Formation Of Dichloroacetamide Research Articles

Effects of Fe(III) on the formation and toxicity alteration of halonitromethanes, dichloroacetonitrile, and dichloroacetamide from polyethyleneimine during UV/chlorine disinfection

Trace iron ions (Fe(III)) are commonly found in water and wastewater, where free chlorine is very likely to coexist with Fe(III) affecting the disinfectant's stability and N-DBPs’ fate during UV/chlorine disinfection, and yet current understanding of these mechanisms is limited. This study investigates the effects of Fe(III) on the formation and toxicity alteration of halonitromethanes (HNMs), dichloroacetonitrile (DCAN), and dichloroacetamide (DCAcAm) from polyethyleneimine (PEI) during UV/chlorine disinfection. Results reveal that the maxima concentrations of HNMs, DCAN, and DCAcAm during UV/chlorine disinfection with additional Fe(III) were 1.39, 1.38, and 1.29 times higher than those without additional Fe(III), instead of being similar to those of Fe(III) inhibited the formation of HNMs, DCAN and DCAcAm during chlorination disinfection. Meanwhile, higher Fe(III) concentration, acidic pH, and higher chlorine dose were more favorable for forming HNMs, DCAN, and DCAcAm during UV/chlorine disinfection, which were highly dependent on the involvement of HO· and Cl·. Fe(III) in the aquatic environment partially hydrolyzed to the photoactive Fe(III)-hydroxyl complexes Fe(OH)2+ and [Fe(H2O)6]3+, which undergone UV photoactivation and coupling reactions with HOCl to achieve effective Fe(III)/Fe(II) interconversion, a process that facilitated the sustainable production of HO·. Extensive product analysis and comparison verified that the HO· production enhanced by the Fe(III)/Fe(II) internal cycle played a primary role in increasing HNMs, DCAN, and DCAcAm productions during UV/chlorine disinfection. Note that the incorporation of Fe(III) increased the cytotoxicity and genotoxicity of HNMs, DCAN, and DCAcAm formed during UV/chlorine disinfection, and yet Fe(III) did not have a significant effect on the acute toxicity of water samples before, during, and after UV/chlorine disinfection. The new findings broaden the knowledge of Fe(III) affecting HNMs, DCAN, and DCAcAm formation and toxicity alteration during UV/chlorine disinfection.

Removal performance and mechanism of typical amino acids in water by the peroxymonosulfate/Fe3O4 nanoparticles

Abstract Dissolved organic nitrogen (DON) as precursors of nitrogenous disinfection byproducts (N-DBPs) has become a serious issue for drinking water treatment. Here, Fe3O4/peroxymonosulfate (PMS) system was used to examine the amino acid removal and formation of N-DBPs in the system and the corresponding mechanisms. Results showed a remarked variation in removal efficiency of three typical amino acids, i.e., glutamate (78%), histidine (53%) and phenylalanine (27%) in Fe3O4/PMS system at optimum conditions (0.1 g/L Fe3O4, 1.5 mM PMS, 1 h). Notably, Fe3O4/PMS treatment led to dichloroacetonitrile (DCAN) formation caused by the chlorination of glutamate, phenylalanine and histidine being reduced by 53.3%, 9.7% and 41.9%, respectively. The degradation and subsequent N-DBPs formation in the Fe3O4/PMS system mainly depended on the types and properties of the amino acids. The formation of dichloroacetamide (DCAcAm) exhibited different trends, which may be due to the different R group structure of the three amino acids and the special aromaticity of the imidazole ring in the histidine side chain that facilitates its quick electrophilic substitution and ring-opening reaction. This study highlights that the Fe3O4/PMS system is a promising strategy to remove DON and efficiently eliminate N-DBPs formation in the drinking water treatment process depending on the amino acid type.

