of coagulation on the removal efficiency of different fractions of effluent organic matter (EfOM) from wastewater treatment plants were investigated to identify changes in their structural characteristics and the influences on trihalomethane formation potential (THMFP) and haloacetic acid formation potential (HAAFP). The results indicated that coagulation performed better for the removal of hydrophobic base (HOB) and hydrophobic neutral (HON) fractions than hydrophilic (HI) and hydrophobic acid (HOA) fractions. The removal efficiency was higher under neutral than under acidic conditions for all fractions. As a result, lower levels of THMFP and HAAFP were detected at pH7. The excitation-emission matrix spectra indicated that the HI fraction contained humic acid-like substances that reacted with chlorine to form THMs. The HON fraction contained soluble microbial byproduct-like substances with a higher potential to create HAAs. The results of Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and high-pressure size exclusion chromatography (HP-SEC) of the raw and coagulated water indicated that a higher molecular weight, α-carbon, COOH, aromatic structures, and polysaccharides were associated with a higher production of disinfection byproducts (DBP). These results elucidate the coagulation efficiencies of EfOM fractions associated with different mechanisms and facilitate the prediction of DBP formation by each fraction based on specific structural characteristics.

Emerging disinfection by-products formation of various molecular weight organic matter fractions in raw water contaminated with treated wastewater.

Combining dissolved organic matter (DOM) in raw water (RW) with DOM in treated wastewater (TWW) can react with chlorine and pose emerging disinfection by-products (DBPs). This study evaluated DOM based on the molecular weight (MW) size fractionation, trihalomethane, iodinated-trihalomethane, haloacetonitrile, and trichloronitromethane formation potential (THMFP, I-THMFP, HANFP, and TCNMFP) of the RW from the U-Tapao Canal, Songkhla, Thailand and the RW mixed with TWW (RW + TWW) samples. The RW and RW + TWW were treated by coagulation with poly aluminum chloride. The DOM of RW and RW + TWW and their treated water was distributed most in the MW below 1 kDa. The MWs of 3-10 kDa and 1-3 kDa were the active DOM involved in the specific THMFP for the RW + TWW. The MW of < 1 kDa in the RW + TWW resulted in a slightly high specific I-THMFP and HANFP. The MW of 1 - 3 kDa in the coagulated samples had a high specific I-THMFP. The MW of > 10 kDa in the coagulated RW + TWW was a precursor for a particular HANFP. Monitoring systems for measuring the level of TWW mixed with RW and an effective process to enhance the efficiency of traditional water treatment must be set up to produce a consumer-safe water supply.

Preparation of a novel poly-(di-ionic liquid)/BDD-modified electrode for the detection of tetrachloro-p-benzoquinone.

During the COVID-19 pandemic, the release of toxic disinfection by-products (DBPs) has increased due to the intensive, large-scale use of disinfectants. Halogenated benzoquinones (HBQs) are among the most toxic DBPs, but there is no rapid, convenient, and economical detection method. In this study, a novel PDIL/BDD-modified electrode was prepared in a mixed solvent of dimethyl sulfoxide (DMSO) and acetonitrile (ACN) by electrochemical polymerization with a di-ionic ionic liquid containing alkenyl groups as the monomer. The electrochemical behavior of tetra-chloro-p-benzoquinone (TCBQ) on the modified electrode was studied. By studying the cyclic voltammetry behavior of TCBQ on the PDIL/BDD electrode, it was concluded that the electrode reactions of TCBQ included the reduction of TCBQ to TCBQH2 (C1) and the reduction of bis-quinhydrone imidazole π-π type charge transfer complex to TCBQH2 (C2). By studying the SWV responses of TCBQ in the concentration range of 1-100 ng/L on the PDIL/BDD electrode, it was found that the reduction peak current (Ipa) had a linear relationship with the concentration. The electrochemical SWV technique was used to detect the concentration of trace TCBQ in water and is expected to be used for the detection of other HBQs in drinking water and swimming pool water.

