Chemical and biological oxidation of NOM surrogates and effect on HAA formation

Formation of disinfection by-products (DBPs) can be controlled by removal of disinfection by-product precursors before disinfection. Variable success has been reported, depending on the treatment used and water tested. Chemical and biological oxidations are candidate technologies to control DBP formation. Given the uncertainty over the identity of DBP precursors, the use of surrogates of natural organic matter (NOM) allows fundamental probing of the links between compound character, removal and DBP formation. Nine compounds were chosen to represent NOM and their removal by two advanced oxidation processes (AOPs), UV-C irradiation and biological treatment compared while haloacetic acid (HAA) formation before and after treatment was measured. Although AOPs were able to fully remove all compounds, incomplete mineralisation led to increased HAA levels, dramatically in the case of two amino acids. Biological treatment was effective in removing amino acids but also moderately increased the HAA formation potential (HAAFP) of hydrophilic compounds. These findings indicate waters with high amino acid concentrations will be susceptible to raised HAA levels following AOP treatment and careful process selection for HAA control is required in such cases.     

臭氧/氯消毒中藻类有机物生成消毒副产物的特征

饮用水源地藻华会释放大量藻类有机物(AOM),AOM与氯消毒剂反应生成的消毒副产物(DBPs)会给饮用水用户带来不容忽视的健康风险。为此,探究了臭氧/氯消毒对AOM结构和DBPs生成的影响。结果表明,臭氧氧化能有效去除AOM中芳香蛋白和酚类、叶绿素a、藻蓝蛋白结构物质,但是对腐殖酸类结构的去除效果相对较差。DBPs生成总量随臭氧投加浓度的升高而增加,其中主要是三氯甲烷(TCM);卤代乙腈和卤代酮的生成总量随臭氧投加浓度的变化趋势不明显。延长臭氧接触时间会明显增加1 h氯化中TCM的生成量,氯化24 h时DBPs生成总量与臭氧接触时间无关。在臭氧/氯消毒过程中,AOM的DBPs生成潜能低于天然有机物(NOM)。AOM有利于一溴一氯乙腈的生成,而NOM会生成更多的二氯乙腈。     

Removal of precursors for disinfection by-products (Dbps)--differences between ozone- and OH-radical-induced oxidation

Pre-oxidation is often applied to reduce the formation of disinfection by-products (DBPs). The aim of pre-oxidation is to remove the centers of natural organic matter (NOM) which are responsible for the formation of DBPs. In this paper, the differences between ozone- and OH-radical-induced oxidation to remove DBP-precursors are compared. The experiments were done with water of the River Ruhr (Germany) with a concentration of dissolved organic carbon (DOC) of 2 mg/l. Ozonation was able to remove DBP precursors selectively. After application of an absorbed ozone mass of 1.5 mg/mg DOC, a reduction in the formation potential for (THM-FP) and in the formation potential for organic halogen adsorbable on activated carbon (AOX-FP) down to 68 and 73% of the initial concentration was achieved, respectively. A removal of NOM was not achieved using absorbed ozone masses between 0.5 and 1.5 mg/mg DOC. In the hydrogen peroxide/UV process, in which OH-radicals are the reactive species, an increase in the THM concentration was measured after application of this process with short irradiation times. The maximum value of the THM-FP was 20% higher than the initial THM-FP. After an irradiation time of 1,050 min and a hydrogen peroxide consumption of 5.6 mg/l, the THM-FP and AOX-FP decreased to 75 and 71% of the initial formation potential, respectively. There was no selective removal of DBP precursors because the DOC concentration decreased also to 75% of the initial DOC-concentration after 1,050 min of irradiation.     

Photocatalytic oxidation of DBP precursors using UV with suspended and fixed TiO2

French River water (Nova Scotia, Canada) was separated into six different natural organic matter (NOM) fractions, including hydrophobic acids, bases and neutrals and hydrophilic acids, bases and neutrals. The raw water, as well as each of the NOM fractions were analysed for disinfection by-product (DBP) formation potential before and after advanced oxidation with UV/TiO₂ to determine the efficacy of this treatment for the removal of DBP precursors. The UV/TiO₂ treatment was carried out with a nanostructured thin film (NSTF), coated with TiO₂ which is compared with the use of a TiO₂ suspension. For the raw river water, removals of total trihalomethane formation potential (TTHMFP) and total haloacetic acid formation potential (THAA₉FP) were found to be approximately 20% and 90%, respectively, with 50 mJ/cm² UV exposure and 1 mg/L TiO₂. For the fractionated samples, approximately 75% of both trihalomethane (THM) and haloacetic acid (HAA) precursors were found to be associated with the hydrophobic acid fraction. For this individual fraction the same UV/TiO₂ treatments exhibited approximately 20-25% removal of both TTHMFP and THAA₉FP, suggesting that the fractionation process may have affected the treatability of HAA precursors or may have altered the results of the oxidation processes.     

