Formation of organic chloramines during water disinfection - chlorination versus chloramination

Many of the available studies on formation of organic chloramines during chlorination or chloramination have involved model organic nitrogen compounds (e.g., amino acids), but not naturally occurring organic nitrogen in water. This study assessed organic chloramine formation during chlorination and chloramination of 16 natural organic matter (NOM) solutions and 16 surface waters which contained dissolved organic nitrogen (DON). Chlorination rapidly formed organic chloramines within 10 min, whereas chloramination formed organic chloramination much more slowly, reaching the maximum concentration between 2 and 120 h after the addition of monochloramine into the solutions containing DON. The average organic chloramine formation upon addition of free chlorine and monochloramine into the NOM solutions were 0.78 mg-Cl₂/mg-DON at 10 min and 0.16 mg-Cl₂/mg-DON at 24 h, respectively. Organic chloramine formation upon chlorination and chloramination increased as the dissolved organic carbon/dissolved organic nitrogen (DOC/DON) ratio decreased (i.e., DON contents increased). Chlorination of molecular weight (10,000 Da) fractionated water showed that molecular weight of DON would not impact the amount of organic chloramines produced. Comparison of three different disinfection schemes at water treatment plants (free chlorine, preformed monochloramine, and chlorine/ammonia additions) indicated organic chloramine formation could lead to a possible overestimation of disinfection capacity in many chloraminated water systems that add chlorine followed by an ammonia addition to form monochloramine.     

Monochloramine cometabolism by Nitrosomonas europaea under drinking water conditions

Chloramine is widely used in United States drinking water systems as a secondary disinfectant, which may promote the growth of nitrifying bacteria because ammonia is present. At the onset of nitrification, both nitrifying bacteria and their products exert a monochloramine demand, decreasing the residual disinfectant concentration in water distribution systems. This work investigated another potentially significant mechanism for residual disinfectant loss: monochloramine cometabolism by ammonia-oxidizing bacteria (AOB).Monochloramine cometabolism was studied with the pure culture AOB Nitrosomonas europaea (ATCC 19718) in batch kinetic experiments under drinking water conditions. Three batch reactors were used in each experiment: a positive control to estimate the ammonia kinetic parameters, a negative control to account for abiotic reactions, and a cometabolism reactor to estimate the cometabolism kinetic constants. Kinetic parameters were estimated in AQUASIM with a simultaneous fit to all experimental data. The cometabolism reactors showed a more rapid monochloramine decay than in the negative controls, demonstrating that cometabolism occurs. Cometabolism kinetics were best described by a pseudo first order model with a reductant term to account for ammonia availability. Monochloramine cometabolism kinetics were similar to those of ammonia metabolism, and monochloramine cometabolism was a significant loss mechanism (30–60% of the observed monochloramine decay). These results suggest that monochloramine cometabolism should occur in practice and may be a significant contribution to monochloramine decay during nitrification episodes in drinking water distribution systems.     

Contributions of genotoxic precursors from tributary rivers and sewage effluents to the Yodo River in Japan

The cause of water pollution in the Yodo River was examined regarding the mutagenic potentials formed by chlorination of river waters and sewage effluents along the river. Mutagenicity of the extracts from chlorinated waters was measured by Ames test using S. typhimurium TA100 strain without metabolic activation. Mutagenic formation potentials of sewage effluents were 4-5 times higher than those of the three tributary river waters, the Kizu, Uji and Katsura Rivers. The contribution rates of the pollution loads from the three river waters and total of four sewage effluents to the Yodo River were revealed to be 10.2%, 42.2%, 22.1% and 25.5%, respectively. The rate of the sewage effluents occupied one-fourth and exceeded the rates of the Kizu and Katsura Rivers. The contribution rate of the two sewage effluents to the Katsura River was 46.3%. It could be confirmed that the relationship between COD and MFP in river waters and sewage effluents was very high with a correlation coefficient. These results indicated that the waters inflowing to the Yodo River were contaminated with numerous organic compounds, and the sewage effluents especially contribute to the formation of genotoxicity by the interaction between chlorine and organic components as genotoxic precursors in the purification plants.     

