Trichloronitromethane Formation Research Articles

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.

Enhanced trichloronitromethane formation during chlorine-UV treatment of nitrite-containing water by organic amines

This study explored the risk of trichloronitromethane (TCNM) formation during chlorination of the nitrite-containing water after pre-chlorination and subsequent UV irradiation (i.e., the chlorine-UV process). The competitive reaction between amino acid (AA) and NO2− for chlorine produced organic chloramine and reduced the oxidation from NO2− to NO3−, resulting in a significant enhancement of TCNM in the presence of AA (>5.52 μg L−1) as compared to the absence of AA (0.42 μg L−1). The generation of HO• during UV photolysis of organic chloramines was confirmed. Among the process parameters, pre-chlorination time (from 5 min to 30 min) had no significant effect on TCNM formation; the highest TCNM formation occurred at pH 7 (from pH 6 to pH 8); prolonged UV irradiation time (from 5 min to 30 min) and increased chlorine to AA ratio (Cl2:AA) (from 1 to 3) decreased the TCNM formation. The hydroxylated, chlorinated and nitrosated products were detected. The quantum chemical calculation results indicated the attack of NO2• was more likely to occur at the meta and para positions of benzoic acid (BZA), because of the steric hindrance of the carboxylic group in BZA to the ortho position. Based on the results of the toxicity assessment, pre-chlorination with a higher chlorine dosage could be an effective method of controlling both TCNM formation and acute toxicity. Overall, the results of this study contributed to the understanding of the TCNM formation mechanism as well as optimizing the parameters of the chlorine-UV process to reduce the risk of TCNM formation.

Micropollutant removal and disinfection byproduct control by sequential peroxymonosulfate-UV treatment in water: A case study with sulfamethoxazole

UV/peroxymonosulfate (UV/PMS) advanced oxidation process has attracted significant attention for removal of micropollutants in water. However, during practical water treatment applications, the PMS treatment must be performed before the UV treatment to achieve full contact. In this study, sulfamethoxazole (SMX) was selected as the target micropollutant. Four different operational approaches, including UV alone, PMS alone, simultaneous UV/PMS and sequential PMS-UV, were compared for their differences in SMX removal and disinfection by-product (DBP) formation potentials during chlorine-driven disinfection. Among the four approaches, UV/PMS and PMS-UV achieved over 90% removal efficiencies for SMX without substantial differences. For raw water, the trichloronitromethane (TCNM) formation potential after treatment with PMS-UV was lower than that after UV/PMS treatment. The time interval over which the PMS-UV process was conducted had little effect on the final removal efficiency for SMX. However, a brief (5 min) pre-PMS treatment significantly reduced the TCNM formation potential and the genotoxicity from DBPs. The formation risk for TCNM during chlorination increased markedly with increasing PMS dosages, and the appropriate dosage under these experimental conditions was suggested to be 0.5–1.0 mmol/L. Under alkaline conditions, PMS-UV treatment can enhance SMX degradation as well as dramatically reduced the formation potentials for haloketones, haloacetonitriles and halonitromethanes. This study suggests that proper optimization of UV/PMS processes can remove SMX and reduce its DBP formation.

Effect of UV/Chlorine Oxidation on Disinfection Byproduct Formation from Diverse Model Compounds

Disinfection byproduct (DBP) formation is a potential concern for the UV/chlorine advanced oxidation process (AOP) in water treatment. In this study, 11 model compounds were selected as natural organic matter (NOM) surrogates, including seven active DBP precursors and four poor precursors. The effect of UV/chlorine on their DBP formation in the UV reactor and during 24 h postchlorination was investigated in comparison to dark chlorination. DBPs evaluated included adsorbable organic halides (AOX), trihalomethanes, haloacetic acids (HAAs), haloacetaldehydes (HALs), trichloronitromethane (TCNM), and dichloroacetonitrile (DCAN). UV/chlorine AOP was conducted at a typical UV dose adopted in drinking water treatment and at both pH 6.0 and 7.8 with postchlorination pH kept at pH 7.8. For most of the active DBP precursors, UV/chlorine either decreased their AOX formation potential (FP) and DBPFP by <25% or showed an insignificant impact. Three poor DBP precursors were activated by UV/chlorine oxidation, especially at pH 6.0, with a significant increase of AOXFP and DBPFP percentage-wise, but the absolute increase was low (less than 186 μg-Cl/mg-C and 50 μg DBP/mg-C). UV/chlorine converted some chloroform precursors to HAA or HAL precusors. For N-containing precursors, UV/chlorine increased TCNM formation and decreased DCAN formation, especially at pH 6.