Disinfection byproduct formation in reverse-osmosis concentrated and lyophilized natural organic matter from a drinking water source

Drinking water treatment and disinfection byproduct (DBP) research can be complicated by natural organic matter (NOM) temporal variability. NOM preservation by lyophilization (freeze-drying) has been long practiced to address this issue; however, its applicability for drinking water research has been limited because the selected NOM sources are atypical of most drinking water sources. The purpose of this research was to demonstrate that reconstituted NOM from a lyophilized reverse-osmosis (RO) concentrate of a typical drinking water source closely represents DBP formation in the original NOM. A preliminary experiment assessed DBP formation kinetics and yields in concentrated NOM, which demonstrated that chlorine decays faster in concentrate, in some cases leading to altered DBP speciation. Potential changes in NOM reactivity caused by lyophilization were evaluated by chlorination of lyophilized and reconstituted NOM, its parent RO concentrate, and the source water. Bromide lost during RO concentration was replaced by adding potassium bromide prior to chlorination. Although total measured DBP formation tended to decrease slightly and unidentified halogenated organic formation tended to increase slightly as a result of RO concentration, the changes associated with lyophilization were minor. In lyophilized NOM reconstituted back to source water TOC levels and then chlorinated, the concentrations of 19 of 21 measured DBPs, constituting 96% of the total identified DBP mass, were statistically indistinguishable from those in the chlorinated source water. Furthermore, the concentrations of 16 of 21 DBPs in lyophilized NOM reconstituted back to the RO concentrate TOC levels, constituting 86% DBP mass, were statistically indistinguishable from those in the RO concentrate. This study suggests that lyophilization can be used to preserve concentrated NOM without substantially altering the precursors to DBP formation.     

Effects of pre-ozonation on the removal of THM precursors by coagulation

Pre-ozonation in combination with enhanced coagulation was used to remove NOM from lake water as to control the formation of disinfection by-products, DBPs. The effect of the hydrophobicity/hydrophilicity nature of NOM on the performance of the combined pre-ozonation and coagulation process was studied. The hydrophilicity/hydrophobicity property of NOM was characterized in terms of mass distribution of the phydrophilic and the hydrophobilic fractions of NOM. The optimal condition for the combined pre-ozonation-coagulation was established: pH = ca. 9.0 and ozone dose = 0.45 mg-O₃/mg-DOC. Under the optimal condition, it was able to achieve ∼ 60% of THMFP removal. In terms of THMPF, results also indicated that the distribution between the hydrophilic and the hydrophobic fractions of NOM was 57.3 and 98.7 µg-THMFP/mg-DOC, respectively. Ozonation alters the structures and characteristics of NOM thereby affecting the coagulation effectiveness. Pre-ozonation was effective in removing the hydrophobic NOM, with a decrease of THMFP by ∼ 20% versus ∼ 10% for the hydrophilic fraction. The dosage of coagulant also governed DOC removal. The removal of hydrophobic and hydrophilic NOM were in the range of 27-41 and 2.5-22.7%, respectively at alum dosage of 0.41-1.65 (in Al/DOC) and 0.41-1.65 (in Al/DOC) and ozone dose of 0.58-2.93, mg/mg respectively. The adsorption characteristics of the hydrophilic and the hydrophobic fractions of NOM on aluminum hydroxide (from coagulant alum) were studied. Results indicated that the modified Langmuir isotherm of competitive adsorption was able to describe the adsorption of NOM onto hydrous aluminum hydroxide formed during alum coagulation of the lake waters.     

A pilot plant evaluation of the Magnetic Ion EXchange® process for the removal of dissolved organic carbon at Draycote water treatment works

Natural organic matter (NOM) in water sources is undesirable for customers because it reacts with chlorine to form trihalomethanes (THMs), which can be harmful to health, and other organochlorine compounds that can cause taste complaints. A new Magnetic Ion EXchange process (MIEX^® DOC) has been reported as being successful in removing NOM from raw water. The aim of this research was (a) to evaluate the performance of the MIEX^® process in removing NOM from hard, lowland water on a pilot plant scale and (b) to compare the performance of the MIEX^® process with low pH coagulation DAF, in particular, with respect to reducing THM levels. A 45 and 40% reduction in the amount of NOM and in the levels of THMs, respectively, in chlorine‐dosed water was achieved when the MIEX^® process was used with dissolved air flotation (DAF).     