Effects of activated carbon on the reactions of combined chlorine with phenols

In the presence of ammonia, prechlorination in drinking water treatment results in contact of combined chlorine (monochloramine) with activated carbon, which is used to remove organic compounds from water. Monochloramine reacts very slowly with phenolic compounds in aqueous solution, giving low yields of chlorinated phenols. When monochloramine reacts with phenols adsorbed on granular activated carbon (GAC), however, several oxidized products, principally hydroxylated biphenyls, are formed. Some of the hydroxylated biphenyls are chlorinated (hydroxylated PCBs). Their formation is particularly important because of their potential toxicity. Such compounds are major reaction products from chlorophenol, but they are also formed in small amounts from nonchlorinated phenols. Most of the monochloramine-GAC-phenolic compound reaction products are also produced in similar reactions with free chlorine, indicating that similar reaction mechanisms (free radical mechanisms) take place on carbon's surface. No organic compounds are produced from the reaction of monochloramine with GAC alone.     

Comparison of disinfection byproduct formation from chlorine and alternative disinfectants

Seven diverse natural waters were collected and treated in the laboratory under five oxidation scenarios (chlorine, chloramine, both with and without preozonation, and chlorine dioxide). The impact of these disinfectants on the formation of disinfection byproducts was investigated. Results showed that preozonation decreased the formation of trihalomethanes (THMs), haloacetic acids (HAAs) and total organic halogen (TOX) for most waters during postchlorination. A net increase in THMs, HAAs and TOX was observed for a water of low humic content. Either decreases or increases were observed in dihaloacetic acids and unknown TOX (UTOX) as a result of preozonation when used with chloramination. Chloramines and chlorine dioxide produced a higher percentage of UTOX than free chlorine. They also formed more iodoform and total organic iodine (TOI) than free chlorine in the presence of iodide. Free chlorine produced a much higher level of total organic chlorine (TOCl) and bromine (TOBr) than chloramines and chlorine dioxide in the presence of bromide.     

Etude physicochimique de la chloration de l'eau de mer artificielle contenant de l'azote ammoniacal

Chlorine added to ammonia-free sea-water gives rise to a fast and quantitative oxidation of bromide to hypobromite and hypobromous acid. However as ammonia nitrogen levels commonly found in coastal and estuarine sea-water are sufficiently high and thus not negligible compared to the chlorine dose introduced formation of monochloramine to compete with oxidation of bromine leading to bromamines. The relative importance of these two reactional pathways is estimated considering both bromine determination and study of the electron absorption spectra of chlorinated seawater. In order to avoid substitution reactions taking place in the presence of organic compounds, preliminary experiments have been carried out in artificial and u.v. photo-oxidized sea-water.The nature of the species formed depends on the molar ratio added chlorine vs ammonia-nitrogen concentration of seawater. With Cl/N larger than 1.5, only bromide derivatives are obtained: dibromamine, tribromamine and bromine(I) (HBrO + BrO⁻). Cl/N smaller than 1.5 leads to a mixture of monochloramine, dibromamine and some monobromamine: monochloramine clearly predominates when ammonium concentrations reach higher values. Stoichiometry of ammonia to nitrogen oxidation by chlorine explains this ratio of 1.5 and a strong decrease of the total oxidant concentration is observed under these conditions. Bromamines decompose within the following 30–60 min; only stable compounds remain: either bromine(I) or monochloramine according to Cl/N values. A similar behaviour is observed in natural seawater previously doped with ammonia as to the nature of the products formed for a given Cl/N ratio; however, bromamines decompose more rapidly due to bromination of organic components.     

Effect of free ammonia concentration on monochloramine penetration within a nitrifying biofilm and its effect on activity, viability, and recovery