Enhanced formation of dichloroacetamide and dichloroacetonitrile during chloramination of drinking water and model organic matters in the presence of copper corrosion products

The formation of nitrogenous disinfection byproducts (N-DBPs) occurs in chloraminated water in drinking water distribution systems and may be affected by metal pipe materials and their corrosion products. The effect of copper corrosion products, including Cu2+, CuO, and Cu2O, on the formation of dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm) was investigated during chloramination of natural organic matter (NOM), model precursors (carboxylic acids and amino acids), and real water samples. Copper corrosion products enhanced DCAN and DCAcAm formation during chloramination of NOM by 33%–72% and 11%–80%, respectively. Addition of 15N-labeled monochloramine showed that the copper corrosion products primarily enhanced the formation of DCAN using organic nitrogen and monochloramine as nitrogen sources, and the formation of DCAcAm using monochloramine as the nitrogen source, but had a limited impact on the formation of DCAcAm using organic nitrogen as the nitrogen source. A distinct N-DBP formation pathway in the presence of Cu2+ and CuO was observed using tyrosine as a model compound, which included the formation of 1,4-benzoquinone as a dominant intermediate. On reaction with monochloramine, the 1,4-benzoquinone greatly contributed to enhancement of DCAN and DCAcAm formation using monochloramine as the nitrogen source. During chloramination of real water samples, Cu2+ and CuO enhanced DCAN formation by 9–40% and DCAcAm formation by 16–33%. This study increases our knowledge of copper catalyzed DCAN and DCAcAm formation in copper pipes, which will be meaningful for water safety in distribution systems using chloramine disinfection.

Tetracycline antibiotics as precursors of dichloroacetamide and other disinfection byproducts during chlorination and chloramination

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.

ClO2 pre-oxidation impacts the formation and nitrogen origins of dichloroacetonitrile and dichloroacetamide during subsequent chloramination

Chlorine dioxide (ClO2) can be used as a pre-oxidant when chloramination is performed in water treatment plants. However, the effects of ClO2 pre-oxidation on the formation of nitrogenous disinfection by-products, such as dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm), during chloramination are not well understood. In this study, the effects of ClO2 pre-oxidation on the formation of DCAN and DCAcAm during chloramination of 28 model compounds and seven real water samples were investigated. The sources of nitrogen for DCAN and DCAcAm formation were investigated using 15N-labeled monochloramine. ClO2 pre-oxidation affected DCAN and DCAcAm formation during chloramination of model compounds in different ways. ClO2 pre-oxidation increased unlabeled and 15N-labeled DCAN and DCAcAm formation during chloramination of six amino acids and peptides and five indoles and tertiary amines. ClO2 pre-oxidation decreased DCAN formation but increased DCAcAm formation during chloramination of three hydroxybenzamide compounds, but had the opposite effects for four tetracyclines. ClO2 pre-oxidation generally decreased DCAN and DCAcAm formation during chloramination of the phenolic compounds that are precursors not containing nitrogen. 2-Aminoacetophenone, formamid-trans-muconic acid, and unsaturated ketones were found to be transformation products of ClO2 oxidation of 3-methylindole, salicylamide, and resorcinol, respectively. Possible DCAN and DCAcAm formation pathways during chloramination after ClO2 oxidation were identified. For most of the water samples, ClO2 pre-oxidation decreased the amounts of DCAN and DCAcAm formed during chloramination by 36%–70% and 11%–59%, respectively. This may have been caused by ClO2 oxidation destroying phenolic precursors and macromolecular proteins rather than amino acids in the water samples.

The degradation of chloramphenicol by O3/PMS and the impact of O3-based AOPs pre-oxidation on dichloroacetamide generation in post-chlorination

The frequent detection of chloramphenicol (CAP) in wastewater and surface water gives rise to concerns on its fatal myelosuppression and aplastic anemia. Recently, the combination of ozone and peroxymonosulfate (O3/PMS) has received wide attention in removing pollutants due to the multiple oxidants (i.e., O3, hydroxyl radicals (OH) and sulfate radicals (SO4−)) existed therein. This study showed that O3/PMS could effectively degrade CAP under various conditions. The second-order rate constant of CAP with O3, OH and SO4− was 0.291±0.005, 2.27(±0.03)×109 and 1.02±0.02×108M-1s-1, respectively. The degradation efficiency of CAP was significantly enhanced as PMS concentration or pH increased. Bicarbonate (HCO3−) at concentration of 5 mM slightly inhibited CAP degradation at pH 7. Chloride (Cl−) at concentration of 0.5 mM enhanced CAP removal at pH 7, while this enhancement gradually weakened as Cl− concentration further increased. The degradation efficiency of CAP first increased with increasing natural organic matter (NOM) concentrations (0.1–0.3 mg/L), while it was completely suppressed at higher NOM concentrations (0.5 mg/L). Four degradation products in total of CAP were identified in O3-based processes (i.e., O3, O3/TBA, O3/H2O2, O3/PMS and O3/PMS/tert-butyl alcohol (TBA) systems. Besides, these transformation products by OH, SO4− and/or O3 were also distinguished. Finally, the impact of O3/PMS pre-oxidation on the formation of dichloroacetamide (DCAcAm) from CAP during post-chlorination process was investigated. Compared with the traditional O3 and O3/H2O2 processes, O3/PMS pre-oxidation generally led to the least generation of DCAcAm under similar conditions, where SO4− rather than OH was conducive to relieve the formation of DCAcAm. Moreover, the presence of NOM obviously alleviated the formation of DCAcAm by O3/PMS pre-oxidation.