Insight into the mechanisms of trichloronitromethane formation by vacuum ultraviolet: QSAR model and FTICR-MS analysis

Vacuum ultraviolet (VUV) photolysis is recognized as an environmental-friendly treatment process. Nitrate (NO3−) and natural organic matter (NOM) are widely present in water source. We investigated trichloronitromethane (TCNM) formation during chlorination after VUV photolysis, because TCNM is an unregulated highly toxic disinfection byproduct. In this study: (1) we found reactive nitrogen species that is generated under VUV photolysis of NO3− react with organic matter to form nitrogen-containing compounds and subsequently form TCNM during chlorination; (2) we found the mere presence of 0.1 mmol/L NO3− can result in the formation of up to 63.96 µg/L TCNM; (3) we found the changes in pH (6.0-8.0), chloride (1-4 mmol/L), and bicarbonate (1-4 mmol/L) cannot effectively diminish TCNM formation; and, (4) we established the quantitative structure-activity relationship (QSAR) model, which indicated a linear relationship between TCNM formation and the Hammett constant (σ) of model compounds; and, (5) we characterized TCNM precursors in water matrix after VUV photolysis and found 1161 much more nitrogen-containing compounds with higher aromaticity were generated. Overall, this study indicates more attention should be paid to reducing the formation risk of TCNM when applying VUV photolysis process at scale.

Effects of MPUV/chlorine oxidation and coexisting bromide, ammonia, and nitrate on DBP formation potential of five typical amino acids

Disinfection byproduct (DBP) formation is a potential concern with regard to MPUV/Cl2 application in water treatment. In this study, five typical amino acids (AAs) were selected to investigate their DBP alteration during short-term medium pressure (MP) UV/chlorine oxidation following post-chlorination relative to parallel dark controls. The five selected AAs include two potent DBP precursors (aspartic acid and tryptophan), one modest precursor (asparagine) and two poor precursors (phenylalanine and proline). MPUV/chlorine increased the total DBP formation and DBP-associated cytotoxicity of the two poor precursors phenylalanine (Phe) and proline (Pro) as well as their chlorine demands. Conversely, DBP formation and DBP-associated cytotoxicity of the three modest-to-potent DBP precursors showed the opposite changing trends due to MPUV/Cl2 oxidation. The two aromatic AAs (tryptophan and phenylalanine) were more readily to be affected by MPUV/Cl2 oxidation especially at acidic pH condition. Conversely, DBP formation and DBP-associated cytotoxicity of the three modest-to-potent precursors showed the opposite changing trends due to MPUV/Cl2 oxidation. Among the measured DBPs, the absolute formation potential changes of haloacetic acids and haloacetonitriles were the most prominent. Presence of bromide increased the trihalomethane formation potential of five AAs. Ammonia-spiked samples resulted in notably higher chlorine demands but slightly reduced DBPFP. Photonitration caused increased haloacetonitrile and trichloronitromethane formation but lower overall DBP formation potential and DBP-associated cytotoxicity. Results indicated that increased DBP formation of unreactive aromatic AAs may be problematic with respect to MPUV/Cl2 application, while the presence of inorganic ions may not contribute to further increase in calculated cytotoxicity of measured DBPs.

Impact of nitrite on the formation of trichloronitromethane during the UV-LED/chlorine process

A UV-LED at a fixed wavelength is increasingly employed in the UV/chlorine process to degrade contaminants of emerging concern.