Chloramine has replaced free chorine for secondary disinfection at many water utilities because of disinfection by-product (DBP) regulations. Because chloramination provides a source of ammonia, there is a potential for nitrification when using chloramines. Nitrification in drinking water distribution systems is undesirable and may result in degradation of water quality and subsequent non-compliance with existing regulations. Thus, nitrification control is a major issue and likely to become increasingly important as chloramine use increases. In this study, monochloramine penetration and its effect on nitrifying biofilm activity, viability, and recovery was investigated and evaluated using microelectrodes and confocal laser scanning microscopy (CLSM). Monochloramine was applied to nitrifying biofilm for 24 h at two different chlorine to nitrogen (Cl₂:N) mass ratios (4:1 [4.4 mg Cl₂/L] or 1:1 Cl₂:N [5.3 mg Cl₂/L]), resulting in either a low (0.23 mg N/L) or high (4.2 mg N/L) free ammonia concentration. Subsequently, these biofilm samples were allowed to recover without monochloramine and receiving 4.2 mg N/L free ammonia. Under both monochloramine application conditions, monochloramine fully penetrated into the nitrifying biofilm within 24 h. Despite this complete monochloramine penetration, complete viability loss did not occur, and both biofilm samples subsequently recovered aerobic activity when fed only free ammonia. When monochloramine was applied with a low free ammonia concentration, dissolved oxygen (DO) fully penetrated, but with a high free ammonia concentration, complete cessation of aerobic activity (i.e., oxygen utilization) did not occur and subsequent analysis indicated that oxygen consumption still remained near the substratum. During the ammonia only recovery phase, different spatial recoveries were seen in each of the samples, based on oxygen utilization. It appears that the presence of higher free ammonia concentration allowed a larger biomass to remain active during monochloramine application, particularly the organisms deeper within the biofilm, leading to faster recovery in oxygen utilization when monochloramine was removed. These results suggest that limiting the free ammonia concentration during monochloramine application will slow the onset of nitrification episodes by maintaining the biofilm biomass at a state of lower activity.     

The microcoulometric determination of extractable organic halogen in surface water; Application to surface waters of The Netherlands

In this paper an analytical method is described for the microcoulometric determination of extractable organic halogen, especially chlorine, in surface waters and sediments. The minimum detectable amounts of chlorine are respectivelly 1.0 μg/l (ppb) in water and 0.5 mg/kg (ppm) in sediments. The results of a monitoring program in the river Rhine and several Dutch surface waters with respect to this parameter are presented. The results cover the period January 1973 to December 1975.In 1973, 1974 and 1975 the average daily loads of organic halogen calculated as chlorine in the river Rhine at Lobith were 3300, 3410 and 2050 kg, respectively.The parameter “Extractable Organic Chlorine” (EOCl) is suggested as a useful general indicator for chemical pollution in surface waters and in effluents from industrial plants.     

一氯胺消毒剂检测新技术及应用

讨论了传统一氯胺测定方法在应用中的局限性,并介绍了一种新的检测技术.实际应用表明该技术可以使水厂饮用水消毒中产生尽可能多的一氯胺,还可以使污水处理厂出水消毒中一氯胺的检测精确,而不受有机氯胺、亚硝酸盐和锰的干扰;帮助水厂控制过量投加氯和氨,从而降低成本.     

Monochloramine decay in model and distribution system waters

Chloramines have long been used to provide a disinfecting residual in distribution systems where it is difficult to maintain a free chlorine residual or where disinfection by-product (DBP) formation is of concern. While chloramines are generally considered less reactive than free chlorine, they are inherently unstable even in the absence of reactive substances. These reactions, often referred to as "auto-decomposition", always occur and hence define the maximum stability of monochloramine in water. The effect of additional reactive material must be measured relative to this basic loss process. A thorough understanding of the auto-decomposition reactions is fundamental to the development of mechanisms that account for reactions with additional substances and to the ultimate formation of DBPs. A kinetic model describing auto-decomposition was recently developed. This model is based on studies of isolated individual reactions and on observations of the reactive ammonia-chlorine system as a whole. The work presented here validates and extends this model for use in waters typical of those encountered in distribution systems and under realistic chloramination conditions. The effect of carbonate and temperature on auto-decomposition is discussed. The influence of bromide and nitrite at representative monochloramine concentrations is also examined, and additional reactions to account for their influence on monochloramine decay are presented to demonstrate the ability of the model to incorporate inorganic demand pathways that occur parallel to auto-decomposition.     