Developmental toxicity of bromoacetamide via the thyroid hormone receptors-mediated disruption of thyroid hormone homeostasis in zebrafish embryos.

Bromoacetamide (BAcAm) is a nitrogenous disinfection by-product. We previously found that BAcAm induced developmental toxicity in zebrafish embryos, but the underlying mechanisms remain to be elucidated. Since thyroid hormones (THs) homeostasis is crucial to development, we hypothesized that disruption of THs homeostasis may play a role in the developmental toxicity of BAcAm. In this study, we found BAcAm exposure significantly increased mortality and malformation rate, decreased hatching rate and body length, inhibited the locomotor capacity in zebrafish embryos. BAcAm elevated TSH, T3 and T4 levels, down-regulated T3/T4 ratios, and up-regulated mRNA expression changes of THs related genes (trh, tsh, tg, nis, tpo, dio1, dio2, ugt1ab，klf9 and rho), but down-regulated mRNA expression changes of TH receptors (tr α and tr ß). Up-regulated tr α and tr ß mRNAs by rescue treatment confirmed that both tr α and tr ß were involved in the developmental toxicity of BAcAm. In conclusion, our study indicates disruption of THs homeostasis via the thyroid hormone receptors was responsible for the developmental toxicity of BAcAm.

Age-sex specific and cause-specific health risk and burden of disease induced by exposure to trihalomethanes (THMs) and haloacetic acids (HAAs) from drinking water: An assessment in four urban communities of Bushehr Province, Iran, 2017.

Health risk and burden of disease induced by exposure to trihalomethanes (THMs, four compounds) and haloacetic acids (HAAs, 5 compounds) from drinking water through ingestion, dermal absorption, and inhalation routes were assessed based on one-year water quality monitoring in four urban communities (Bandar Deylam, Borazjan, Bushehr, and Choghadak) of Bushehr Province, Iran. The total average concentrations of THMs and HAAs at all the communities level were determined to be 92.9 ± 43.7 and 70.6 ± 26.5 µg/L, respectively. The dominant components of the THMs and HAAs were determined to be tribromomethane (TBM, 41.6%) and monobromoacetic acid (MBAA, 60.8%), respectively. The average contributions of ingestion, dermal absorption, and inhalation routes in exposure to the chlorination by-products (CBPs) were respectively 65.0, 15.4, and 19.6%. The total average non-carcinogenic risk as the hazard index (HI) and incremental lifetime cancer risk (ILCR) of the CBPs at all the communities level were found to be 4.03 × 10-1 and 3.16 × 10-4, respectively. The total attributable deaths, death rate (per 100,000 people), age-weighted disability-adjusted life years (DALYs), and age-weighted DALY rate for all ages both sexes combined at all the communities level were estimated to be 1.0 (uncertainty interval: UI 95% 0.3 to 2.8), 0.27 (0.08-0.75), 30.8 (11.3-100.1), and 8.1 (3.0-26.4), respectively. The average contribution of mortality (years of life lost due to premature mortality: YLLs) in the attributable burden of disease was 94.7% (94.4-95.6). Although in most of cases the average levels of the CBPs were in the permissible range of Iranian standards for drinking water quality, the average values of ILCRs as well as attributable burden of disease were not acceptable (the ILCRs were higher than the boundary limit of 10-5); therefore, implementation of interventions for reducing exposure to CBPs through drinking water especially in Kowsar Dam Water Treatment Plant is strictly recommended.

Microbial reduction of bromate: current status and prospects.