Unexpected Role of Nitrite in Promoting Transformation of Sulfonamide Antibiotics by Peracetic Acid: Reactive Nitrogen Species Contribution and Harmful Disinfection Byproduct Formation Potential

Peracetic acid (PAA) is an emerging oxidant and disinfectant for wastewater (WW) treatment due to limited harmful disinfection byproduct (DBP) formation. Nitrite (NO2-) is a ubiquitous anion in water, but the impact of NO2- on PAA oxidation and disinfection has been largely overlooked. This work found for the first time that NO2- could significantly promote the oxidation of sulfonamide antibiotics (SAs) by PAA. Unexpectedly, the reactive nitrogen species (RNS), for example, peroxynitrite (ONOO-), rather than conventional organic radicals (R-O•) or reactive oxygen species (ROS), played major roles in SAs degradation. A kinetic model based on first-principles was developed to elucidate the reaction mechanism and simulate reaction kinetics of the PAA/NO2- process. Structural activity assessment and quantum chemical calculations showed that RNS tended to react with an aromatic amine group, resulting in more conversion of NO2--N to organic-N. The formation of nitrated and nitrosated byproducts and the enhancement of trichloronitromethane formation potential might be a prevalent problem in the PAA/NO2- process. This study provides new insights into the reaction of PAA with NO2- and sheds light on the potential risks of PAA in WW treatment in the presence of NO2-.

An expected formation of TCNM from chlorination of bisphenol A with ultrasonic pretreatment: A new nitrogen source for N-DBP from N2 in air

Ultrasonic irradiation has been widely adopted to remove emerging contaminants (ECs) in water, while little attention has been given to the impact of ultrasonic pretreatment on the downstream formation of disinfection byproducts (DBPs). In this study, bisphenol A (BPA), a typical EC that is frequently detected in water, was selected as a model contaminant to investigate the influence of ultrasonic pretreatment on DBP formation during the chlorination process. The ultrasonic degradation behaviors of BPA fit the heterogeneous Langmuir-Hinshelwood (L-H) model well, indicating that BPA undergoes decomposition by free radical reactions predominantly at the water-bubble interface. Interestingly, compared to direct chlorination, the ultrasonic pretreatment obviously enhanced trichloronitromethane (TCNM) formation from subsequent chlorination. The LC/MS/MS technique was applied to analyze the transformation products of BPA. In addition to hydroxyl radicals (OH) dominating hydroxylation of the aromatic ring and cleavage of the CC bond, an ultrasonic-induced nitration mechanism was also involved in BPA degradation, and the formed nitration products may be responsible for TCNM formation during subsequent chlorination. Factors affecting the ultrasonic degradation rate of BPA as well as DBP formation were also investigated. Generally, dissolved O2, higher ultrasonic frequency and higher power favored BPA degradation, whereas the presence of HCO3− and HA hindered BPA degradation, and Cl− showed a minor influence. TCNM formation was largely diminished by sparging with O2 or N2 alone. Higher ultrasonic frequency and power enhanced the TCM and TCNM formation. The presence of HA promoted THM formation, while HCO3− inhibited TCNM formation. Therefore, once ultrasonic treatment is adopted as an alternative water treatment, its impact on subsequent DBP formation requires further study.

Enhanced formation of trichloronitromethane precursors during UV/monochloramine treatment

This study systematically investigates the formation of trichloronitromethane (TCNM) from 2 natural waters, 6 humic substances and 16 phenolic compounds during UV/monochloramine (UV/NH2Cl) followed by post-chloramination. Using 15N-NH2Cl as an isotope tracer, we found that 15N-TCNM accounted for 70.7–76.5% of total TCNM during UV/NH2Cl treated 2 natural waters, which was significantly higher than the proportion of 15N-TCNM in chloramination (NH2Cl alone). This is a direct evidence that NH2Cl, rather than the nitrogenous matters in waters, was the predominant nitrogen source of TCNM during UV/NH2Cl treatment. Phenol derivatives with meta-substituents and with electron-withdrawing groups facilitated the formation of TCNM precursors during UV/NH2Cl treatment. Significant correlations were found between Hammett constants (σ) of substituents and TCNM formation potentials. The formation mechanisms of TCNM were revealed using resorcinol as a representative phenolic compound. During UV/NH2Cl treatment, HO•, reactive chlorine species and reactive nitrogen species contributed to 28.1%, 29.0% and 19.4% of resorcinol degradation. Five nitro(so)-intermediates were identified as the main TCNM precursors. The formation pathways of TCNM were proposed. Alkaline pH was recommended to reduce the formation of TCNM precursors during UV/NH2Cl treatment.