Different removal efficiency of disinfection-byproduct precursors between dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm) by up-flow biological activated carbon (UBAC) process.

Up-flow biological activated carbon (UBAC) filter has been widely used in waterworks due to its less hydraulic loss, stronger biodegradation ability, and the prevention of excessive biomass growth relative to down-flow BAC treatment. In this study, the different removal efficiency (DRE) of disinfection byproduct precursors between dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm) was evaluated when UBAC filter was used as advanced treatment process. Results showed that the UBAC filter with approximately 36months of usage time had a poor performance in the removal of DCAcAm formation potential (FP) (i.e. 9.3-19.1%) compared to DCAN FP (i.e., 22.5-34.1%). After chlorination of UBAC effluent, the hydrolysis of DCAN to form DCAcAm only partly contributed to the DRE variations of both DCAN FP and DCAcAm FP. Using the high-throughput sequencing technology and the redundancy analysis (RDA), the second dominant genus Bacillus in UBAC filter, which may transform precursors of DCAN into inorganic matters, could be another reason that led to the DRE in DCAN and DCAcAm FP. The formation and leakage of soluble microbial products (SMPs) was identified by excitation-emission matrix (EEM) peak intensities as well as variation of biological index (BIX). The SMPs released into UBAC effluent, favoring the formation of DCAcAm, also contributed to the precursors of both DCAN and DCAcAm, causing a poor removal performance in DCAcAm FP by UBAC filter.

Effect of reduced sulfur group on the formation of CX3R-type disinfection by-products during chlor(am)ination of reduced sulfur compounds

Previous studies have examined the effects of peptide bond and unsaturated bond on the formation of disinfection by-products (DBPs). However, limited information has been available for the impact of reduced sulfur group on the formation of DBPs. This study investigated the formation of carbonaceous and nitrogenous DBPs (C-DBPs and N-DBPs) with a similar structure of ''CX3R'' (X = H, Cl, Br or I, R = functional group), including trihalomethanes, haloacetaldehydes, haloketones, haloacetonitriles, haloacetamides and halonitromethanes, during chlor(am)ination of three reduced sulfur compounds (RSCs), such as N-acetylcysteine, glutathione and glutathiol. Results showed that all DBPs except dichloroacetonitrile (DCAN) continuously increased with increasing Cl2 or NH2Cl doses in this study. The chlor(am)ination of three RSCs with lower disinfectant doses (the molar ratio of disinfectant to precursor ≤5) generated low DBPs compare to non-RSCs. More chloroform was observed in alkaline condition, while weak acidic condition was in favor of DCAN and dichloroacetamide formation. The results of frontier electron density calculation reported that the much higher reactivity for Cl2 and NH2Cl toward reduced sulfur group in RSCs protects other groups, which account for the formation of CX3R-type DBPs. This phenomenon has important environmental implications. When RSCs are present in the water, Cl2 or NH2Cl will reacts preferably with them rather than non-RSCs to form RSO3H as the major products. Hence, the trade-offs of between the products generated upon S-chlorination, which account for the formation RSO3H, and alkyl halogenation and N-chlorination, which account for the formation of CX3R-type DBPs, influence the formation of CX3R-type DBPs.