Bromate is a disinfection byproduct (DBP) that forms during the ozonation of bromide-containing natural water, which may cause health risks to humans. In this review, we provide an overview of the mechanism of bromate formation, microbial communities and bioreactors that are responsible for bromate reduction. Bromate can be formed through two pathways of bromide oxidation by ozone or by ·OH, and it can be removed by biological approaches. Members belonging to phyla of Spirochaetes, Proteobacteria, Firmicutes, Actinobacteria, Clostridium, Deinococcus-Thermus and Bacteroidetes have been identified as capable of reducing bromate to bromide. Multiple configurations of biofilm bioreactors have been employed to cultivate microbial communities to perform bromate removal. The rapid development of multiomics has and will continue to accelerate the elucidation of the mechanisms involved in bromate and other DBP conversions, as well as the interaction patterns among different bacterial subdivisions in the bioremoval of DBPs.

Probing size characteristics of disinfection by-products precursors during the bioavailability study of soluble microbial products using ultrafiltration fractionation.

Soluble microbial products (SMPs) discharged into surface water may increase the formation of disinfection by-products (DBPs) in downstream drinking water treatment plants. In this study, ultrafiltration (UF) fractionation was used to separate SMPs into homogenous components. An aerobic microbial experiment was conducted to evaluate the bioavailability of individual molecular weight (MW) fractions of SMPs in surface water and the impact on their DBP formation, facilitating the interpretation of SMPs characterization and DBPs reactivity. For SMPs, organics with MW < 1 kDa were the primary fraction, containing the most abundant humic substances. The 30 kDa < MW < 100 kDa fraction was the lowest in SMPs but had the highest SUVA values. After biodegradation, the bioavailability of physical fractions increased with the increasing MW size. However, the SUVA value, except for MW < 1 kDa, increased in individual fraction after biodegradation. Low molecular weight SMPs fractions (MW<10 kDa) were major precursors for DBP in which trichloromethane (TCM) was the most abundant. The 10 kDa  100KDa had relative abundant dichloroacetonitrile (DCAN) formation. After biodegradation, TCM precursors with MW < 1 kDa were removed by approximately 20%, whereas the increase of TCM formation was observed in 1 kDa < MW < 100 kDa fraction. CH formation from 1 kDa < MW < 10 kDa increased considerably, but those from 10 kDa < MW < 30 kDa decreased after biodegradation, as a result of the biotransformation of large organic acids to small organic acids. In terms of DBP reactivity, the TCM yield for the MW < 1 kDa fraction had no significant change while the 30 kDa < MW < 100 kDa fraction exhibited the greatest increase (approximately 8 times) in TCM yield.

Investigation of the effective factors on the mutagen X formation in drinking water by response surface methodology.

Mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) is known as a potent factor in inducing DNA damage and increasing cancer risk. MX is a chlorination disinfection byproduct that comes from the reaction of humic acids and chlorine in drinking water. The purpose of this study was to evaluate the effects of significant factors (including pH, reaction time, chlorine and the concentration of organic materials (TOC)) and their interactions on the MX formation rate in chlorinated drinking water using Box-Behnken Design (BBD) and response surface method (RSM). For this purpose, the simulation of water chlorination disinfection process was carried out in a laboratory scale. A quadratic model was chosen to determine the mathematical relations between the response and the effective factors. All linear parameters, as well as second-degree components except chlorine, were statistically significant. Also, the interactions of contact time with TOC, free chlorine residual with TOC, and chlorine with pH were also statistically significant. Statistical results showed that the pH had a great effect on the potential of MX formation, and then the factors of TOC, chlorine and contact time were effective, respectively. The percentage of contribution (PC) of each component in the formation of MX. The highest significant percentage of contribution (48.36%) was allocated to the pH. Under the optimum conditions (contact time of 48.38 min, chlorine concentration of 0.79 mg/L, TOC concentration of 0.53 mg/L, and pH of 7.98), minimum value of MX was equal to 28.6.

[Determination of trichloroaldehyde in drinking water using liquid-liquid extraction and gas chromatography].