UV-induced activation of organic chloramine: Radicals generation, transformation pathway and DBP formation

Organic chloramines of little disinfection efficacy commonly exist in disinfection process (chlor(am)ination) due to the wide presence of organic amines in water, of which N-chlorodimethylamine (CDMA) is a typical one. For the first time, UV photolysis for the activation of CDMA was investigated. UV photolysis caused the cleavage of N-Cl bond in CDMA to form Cl• and subsequently HO•, both of which are dominant contributors to the destruction of model contaminant bisphenol A (BPA). Typical spectra of HO• were detected by electron paramagnetic resonance (EPR) experiments, while spectra of reactive nitrogen species (RNS) were not detected during UV photolysis of CDMA. The increase of pH (6.0–8.0), HCO3−/CO32−, Cl− and nature organic matter inhibited the degradation of BPA. We proposed pathways of CDMA and BPA degradation based on the identified transformation products. UV photolysis of CDMA and BPA reduced the formation of N-nitrosodimethylamine (NDMA) at pH 8.0, but increased the formation of trichloronitromethane (TCNM) at pH 7.0 and 8.0. The increasing toxicity and the formation of TCNM and NDMA gave us a hint that formation of organic chloramines should be concerned.

UV254 irradiation of N-chloro-α-amino acids: Kinetics, mechanisms, and N-DBP formation potentials

This study explores the degradation kinetics and mechanisms of N-chloro-α-amino acids and the changes in the formation potential of nitrogenous disinfection byproducts (N-DBPs) upon UV254 irradiation. UV254 irradiation significantly accelerated the degradation of all the tested N-chloro-α-amino acids compared to those in the dark. Both direct photolysis-induced cleavage of the N-Cl bonds and radical oxidation (e.g., Cl• and Cl2•−) involved reactions that contributed to their enhanced degradation. The fluence-based photolysis rate constants of the N-chloro-α-amino acids varied in the range of (1.06—5.47) × 10−3 cm2 mJ−1 at pH 6.0 and (0.74—2.79) × 10−3 cm2 mJ−1 at pH 8.0. The apparent quantum yields (Φapp) of the majority of the N-chloro-α-amino acids were in the range of 0.41−0.95 at pH 6.0 and 0.22−0.79 at pH 8.0, except N-chloroaspartic acid, N-chlorohistidine, and N-chloroalanine. UV254 irradiation significantly enhanced the formation of trichloronitromethane (TCNM) from the tested N-chloro-α-amino acids after post-chlorination, but exhibited various effects on the formation of dichloroacetonitrile (DCAN). A longer UV254 irradiation time generated more TCNM, and a lower pH produced more DCAN from the N-chloro-α-amino acids. The degradation pathways of N-chlorotyrosine, as a representative N-chloro-α-amino acid, are proposed, and the β-scission and 1,2-H shift pathways led to the formation of different precursors of TCNM and DCAN. The results of this study improve our understanding of the fate of N-chloro-α-amino acids under UV254 irradiation and post-chlorination.

Formation and influence factors of halonitromethanes in chlorination of nitro-aromatic compounds