A comparison of pilot-scale photocatalysis and enhanced coagulation for disinfection byproduct mitigation

This study evaluated pilot-scale photocatalysis and enhanced coagulation for their ability to remove or destroy disinfection byproduct (DBP) precursors, trihalomethane (THM) formation potential (FP), and THMs in two Arizona surface waters. Limited photocatalysis (<5 kWh/m³) achieved reductions in most of the DBP precursor parameters (e.g., DOC, UV₂₅₄, and bromide) but led to increased chlorine demand and THMFP. In contrast, enhanced coagulation achieved reductions in the DBP precursors and THMFP. Extended photocatalysis (<320 kWh/m³) decreased THMFP once the energy consumption exceeded 20 kWh/m³. The photocatalytic energy requirements for THM destruction were considerably lower (EEO = 20-60 kWh/m³) than when focusing on precursor destruction and THMFP. However, rechlorination increased the total THM (TTHM) concentration well beyond the raw value, thereby negating the energy benefits of this application. Enhanced coagulation achieved consistent 20-30% removals of preformed THMs. Outstanding issues need to be addressed before TiO₂ photocatalysis is considered feasible for DBP mitigation; traditional strategies, including enhanced coagulation, may be more appropriate.     

Improving on SUVA 254 using fluorescence-PARAFAC analysis and asymmetric flow-field flow fractionation for assessing disinfection byproduct formation and control

Several challenges with disinfection byproduct (DBP) control stem from the complexity and diversity of dissolved organic matter (DOM), which is ubiquitous in natural waters and reacts with disinfectants to form DBPs. Fluorescence parallel factor (PARAFAC) analysis and asymmetric flow-field flow fractionation (AF4) were used in combination with free chlorine DBP formation potential (DBPFP) tests to study the physicochemical DOM properties and DBP formation in raw- and alum-coagulated waters. Enhanced coagulation with alum became more effective at removing DBP-precursors as the pH decreased from 8 to 6. AF4-UV₂₅₄ fractograms indicated enhanced coagulation at pH 6 preferentially removed larger DOM, whereas no preferential size removal occurred at pH 8. Fluorescence-PARAFAC analysis revealed the presence of one protein-like and three humic-like fluorophore groups; stronger linear correlations were found between chloroform and the maximum intensity (F_MAX) of a humic-like fluorophore (r² = 0.84) than with SUVA₂₅₄ (r² = 0.51). This result indicated that the fluorescence-PARAFAC approach used here was an improvement on SUVA₂₅₄, i.e., fluorescence-based measurements were stronger predictors of chloroform formation.     

饮用水氯消毒生成DBPs的影响因素及其控制工艺

阐述了饮用水消毒副产物(DBPs)产生的影响因素,分析了天然有机物(NOM)、温度、pH、接触时间、氯用量和余氯浓度等各种因素对产生DBPs种类和数量的影响,提出了控制DBPs应从去除其前体物NOM,改变消毒工艺或采用新的消毒剂以及去除已生成的DBPs三方面入手.     

Disinfection by-products formation and precursors transformation during chlorination and chloramination of highly-polluted source water: Significance of ammonia

Many studies have demonstrated the different trends of disinfection by-products (DBPs) formation between chlorination and chloramination. However, the reactions between precursors and disinfectants are widely assumed to be “black box” and the reasons for abovementioned difference are not well illustrated. This study focused on source water with high levels of natural organic matter (NOM) and bromide, and compared the transformation of NOM specific characteristics and the ratios of specific DBPs as an equivalent of chlorine to total organic halogen (TOX) among three disinfection scenarios of chlorination, chloramination and chlorine–chloramine sequential treatment (Cl₂–NH₂Cl process). A three-reaction-phrases model was proposed thereafter to illustrate the major reactions involved in, i.e., stage-I: rapid consumption of fast reactive sites (DOC₁), which transformed to slow reactive sites (DOC₂) and measured DBPs, i.e., trihalomethanes, haloacetic acids, etc; stage-II: oxidation and/or halogenation of DOC₂ into unknown TOX (UTOX) intermediates; stage-III: oxidation of UTOX intermediates into measured DBPs. The effect of ammonia was also quantified. Ammonia is observed to inhibit the formation of measured DBPs by 68–92%, 94–99%, and 92–95% of that in chlorination in Stage-I, II, and III, respectively, and the formation of UTOX is reduced by 2–80%, 60–94%, and 82–93% accordingly. These effects lead to the steady accumulation of DBPs intermediates such as UTOX, and to the elevated UTOX/TOX during chloramination and Cl₂–NH₂Cl process thereafter. The results illustrate the mechanism of ammonia participating in DBPs formation, and are valuable to fill in the gap between the transformation of precursors and the formation of different DBPs.     