OBJECTIVE: To establish a liquid-liquid extraction and gas chromatography method for the determination of trichloroacetaldehyde in drinking water. METHODS: Chromatography parameters and extraction parameters, such as extraction solvent, salting out reagents, internal standards and pH were tested and selected. Using the optimized parameters, methods validation and comparison with the national standard examination method was also conducted. RESULTS: Employing the optimized extraction and instrumental analytic parameters, good correlation coefficient was obtained in the linear range of 0.20-20.0 µg/L, with r greater than 0.999. The methods detection limit was 0.030 µg/L. When spiked concentration was 1.0 µg/L for pure water and tap water, the recoveries were 94.8% and 93.7%, respectively, and relative standard deviation was 2.9% and 3.4%, respectively. When spiked concentration was 16.0 µg/L for pure water and tap water, the recoveries were both 101% and relative standard deviation was 1.0% and 1.3%, respectively. Paired samples t test showed that the result obtained with this method were generally lower than that acquired from the national standard examination method. CONCLUSION: This method is sensitive and accurate, and it is suitable for the determination of trichloroaldehyde in drinking water.

Enhanced removal of organic matter and typical disinfection byproduct precursors in combined iron-carbon micro electrolysis-UBAF process for drinking water pre-treatment.

The organic matter and two types of disinfection byproduct (DBP) precursors in micro-polluted source water were removed using an iron-carbon micro-electrolysis (ICME) combined with up-flow biological aerated filter (UBAF) process. Two pilot-scale experiments (ICME-UBAF and UBAF alone) were used to investigate the effect of the ICME system on the removal of organic matter and DBP precursors. The results showed that ICME pretreatment removed 15.6% of dissolved organic matter (DOM) and significantly improved the removal rate in the subsequent UBAF process. The ICME system removed 31% of trichloromethane (TCM) precursors and 20% of dichloroacetonitrile (DCAN) precursors. The results of measurements of the molecular weight distribution and hydrophilic fractions of DOM and DBP precursors showed that ICME pretreatment played a key role in breaking large-molecular-weight organic matter into low-molecular-weight components, and the hydrophobic fraction into hydrophilic compounds, which was favorable for subsequent biodegradation by UBAF. Three-dimensional fluorescence spectroscopy (3D-EEM) further indicated that the ICME system improved the removal of TCM and DCAN precursors. The biomass analysis indicated the presence of a larger and more diverse microbial community in the ICME-UBAF system than for the UBAF alone. The high-throughput sequencing results revealed that domination of the genera Sphingomonas, Brevundimonas and Sphingorhabdus contributed to the better removal of organic matter and two types of DBP precursors. Also, Nitrosomonas and Pseudomonas were beneficial for ammonia removal.

Determination of bromate via the chemiluminescence generated in the sulfite and carbon quantum dot system.

The authors describe a chemiluminescence (CL)-based assay for the determination of bromate. The method is based on the use of a solution of carbon quantum dots (CQDs) and sulfite. Strong CL (peak at 490 nm) is observed when bromate is injected into the solution. The CL increases linearly in the 0.3 to 10 µmol L-1 bromate concentration range, giving a 0.1 µmol L-1 limit of detection (at an S/N ratio of 3). A possible CL mechanism is suggested that involves a redox reaction between the CQDs, bromate and sulfite in the acidic medium. This leads to the formation of hole-injected and electron-injected CQDs. Radiative recombination of oxidant-injected holes and electrons in the CQDs accounts for the occurrence of CL. This mechanism contradicts the previous assumption that the transfer of energy occurs from SO2* to the CQDs. Although nitrite may interfere in the determination of bromate, its effect can be eliminated by adding sulfamic acid. The assay is sensitive and represents a new tool for the determination of bromate, which is a carcinogen. Graphical abstract Under acidic condition, carbon quantum dots (CQDs) can react with sulfite and bromate transforming to hole-injected CQDs (CQDs•-) and electron-injected CQDs (CQDs•+), respectively. Thereafter, strong chemiluminescence (490 nm) aroused from the radiative electron-hole annihilation between CQDs•- and CQDs•+.