Halonitromethanes (HNMs), typical nitrogenous disinfection byproducts generated during disinfection of chlorination and chloramination, are widely detected in drinking water. This study investigated the formation of two dominant HNMs, trichloronitromethane (TCNM) and dichloronitromethane (DCNM) during chlorination/chloramination of ten nitro-aromatic compounds (NACs), including six aromatic mono-nitro compounds, three aromatic di-nitro compounds and one aromatic tri-nitro compound. The results showed that 2-nitrophenol and 3-nitrophenol could be the main precursors of TCNM and DCNM, and the yields of TCNM were one order of magnitude higher than that of DCNM. HNMs formation in chlorination was much higher than that in chloramination. However, HNMs were hardly produced during chlorination and chloramination of the other eight NACs. In chlorination of 2-nitrophenol, a pH range of 5.0–7.0 facilitated the TCNM formation. Besides, the concentration of ferric and manganese ions had different influences on TCNM formation. While the concentration ranges were 0–2 mg/L, ferric ion significantly decreased TCNM formation but manganese ion had not any influence on TCNM formation. Contrary to a previous finding, nitrite significantly reduced TCNM formation, which implied that nitrite has different effects on TCNM formation from various precursors. Moreover, dissolved organic matter (DOM, 0–5 mg/L as C) significantly influenced the formation of TCNM in chlorination of 2-nitrophenol despite the low TCNM formation in chlorination of DOM. Several chlorinated intermediates were detected and identified as mono/di/tri-chloro-2-nitrophenol during chlorination of 2-nitrophenol. It is effectively to reduce the production of TCNM and DCNM formation from chlorination of 2-nitrophenol by controlling disinfection conditions in drinking water.

DBP formation and toxicity alteration during UV/chlorine treatment of wastewater and the effects of ammonia and bromide

The UV/chlorine process is efficient for the abatement of micropollutants; yet, the formation of disinfection by-products (DBPs) and the toxicity can be altered during the treatment. This study investigated effluent organic matter characterization, DBP formation and toxicity alteration after the UV/chlorine treatment of wastewater; particularly, typical water matrix components in wastewater, namely, ammonia and bromide, were studied. The raw wastewater contained low levels of ammonia (3 µM) and bromide (0.5 µM). The UV/chlorine treatment efficiently eliminated 90 – 94% of fluorescent components. Compared with chlorination alone, a 20 min UV/chlorine treatment increased the formation of trihalomethanes (THMs), haloacetic acids (HAAs), chloral hydrate (CH), haloacetonitriles (HANs), trichloronitromethane (TCNM) and haloacetamides (HAcAms) by 90 – 508%. In post-chlorination after the UV/chlorine treatment, the formation of CH, HANs, TCNM and HAcAms increased by 77 – 274%, whereas the formation of both THMs and HAAs increased slightly by 11%. Meanwhile, the calculated cytotoxicity and genotoxicity of DBPs increased considerably after the UV/chlorine treatment and in post-chlorination, primarily due to the increased formation of HAAs and nitrogenous DBPs (N-DBPs). However, the acute toxicity of the wastewater to Vibrio fischeri and genotoxicity determined by the umu test decreased by 19% and 76%, respectively, after the 20 min UV/chlorine treatment. An additional 200 µM ammonia decreased the formation of all detected DBPs during the UV/chlorine treatment and 24 h post-chlorination, except that TCNM formation increased by 11% during post-chlorination. The acute toxicity of wastewater spiked with 200 µM ammonia was 32% lower than that of raw wastewater after the UV/chlorine treatment, but the genotoxicity was 58% higher. The addition of 1 mg/L bromide to the UV/chlorine process dramatically increased the formation of brominated DBPs and the overall calculated cytotoxicity and genotoxicity of DBPs. However, the acute toxicity and genotoxicity of the wastewater decreased by 7% and 100%, respectively, when bromide was added to the UV/chlorine treatment. This study illuminated that UV/chlorine treatment can decrease acute and geno- toxicities of wastewater efficiently.

Factors affecting UV/persulfate treatment of phenacetin and its disinfection byproduct formation potential