Effect of copper corrosion products on the formation and speciation of haloacetamides and haloacetonitriles during chlorination

The catalytic effect of copper corrosion products, including copper ions, cupric oxide, and cuprous oxide, on the formation of haloacetamides and haloacetonitriles during chlorination of natural organic matter (NOM), model nitrogenous precursors, and real water samples was investigated. During chlorination of NOM, the presence of these copper corrosion products facilitated chlorine decay, and enhanced the formation of dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm) with enhancement ratios of 45–59% and 64–137% after 10 h contact time, respectively. Six amino acids were selected as nitrogenous NOM surrogates for chlorination, and the results show that the enhancement of DCAN and DCAcAm formation by copper corrosion products was only observed for slow reacting amino acids, including glutamine, glutamic acid, and phenylamine, suggesting that copper corrosion products may enhance DCAN and DCAcAm formation by catalyzing NOM portions that are relatively inefficient precursors. When bromide and copper corrosion products were present, the formation of dihaloacetonitriles (DHANs) and dihaloacetamides (DHAcAms) could be enhanced during chlorination of NOM, but the degrees of bromine substitution for DHANs and DHAcAms decreased. Although copper corrosion products facilitated DHAN and DHAcAm hydrolysis with the facilitation increasing as the halogens shifted from chlorine to bromine, increased DHAN and DHAcAm concentrations was observed during chlorination of real water samples in the presence of copper corrosion products, confirming that the copper corrosion products had a catalytic effect on DHAN and DHAcAm formation that exceeded their catalytic effect on DHAN and DHAcAm hydrolysis. This study provides basic knowledge of disinfectant residuals and the fate of haloacetonitriles and haloacetamides in drinking water distribution systems where copper is used, which will be helpful for the management of safe water distribution.

Degradation of acrylamide during chlorination as a precursor of haloacetonitriles and haloacetamides

Acrylamide is a monomer of polyacrylamide, which is widely used in the water treatment process as a flocculant. The degradation kinetics and formation of disinfection by-products (DBPs) during acrylamide chlorination were investigated in this study. The reaction between chlorine and acrylamide followed a pseudo-first-order kinetics. A kinetic model regarding acrylamide chlorination was established and the rate constants of each predominant elementary reaction (i.e., the base-catalyzed reaction of acrylamide with ClO− as well as the reactions of acrylamide with HOCl and ClO−) were calculated as 7.89×107M−2h−1, 7.72×101M−1h−1, and 1.65×103M−1h−1, respectively. The presence of Br− in water led to the formation of HOBr and accelerated the rate of acrylamide degradation by chlorine. The reaction rate constant of acrylamide with HOBr was calculated as 1.33×103M−1h−1. The degradation pathways of acrylamide chlorination were proposed according to the intermediates identified using ultra-performance liquid chromatography and electrospray ionization-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF/MS). Five chlorinated DBPs including chloroform (CF), dichloroacetonitrile (DCAN), trichloroacetonitrile (TCAN), dichloroacetamide (DCAcAm), and trichloroacetamide (TCAcAm) were identified during acrylamide chlorination. The formation of CF, DCAN, DCAcAm, and TCAcAm kept increasing, while that of TCAN increased and then decreased with increasing reaction time. As the chlorine dosage increased from 0.75 to 4.5mM, DCAN became the dominant DBP. Large amounts of CF, DCAN, and TCAN were formed at basic pHs. The hydrolysis of DCAN and TCAN led to the formation of DCAcAm and TCAcAm, respectively. The results of this study elucidated that acrylamide can be a precursor for the formation of haloacetonitriles (HANs) and haloacetamides (HAcAms) during drinking water treatment.

Factors affecting the formation of nitrogenous disinfection by-products during chlorination of aspartic acid in drinking water

The formation of emerging nitrogenous disinfection by-products (N-DBPs) from the chlorination of aspartic acid (Asp) was investigated. The yield of dichloroacetonitrile (DCAN) was higher than other N-DBPs, such as dichloroacetamide(DCAcAm) and chloropicrin (TCNM) during the chlorination of Asp. The formation of DCAN, DCAcAm, and TCNM all showed a trend of first increasing and then decreasing during the chlorination of Asp with increasing contact time. The dosage of chlorine had an impact on the formation of DCAN, DCAcAm, and TCNM. The highest yields of DCAN and DCAcAm appeared when the Cl2/Asp molar ratio was about 20, the yield of TCNM increased with increasing the Cl2/Asp molar ratio from 5 to 30 and TCNM was not produced when the ratio was less than 5. Cyanogen chloride (CNCl) was detected when the Cl2/Asp molar ratio was lower than 5. N-DBPs formation was influenced by pH. DCAN formation increased with increasing pH from 5 to 6 and then decreased with increasing pH from 6 to 9, but DCAcAm and TCNM increased with increasing pH from 5 to 8 and then decreased. Higher temperatures reduced the formation of DCAN and DCAcAm, but increased TCNM formation. DCAN and DCAcAm formation decreased, and relatively stable TCNM formation increased, with increasing free chlorine contact time during chloramination. N-nitrosodimethylamine (NDMA) was produced during chloramination of Asp and increased with prolonged chloramination contact time. The presence of bromide ions enhanced the yields of haloacetonitriles and shifted N-DBPs to more brominated species.