The influence of disinfection on aquatic biodegradable organic carbon formation

The aim of this paper was to assess the extent of biodegradable dissolved organic carbon formation upon disinfection of water with chlorine dioxide. Wide diversity of natural waters has been subjected to reactions with various amounts of ClO₂. For comparison examined waters have also been treated with ozone and chlorine. The application of chlorine dioxide and ozone significantly changed the molecular weight distribution of aquatic organic matter. As a result significant amounts of biodegradable carboxylic acids and aldehydes were generated. The formic, acetic, oxalic and ketomalonic acids as well as formaldehyde, acetaldehyde, glyoxal, methylglyoxal were identified. The productivity of aldehydes calculated for all examined waters and disinfectants amounted 12.7-47.7 μg mg⁻¹ DOC in the case of ozonation, 1.3-8.1 μg mg⁻¹ DOC after chlorination and 1.7-9.4 μg mg⁻¹ DOC for ClO₂ treatment. The highest total concentration of carboxylic acids was determined after the ozonation processes. In this case the organic acids' formation potential was in the range 10.8-62.8 μg mg⁻¹ DOC. Relatively high formation potential (5.3-17.9 μg mg⁻¹ DOC) was determined after the oxidation with ClO₂ as well. In the case of chlorination, the productivity of organic acids was low and did not exceed 3.4 μg mg⁻¹ DOC. The relatively high correlation between BDOC formation and carboxylic acids' formation potential was observed. Thus, carboxylic acids' formation potential may be used as a measure of water potential to form BDOC.     

Formation of disinfection by-products in indoor swimming pool water: the contribution from filling water natural organic matter and swimmer body fluids

The contribution and role of different precursors in the formation of three class of disinfection by-products (DBPs) [trihalomethanes (THMs), haloacetic acids (HAAs), and halonitromethanes (HNMs)] in swimming pool waters were examined using filling waters obtained from five drinking water treatment plant (WTP) effluents and three body fluid analogs (BFAs). BFAs exerted higher chlorine demands as compared to natural organic matter (NOM) in filling waters. BFAs exhibited higher HAA formation potentials than THM formation potentials, while the opposite was observed for the filling water NOM. There was no appreciable difference in the HNM formation potentials of BFAs and filling water NOM. Different components in the BFAs tested exhibited different degree and type of DBP formation. Citric acid had significantly higher THM and HAA yields than other BFA components. The effect of temperature was greater on THM formation, whereas the effect of contact time had more impact on HAA formation. Experiments with filling waters collected from WTP effluents at three different times showed more variability in HAA than THM formation at the WTPs studied.     

A N-Nitrosodimethylamine (NDMA) precursor analysis for chlorination of water and wastewater

N-nitrosodimethylamine (NDMA) is a potent carcinogen formed during chloramination of water and wastewater treatment plant effluents. A procedure is described for quantifying the concentration of the organic precursors of NDMA that could be formed during chlorination of wastewaters and natural waters. The method involves applying a high dose of monochloramine to a pH-buffered sample followed by a 10-day contact period, during which the monochloramine decays at a rate unrelated to the composition of the sample. Analyses of samples of municipal wastewater effluents and surface waters indicate that the method provides a robust and reproducible measurement of NDMA precursors over a wide range of conditions. A sensitive GC/CI/MS/MS analytical procedure for dimethylamine also is described and used to demonstrate that NDMA formation during chlorination of wastewater and natural waters cannot be explained by dimethylamine concentrations alone.     

Comportement des acides amines dissous du milieu marin apres injection de chlore

Evidence that dissolved organic matter is one of the most significant sources of chlorine demand of seawaters (Fig. 1) used in cooling circuits is now well recognized. Nevertheless the specific role of the different kinds of compounds which form this organic material has seldom been studied and even less quantified; this is not surprising as less than 20% of the organic substances are identified. In this paper our objective was to define more quantitatively the effect of the dissolved free and combined amino-acids in the oxidant decay. Two main criteria justified the choice of these solutes:

1. (i)|the reactivity of chlorine and/or bromine towards amino groups;

2. (ii)|the role of these nitrogenous compounds in some biological mechanisms.

What happens to the halogen added and to the organic species during the first 20 min was investigated. The experimental conditions selected (concentrations, salinity, temperature and acidity) are those encountered in practice.The reactivity of the amino-acids towards chlorine is of course influenced by physicochemical properties such as the pH, but is particularly dependent upon the nature of the amino group. Whereas β and γ free amino-acids (Fig. 3) as also combined species (proteins) (Table 2) yield stable halogenocompounds like those produced with aliphatic amines (Fig. 2), α free amino-acids (COOH---CH---NH₂)|R on the other hand yield unstable haloamines which decompose rapidly (Fig. 4). Regarding these results, only the reactivity of the α compounds was afterwards studied as they are the largest fraction of the free amino-acids encountered in natural waters.After investigating the role of the side groups R in the kinetics and the efficiency of the consumption of the oxidant we examined, by liquid chromatography, the depletion of the nitrogenous species (Table 3). In each case the HPLC data relative to changes in the level of the organic compounds agree with those reported for the residual oxidant decay.A few experiments carried out on samples of seawater (Table 4) treated with 1 ppm of chlorine showed that around 5% of chlorine which dissipated during the first 3 min are consumed by the dissolved free amino-acids, the depletion of which is about 50%.     