The pollution of aquatic bodies in the natural environment by pharmaceuticals has become a matter of increasing concern. In this study, we investigated the effects of the various influencing factors on the degradation of phenacetin (PNT) and its disinfection byproduct formation potentials (DBPFPs) by UV/persulfate (UV/PS) treatment. We first examined the effects of factors such as the PS concentration, pH, HCO3–, NO3–, NO2–, and natural organic matter (NOM) on the PNT degradation kinetics. The PNT degradation rate exhibited a positive correlation with the PS concentration. The PNT degradation rate was also pH-dependent, and it was highest under mild-alkalinity conditions. The presence of NO3–, NO2–, and NOM all inhibited PNT degradation, whereas HCO3– slightly accelerated PNT degradation. We next adopted LC/MS/MS to identify the degradation products of PNT, and the possible degradation pathways were proposed accordingly. The effects of UV/PS pretreatment on the DBPs from chlorination exhibit a close relationship with the abovementioned factors influencing the PNT degradation performance. Upon prolonging the pretreatment time and increasing the PS concentration, it was observed that trichloromethane (TCM) formation continuously decreased, while dichloroacetonitrile (DCAN) and trichloronitromethane (TCNM) exhibited patterns of increase and subsequent decrease in concentration. Mild alkalinity enhanced TCM formation and largely restrained DCAN and TCNM formation. Additionally, the presence of NOM enhanced TCM formation, while HCO3– hardly affected DBP formation. Meanwhile, NO2– profoundly affected the formation of TCNM. Therefore, these factors influencing PNT degradation by UV/PS should be carefully considered when integrating such technology as an alternative pretreatment for PNT-polluted water before disinfection.

Molecular mechanism of trichloronitromethane formation from &amp;lt;italic&amp;gt;p&amp;lt;/italic&amp;gt;-toluidine during chlorine disinfection of water

Molecular mechanism of trichloronitromethane formation from &amp;lt;italic&amp;gt;p&amp;lt;/italic&amp;gt;-toluidine during chlorine disinfection of water

Has the formation of disinfection by-products been overestimated? Membrane leakage from syringe filter heads serves as unexpected precursors

Syringe filters are widely used for sample pretreatments in laboratories. This study found that, surprisingly, these filters can leak dissolved organic carbon (DOC) that can potentially serve as precursors of disinfection by-products (DBPs). Nine common types of syringe filters were assessed. The results showed that the DOC of ultrapure water increased after syringe filtration. The DOC shed from filter membranes was characterized, whose spectra showed that the main compounds exhibited a low apparent molecular weight. Five classes of DBPs were investigated including trihalomethanes, haloacetaldehydes, haloacetonitriles, haloacetamides and halonitromethanes, among which trichloromethane (TCM), dichloroacetaldehyde (DCAL), trichloroacetaldehyde (TCAL), dichloroacetonitrile (DCAN), and trichloronitromethane (TCNM) were principally detected. The DBP formation was affected by chlorination time and membrane types. In general, the use of the poly vinylidene fluoride membrane resulted in the highest formation of TCM and TCAL, whereas nylon and mixed cellulose esters membranes contributed significantly to the formation of DCAN and TCNM, respectively. The shedding DOC and the formation of TCM, DCAL and TCAL from filter membranes were mitigated effectively by pre-washing; however, the contribution of membrane leakage to DCAN and TCNM formation was still notable, even with a pre-wash volume of 50 mL. When unwashed syringe filters were used for a real water sample, the DBP formation increased by up to 73.2% compared to the pre-washed ones; particularly for TCNM it was always over 15%. Therefore, for better quality control in laboratories, more attention should be paid to the syringe filters during sample pre-treatments, particularly when DBP formation is being investigated.

Effects of Pre-Oxidation on Haloacetonitrile and Trichloronitromethane Formation during Subsequent Chlorination of Nitrogenous Organic Compounds.

The reaction between organic matter and disinfectants leads to the formation of disinfection byproducts (DBPs) in drinking water. With the improvement of detection technology and in-depth research, more than 1000 kinds of DBPs have been detected in drinking water. Nitrogenous DBPs (N-DBPs) are more genotoxic and cytotoxic than the regulated DBPs. The main methods are enhanced coagulation, pretreatment, and depth technologies which based are on conventional technology. Amino acids (AAs) are widely found in surface waters and play an important role by providing precursors from which toxic nitrogenous disinfection by-products (N-DBPs) are generated in chlorinated drinking water. The formation of N-DBPs, including dichloroacetonitrile, trichloroacetonitrile, and trichloronitromethane (TCNM), was investigated by analyzing chlorinated water using ozone (OZ), permanganate (PM), and ferrate (Fe(VI)) pre-oxidation processes. This paper has considered the control of pre-oxidation over N-DBPs formation of AAs, OZ, PM, and Fe(VI) pre-oxidation reduced the haloacetonitrile formation in the downstream chlorination. PM pre-oxidation decreased the TCNM formation during the subsequent chlorination, while Fe(VI) pre-oxidation had no significant influence on the TCNM formation, and OZ pre-oxidation increased the formation. OZ pre-oxidation formed the lowest degree of bromine substitution during subsequent chlorination of aspartic acid in the presence of bromide. Among the three oxidants, PM pre-oxidation was expected to be the best choice for reducing the estimated genotoxicity and cytotoxicity of the sum of the measured haloacetonitriles (HANs) and TCNM without bromide. Fe(VI) pre-oxidation had the best performance in the presence of bromide.