Zero valent iron produces dichloroacetamide from chloramphenicol antibiotics in the absence of chlorine and chloramines

Dichloroacetamide (DCAcAm) is an important type of nitrogenous disinfection byproduct. This study is the first to report that DCAcAm can be formed in the absence of chlorinated disinfectants (chlorine and chloramines). This can occur through reduction of three chloramphenicol (CAP) antibiotics by zero valent iron (ZVI). The effects of key experimental parameters, including reaction time, ZVI dose, pH, temperature, water type, and the presence of humic acid (HA) on the formation of DCAcAm were ascertained. The DCAcAm yields from three CAPs all presented the trend of increasing first and then decreasing with time and also increased with increasing ZVI dosage. DCAcAm yields from the ZVI reduction route were higher than those resulting from the chlorination of some previously identified DCAcAm precursors. Acidic conditions favored the formation of DCAcAm by the ZVI route. In addition, lower temperatures increased DCAcAm yields at extended contact times (>12 h). DCAcAm formed from the three CAPs in the presence of HA was lower than in the absence of HA. The formation potential of DCAcAm from the reduction of authentic waters spiked with CAPs by ZVI showed good linear correlations with initial concentrations of the three CAPs. This allows the formation of DCAcAm from the reduction of CAPs by ZVI to be predicted. Given that many wastewater and drinking water distribution networks contain unlined cast iron pipes, reactions between CAPs and ZVI may contribute to the formation of DCAcAm in such systems.

Contribution of the Antibiotic Chloramphenicol and Its Analogues as Precursors of Dichloroacetamide and Other Disinfection Byproducts in Drinking Water.

Dichloroacetamide (DCAcAm), a disinfection byproduct, has been detected in drinking water. Previous research showed that amino acids may be DCAcAm precursors. However, other precursors may be present. This study explored the contribution of the antibiotic chloramphenicol (CAP) and two of its analogues (thiamphenicol, TAP; florfenicol, FF) (referred to collectively as CAPs), which occur in wastewater-impacted source waters, to the formation of DCAcAm. Their formation yields were compared to free and combined amino acids, and they were investigated in filtered waters from drinking-water-treatment plants, heavily wastewater-impacted natural waters, and secondary effluents from wastewater treatment plants. CAPs had greater DCAcAm formation potential than two representative amino acid precursors. However, in drinking waters with ng/L levels of CAPs, they will not contribute as much to DCAcAm formation as the μg/L levels of amino acids. Also, the effect of advanced oxidation processes (AOPs) on DCAcAm formation from CAPs in real water samples during subsequent chlorination was evaluated. Preoxidation of CAPs with AOPs reduced the formation of DCAcAm during postchlorination. The results of this study suggest that CAPs should be considered as possible precursors of DCAcAm, especially in heavily wastewater-impacted waters.

Formation of haloacetonitriles and haloacetamides and their precursors during chlorination of secondary effluents.

The formation of dichloroacetonitrile (DCAN), dichloroacetamide (DCAcAm) and trichloroacetamide (TCAcAm) during chlorination of secondary effluents was evaluated under different conditions. The formation of DCAN and DCAcAm increased, then decreased with increasing contact time and chlorine dose, while TCAcAm formation increased continually, exceeding DCAcAm formation after a relatively long contact time or in response to a relatively high chlorine dose (20-80 mg L(-1)). Increasing the sample pH from 6 to 9 reduced the formation of DCAN and TCAcAm, while DCAcAm formation was highest at pH 8. Precursors in the secondary effluent were characterized by separating the organic matter into several fractions using membrane filtration and XAD resins and then measuring the formation of DCAN, DCAcAm and TCAcAm from each fraction during chlorination. Dissolved organic matter (DOM) with a molecular weight less than 1 kDa dominated the formation of DCAcAm and TCAcAm. However, particle-associated DCAN precursors were detected in addition to potent DCAN precursors in the DOM fractions. Among the XAD fractions of DOM, the hydrophilic neutral fraction prevailed in the secondary effluent and produced the most DCAN, DCAcAm and TCAcAm per volume, and the hydrophilic basic fraction with a low organic content had the highest yields of DCAN, DCAcAm and TCAcAm on a DOC basis, so their dominant precursors were associated with hydrophilic matter.