Modeling monochloramine loss in the presence of natural organic matter

A comprehensive model describing monochloramine loss in the presence of natural organic matter (NOM) is presented. The model incorporates simultaneous monochloramine autodecomposition and reaction pathways resulting in NOM oxidation. These competing pathways were resolved numerically using an iterative process evaluating hypothesized reactions describing NOM oxidation by monochloramine under various experimental conditions. The reaction of monochloramine with NOM was described as biphasic using four NOM specific reaction parameters. NOM pathway 1 involves a direct reaction of monochloramine with NOM (k_doc1=1.05×10⁴-3.45×10⁴ M⁻¹ h⁻¹). NOM pathway 2 is slower in terms of monochloramine loss and attributable to free chorine (HOCl) derived from monochloramine hydrolysis (k_doc2=5.72×10⁵-6.98×10⁵ M⁻¹ h⁻¹), which accounted for the majority of monochloramine loss. Also, the free chlorine reactive site fraction in the NOM structure was found to correlate to specific ultraviolet absorbance at 280 nm (SUVA₂₈₀). Modeling monochloramine loss allowed for insight into disinfectant reaction pathways involving NOM oxidation. This knowledge is of value in assessing monochloramine stability in distribution systems and reaction pathways leading to disinfection by-product (DBP) formation.     

Using soil biomass as an indicator for the biological removal of effluent-derived organic carbon during soil infiltration

This study investigates the relationship between soil biomass and organic carbon removal during the infiltration of conventionally treated effluents used for groundwater recharge during soil-aquifer treatment (SAT). Investigations were conducted on samples collected from full-scale SAT sites, revealing a positive correlation between biodegradable organic carbon (BOC) concentrations in the recharged effluents and total viable soil biomass concentrations in the infiltration zone of soil samples collected from respective recharge basins. Findings of this study suggest that BOC limits soil biomass growth and was able to support a steady-state concentration of viable soil biomass that is characteristic to BOC concentrations introduced with the recharged effluents. All investigated sites indicate that BOC is primarily removed within 30 cm soil depth leading to a significant increase in soil biomass levels (measured as substrate induced respiration (SIR), total viable biomass, and dehydrogenase activity (DHA)). Controlled biological column studies revealed that the primary components of BOC in domestic effluents are organic colloids. Findings of this study support that hydrophobic acids, commonly believed to be recalcitrant, may also be attenuated by biological processes during soil infiltration.     

Occurrence and treatment of wastewater-derived organic nitrogen

Dissolved organic nitrogen (DON) derived from wastewater effluent can participate in reactions that lead to formation of nitrogenous chlorination by-products, membrane fouling, eutrophication, and nitrification issues, so management of DON is important for both wastewater reuse applications and nutrient-sensitive watersheds that receive discharges from treated wastewater. This study documents DON occurrence in full-scale water/wastewater (W/WW) treatment plant effluents and assesses the removal of wastewater-derived DON by several processes (biodegradation, coagulation, softening, and powdered activated carbon [PAC] adsorption) used for advanced treatment in wastewater reuse applications. After varying levels of wastewater treatment, the dominant aqueous nitrogenous species shifts from ammonia to nitrate after aerobic processes and nitrate to DON in tertiary treatment effluents. The fraction of DON in total dissolved nitrogen (TDN) accounts for at most 52% in tertiary treated effluents (median = 13%) and 54% in surface waters impacted by upstream wastewater discharges (median = 31%). The 5-day biodegradability/bioavailability of DON (39%) was higher, on average, than that of dissolved organic carbon (DOC, 26%); however, upon chlorination, the DON removal (3%) decreased significantly. Alum coagulation (with ≥8 mg/L alum per mg/L DOC) and lime softening (with pH 11.3-11.5) removed <25% of DON and DOC without selectivity. PAC adsorption preferentially removed more DOC than DON by 10% on average. The results provided herein hence shed light on approaches for reducing organic nitrogen content in treated wastewater.     