Nitrogen conversion from ammonia to trichloronitromethane: Potential risk during UV/chlorine process

In this study, the potential formation of trichloronitromethane (TCNM) from model organic compounds in ammonia-containing water treated by UV/chlorine process was evaluated. Monochloramine generated from the reaction of chlorine and ammonia can be photolyzed to produce NO2− and reactive nitrogen species (RNS), which play important roles in the formation of TCNM during the subsequent chlorination. The results showed that increase of nitrogen to chlorine molar ratio (from 0 to 1.0) and pH (from 6.5 to 8.0) enhanced the formation of TCNM, mainly due to the increased yield of NO2− and RNS from the photolyzed monochloramine. The formation of TCNM was interestingly found to be linearly correlated with Hammett constants of the model precursors, which is theoretically related to the rate constants of RNS with model compounds. Enhanced formation of TCNM was also observed during the treatment of natural organic matter by UV/chlorine process in ammonia-containing water. The toxicity assessment showed that TCNM significantly increased the genotoxicity of formed DBPs. Furthermore, the electrophilic substitution reaction of •NO2 was proved to more likely occur on the ortho and para position of phenol according to the calculation of Gaussian program, and a possible reaction pathway of phenol and •NO2 was proposed based on the calculated results.

Reactive Nitrogen Species Are Also Involved in the Transformation of Micropollutants by the UV/Monochloramine Process.

The UV/monochloramine (NH2Cl) process is an emerging advanced oxidation process (AOP) in water treatment via radicals produced from the UV photolysis of NH2Cl. This study investigated the degradation of micropollutants by the UV/NH2Cl AOP, with ibuprofen (IBP) and naproxen (NPX) selected as representative micropollutants. Hydroxyl radical (HO•) and chlorine atom (Cl•) were identified in the process, and unexpectedly, we found that reactive nitrogen species (RNS) also played important roles in the transformation of micropollutants. The electron paramagnetic resonance (EPR) analysis proved the production of •NO as well as HO•. The concentrations of HO•, Cl•, and •NO in UV/NH2Cl remained constant at pH 6.0-8.6, resulting in the slightly changed UV fluence-based pseudo-first-order rate constants (k') of IBP and NPX, which were about 1.65 × 10-3 and 2.54 × 10-3 cm2/mJ, respectively. For IBP, the relative contribution of RNS to k' was 27.8% at pH 7 and 50 μM NH2Cl, which was higher than that of Cl• (6.5%) but lower than that of HO• (58.7%). For NPX, the relative contribution of RNS to k' was 13.6%, which was lower than both Cl• (23.2%) and HO• (46.9%). The concentrations of HO•, Cl•, and •NO increased with the increasing NH2Cl dosage. Water matrix components of natural organic matter (NOM) and bicarbonate can scavenge HO•, Cl•, and RNS. The presence of 5 mg/L NOM decreased the k' of IBP and NPX by 66.9 and 57.6%, respectively, while 2 mM bicarbonate decreased the k' of IBP by 57.4% but increased the k' of NPX by 10.5% due to the contribution of CO3•- to NPX degradation. Products containing nitroso-, hydroxyl-, and chlorine-groups were detected during the degradation of IBP and NPX by UV/NH2Cl, indicating the role of nitrogen oxide radical (•NO) as well as HO• and Cl•. Trichloronitromethane formation was strongly enhanced in the UV/NH2Cl-treated samples, further indicating the important roles of RNS in this process. This study first demonstrates the involvement of RNS in the transformation of micropollutants in UV/NH2Cl.