Formation of haloacetonitriles and haloacetamides during chlorination of pure culture bacteria

The increasing reuse of organic nitrogen-rich wastewater raises concerns regarding the formation of nitrogenous disinfection by-products (N-DBPs), such as haloacetonitriles and haloacetamides. Previous research mainly focused on N-DBPs formation from dissolved organic matter in wastewater. In this study, dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm) formation from particles in the secondary effluents of a domestic wastewater treatment plant during chlorination was assessed to account for 26–46% of the total formation. As part of particles in wastewater, bacterial cells enriched in organic nitrogen are considered a potential source for the formation of N-DBPs during chlorination. The formation of DCAN, DCAcAm and trichloroacetamide (TCAcAm) during the chlorination of a Gram-negative bacterium of Escherichia coli (E. coli) and a Gram-positive bacterium of Enterococcus faecalis (E. faecalis) were then evaluated. Compared with dissolved organic matter in the secondary effluent, bacterial cells formed more DCAN, DCAcAm and TCAcAm during chlorination. E. faecalis formed more DCAN, but less DCAcAm and TCAcAm than E. coli did under most chlorination conditions. Moreover, the effects of contact time, chlorine dose, pH value and ammonia nitrogen concentration on the N-DBPs formation from the two bacterial suspensions were investigated. Under the chlorination conditions in this study, DCAN formation from the bacterial suspensions initially increased and then decreased, while TCAcAm formation increased with increasing contact time and chlorine dose. DCAcAm formation from the bacterial suspensions increased with the prolonged contact time, and increased and then decreased with increasing chlorine dose. DCAN, DCAcAm and TCAcAm formation was favored under neutral pH condition, but was reduced with the addition of ammonia during the chlorination of the two bacterial suspensions.

Dichloroacetonitrile and Dichloroacetamide Can Form Independently during Chlorination and Chloramination of Drinking Waters, Model Organic Matters, and Wastewater Effluents

The increasing usage of organic nitrogen-rich wastewater- or algal-impacted waters, and chloramines for secondary disinfection, raises concerns regarding the formation of haloacetonitriles, haloacetamides and other nitrogenous disinfection byproducts (N-DBPs). Previous research obtained contradictory results regarding the relative importance of chlorination or chloramination for promoting these byproducts, but applied chlorine and chloramines at different doses and exposure periods. Additionally, mechanistic work, mostly using model precursors, suggested that haloacetonitrile and haloacetamide formation should be correlated because hydrolysis of haloacetonitriles forms haloacetamides. In this work, the formation of dichloroacetonitrile (DCAN) and dichloroacetamide (DCAcAm) were compared across a range of chlorine and chloramine exposures for drinking waters, wastewater effluents, algal extracellular polymeric substances (EPS), NOM isolates and model precursors. While chlorination favored formation of DCAN over DCAcAm, chloramination nearly always formed more DCAcAm than DCAN, suggesting the existence of haloacetamide formation pathways that are independent of the hydrolysis of haloacetonitriles. Experiments with asparagine as a model precursor also suggested DCAcAm formation without a DCAN intermediate. Application of (15)N-labeled monochloramine indicated initial rapid formation of both DCAN and DCAcAm by pathways where the nitrogen originated from organic nitrogen precursors. However, slower formation occurred by pathways involving chloramine incorporation into organic precursors. While wastewater effluents and algal EPS tended to be more potent precursors for DCAN during chlorination, humic materials were more potent precursors for DCAcAm during chlorination and for both DCAN and DCAcAm during chloramination. These results suggest that, rather than considering haloacetamides as haloacetonitrile hydrolysis products, they should be treated as a separate N-DBP class associated with chloramination. While use of impaired waters may promote DCAN formation during chlorination, use of chloramines may promote haloacetamide formation for a wider array of waters.

A predictive model for the formation potential of dichloroacetamide, a nitrogenous disinfection by-product formed during chlorination

Nitrogenous disinfection by-products have increasingly become a public health concern in the drinking water industry because they have been found to be more geno- and cytotoxic than most of the currently regulated disinfection by-products. Dichloroacetamide, a nitrogenous disinfection by-product which is formed during chlorination in water treatment, has increasingly received attention due to its elevated genotoxicity and cytotoxicity relative to the currently regulated disinfection by-products. In this study, a power function model with parameters of dissolved organic nitrogen, dissolved organic carbon, bromide, soluble microbial products, and aromatic proteins was developed to successfully predict dichloroacetamide formation potential. The inclusion of soluble microbial product and aromatic protein into the model significantly improved the prediction, suggesting that soluble microbial product and aromatic protein play a significant role in the formation of dichloroacetamide. Additionally, the performance of the predictive model appeared to be somewhat affected by the characteristics of raw water used to develop the model.