Factors influencing the effect of bleached kraft mill effluents on drinking water quality

The taste and odour of drinking waters contaminated with bleached kraft mill effluent (BKME) were investigated. Mill effluents with a wide range of odour thresholds were selected and the effects of biological treatment, conventional water purification, carbon filtration, residual chlorine concentration, and recipient water quality were evaluated. No correlation was found between the original odour of BKME and the drinking water impairment. The taste and odour of drinking water prepared from pure glacial-fed river water to which biotreated BKMEs from three separate pulp mills were added was found to be impaired at effluent concentrations ranging from 0.1 to 0.4%. Effluent biotreatment, conventional water purification, and carbon filtration significantly reduced, but did not completely eliminate, BKME-associated taste and odour in potable water samples. The concentration of residual chlorine in the finished drinking water samples was an important factor influencing the degree of taste impairment.     

Occurrence and formation potential of N-nitrosodimethylamine in ground water and river water in Tokyo

N-nitrosodimethylamine (NDMA), a disinfection byproduct of water and wastewater treatment processes, is a potent carcinogen. We investigated its occurrence and the potential for its formation by chlorination (NDMA-FP_2Cl) and by chloramination (NDMA-FP_2NHCl) in ground water and river water in Tokyo. To characterize NDMA precursors, we revealed their molecular weight distributions in ground water and river water. We collected 23 ground water and 18 river water samples and analyzed NDMA by liquid chromatography-tandem mass spectrometry. NDMA-FP_2Cl was evaluated by chlorinating water samples with free chlorine for 24 h at pH 7.0 while residual free chlorine was kept at 1.0-2.0 mgCl₂/L. NDMA-FP_2NHCl was evaluated by dosing water samples with monochloramine at 140 mgCl₂/L for 10 days at pH 6.8. NDMA precursors and dissolved organic carbon (DOC) were fractionated by filtration through 30-, 3-, and 0.5 kDa membranes. NDMA concentrations were <0.5-5.2 ng/L (median: 0.9 ng/L) in ground water and <0.5-3.4 ng/L (2.2 ng/L) in river water. NDMA concentrations in ground water were slightly lower than or comparable to those in river water. Concentrations of NDMA-FP_2Cl were not much higher than concentrations of NDMA except in samples containing high concentrations of NH₃ and NDMA precursors. The increased NDMA was possibly caused by reactions between NDMA precursors and monochloramine unintentionally formed by the reaction between free chlorine and NH₃ in the samples. NDMA precursors ranged from 4 to 84 ng-NDMA eq./L in ground water and from 11 to 185 ng-NDMA eq./L in river water. Those in ground water were significantly lower than those in river water, suggesting that NDMA precursors were biodegraded, adsorbed, or volatilized during infiltration. The molecular weight of NDMA precursors in river water was dominant in the <0.5 kDa fraction, followed by 0.5-3 kDa. However, their distribution was inconsistent in ground water: one was dominant in the <0.5 kDa fraction, and the other in 0.5-3 kDa. Molecular weight distributions of NDMA precursors were very different from those of DOC. This is the first study to reveal the widespread occurrence and characterization of NDMA precursors in ground water.     

THM, HAA and CNCl formation from UV irradiation and chlor(am)ination of selected organic waters

The formation of disinfection by-products (DBPs), including chloroform, dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), and cyanogen chloride (CNCl) after sequential exposure of four organic waters to UV irradiation via either low- or medium-pressure lamps and free chlorine (or preformed monochloramine) under practical conditions was simulated. Statistically significant changes in the DBP formation from chlorination due to the additional UV irradiation are commonly observed under testing conditions, although some of these changes are not practically significant. The impacts from UV exposure were found to be most significant in chloroform formation (up to 40 microg/L) among the four tested DBPs. Organics from rivers were more sensitive to UV alteration than was the organic drawn from soil. This difference could not be explained by the specific UV absorbance (SUVA) values. In most cases, irradiation with the medium-pressure UV lamp gave similar or slightly larger changes in DBP yields, compared with the corresponding trials using the low-pressure lamp. Different application sequences could significantly change the relative quantities of DBPs but no general trend was identified. Case-specific evaluation of the formation of chloroform and CNCl is necessary.