Ozone–biological activated carbon integrated treatment for removal of precursors of halogenated nitrogenous disinfection by-products

Pilot-scale tests were performed to reduce the formation of several nitrogenous and carbonaceous disinfection by-products (DBPs) with an integrated ozone and biological activated carbon (O3–BAC) treatment process following conventional water treatment processes (coagulation–sedimentation–filtration). Relative to the conventional processes alone, O3–BAC significantly improved the removal of turbidity, dissolved organic carbon, UV254, NH4+ and dissolved organic nitrogen from 98–99%, 58–72%, 31–53%, 16–93% and 35–74%, respectively, and enhanced the removal efficiency of the precursors for the measured DBPs. The conventional process was almost ineffective in removing the precursors of trichloronitromethane (TCNM) and dichloroacetamide (DCAcAm). Ozonation could not substantially reduce the formation of DCAcAm, and actually increased the formation potential of TCNM; it chemically altered the molecular structures of the precursors and increased the biodegradability of N-containing organic compounds. Consequently, the subsequent BAC filtration substantially reduced the formation of the both TCNM and DCAcAm, thus highlighting a synergistic effect of O3 and BAC. Additionally, O3–BAC was effective at controlling the formation of the total organic halogen, which can be considered as an indicator of the formation of unidentified DBPs.

Impacts of drinking water pretreatments on the formation of nitrogenous disinfection by-products

The formation of disinfection by-products (DBPs), including both nitrogenous DBPs (N-DBPs) and carbonaceous DBPs (C-DBPs), was investigated by analyzing chlorinated water samples following the application of three pretreatment processes: (i) powdered activated carbon (PAC) adsorption; (ii) KMnO 4 oxidation and (iii) biological contact oxidation (BCO), coupled with conventional water treatment processes. PAC adsorption can remove effectively the precursors of chloroform (42.7%), dichloroacetonitrile (28.6%), dichloroacetamide (DCAcAm) (27.2%) and trichloronitromethane (35.7%), which were higher than that pretreated by KMnO 4 oxidation and/or BCO process. The removal efficiency of dissolved organic carbon by BCO process (76.5%) -was superior to that by PAC adsorption (69.9%) and KMnO 4 oxidation (61.4%). However, BCO increased the dissolved organic nitrogen (DON) concentration which caused more N-DBPs to be formed during subsequent chlorination. Soluble microbial products including numerous DON compounds were produced in the BCO process and were observed to play an essential role in the formation of DCAcAm in particular.

Precursors of Dichloroacetamide, an Emerging Nitrogenous DBP Formed during Chlorination or Chloramination

Haloacetamides (HAcAms) are an emerging class of nitrogenous disinfection byproducts (N-DBPs). However, there is a limited understanding about the precursors of HAcAms. In this study, we screened the precursors of dichloroacetamide (DCAcAm), the most commonly identified HAcAm in chlorinated or chloraminated drinking water. DCAcAm formation potential (FP) of raw water samples collected in different months from a reservoir in China was determined during chlorination, and the highest DCAcAm FP typically occurred in the summer samples. Dissolved organic matter (DOM) in a representative summer raw water sample was separated into six fractions by a series of resin elutions. Among them, hydrophilic acid (HiA) DOM showed the maximum DCAcAm FP, followed by hydrophilic bases (HiB) and, to a much lower extent, hydrophobic acids (HoA). Fluorescence excitation-emission matrix (EEM) spectra revealed that a mass of protein-like substances in the HiA fraction, made up of amino acids (AAs), were the likely DCAcAm precursors. Finally, we investigated the DCAcAm yields of 20 AAs during chlorination. Among them, seven AAs (aspartic acid, histidine, tyrosine, tryptophan, glutamine, asparagine, phenylalanine) could form DCAcAm during chlorination, with the corresponding DCAcAm yields of 0.231, 0.189, 0.153, 0.104, 0.078, 0.058, and 0.050 mmol/mol AA.