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.     

The effects of combined ozonation and filtration on disinfection by-product formation

The effects of combined ozonation and membrane filtration on the removal of the natural organic matter (NOM) and the formation of disinfection by-products (DBPs) were investigated. Ozonation/filtration resulted in a reduction of up to 50% in the dissolved organic carbon (DOC) concentration. Furthermore, humic substances were converted to non-humic substances, with changes in the humic and non-humic substance concentrations of up to −50% and +20%, respectively. Ozonation/filtration resulted in the formation of partially oxidized compounds from NOM that were less reactive with chlorine, decreasing the concentration of simulated distribution system total trihalomethanes (SDS TTHMs) and simulated distribution system halo acetic acids (SDS HAAs) by up to 80% and 65%, respectively. Reducing the molecular weight cut-off (MWCO) of the membranes resulted in reductions in the concentrations of SDS TTHMs and SDS HAAs. Using a membrane with a 5 kD MWCO, the minimum gaseous ozone concentration required to bring about effective NOM degradation and meet regulatory requirements for chlorinated DBPs was 2.5 g/m³.     

Bioanalytical and chemical assessment of the disinfection by-product formation potential: Role of organic matter

Disinfection by-products (DBP) formed from natural organic matter and disinfectants like chlorine and chloramine may cause adverse health effects. Here, we evaluate how the quantity and quality of natural organic matter and other precursors influence the formation of DBPs during chlorination and chloramination using a comprehensive approach including chemical analysis of regulated and emerging DBPs, total organic halogen quantification, organic matter characterisation and bioanalytical tools. In vitro bioassays allow us to assess the hazard potential of DBPs early in the chain of cellular events, when the DBPs react with their molecular target(s) and activate stress response and defence mechanisms. Given the reactive properties of known DBPs, a suite of bioassays targeting reactive modes of toxic action including genotoxicity and sensitive early warning endpoints such as protein damage and oxidative stress were evaluated in addition to cytotoxicity. Coagulated surface water was collected from three different drinking water treatment plants, along with reverse osmosis permeate from a desalination plant, and DBP formation potential was assessed after chlorination and chloramination. While effects were low or below the limit of detection before disinfection, the observed effects and DBP levels increased after disinfection and were generally higher after chlorination than after chloramination, indicating that chlorination forms higher concentrations of DBPs or more potent DBPs in the studied waters. Bacterial cytotoxicity, assessed using the bioluminescence inhibition assay, and induction of the oxidative stress response were the most sensitive endpoints, followed by genotoxicity. Source waters with higher dissolved organic carbon levels induced increased DBP formation and caused greater effects in the endpoints related to DNA damage repair, glutathione conjugation/protein damage and the Nrf2 oxidative stress response pathway after disinfection. Fractionation studies indicated that all molecular weight fractions of organic carbon contributed to the DBP formation potential, with the humic rich fractions forming the greatest amount of DBPs, while the low molecular weight fractions formed more brominated DBPs due to the high bromide to organic carbon ratio. The presence of higher bromide concentrations also led to a higher fraction of brominated DBPs as well as proportionally higher effects. This study demonstrates how a suite of analytical and bioanalytical tools can be used to effectively characterise the precursors and formation potential of DBPs.     

Natural organic matter and DBP formation potential in Alaskan water supplies

Disinfection by-products (DBP) are formed when natural organic matter (NOM) in water reacts with a disinfectant, usually chlorine. DBPs are a health risk element and regulated under the Safe Drinking Water Act. A study was conducted to evaluate the characteristics of NOM that contribute to DBPs in 17 different drinking water systems in Alaska. In order to determine the nature of the organic matter contributing to DBPs, DBP formation potential was compared with standard water quality parameters such as UV-254, color and dissolved organic carbon (DOC), as well as pyrolysis-gas chromatography/mass spectrometry (GC/MS). Results showed strong correlations between UV-254 and DBP formation potential for all waters studied. DOC, on the other hand, was less strongly correlated to DBP formation potential. Unlike previous studies, the total trihalomethane and haloacetic acid formation potentials were equal on a mass concentration basis for the waters studied. Pyrolysis-GC/MS indicated that NOM contributing to DBPs were primarily phenolic compounds. This finding was consistent with previous studies; however, unlike other studies, no correlation was found between aliphatic compounds in the raw waters and DBP formation potential.     

Identification of potential nitrogenous organic precursors for C-, N-DBPs and characterization of their DBPs formation

Nitrosamines are a class of emerging disinfection by-products (DBPs), which are mainly formed when water is treated by chloramination. Nitrosamines are highly carcinogenic and are hence a major concern for drinking water supplies. Although dissolved organic nitrogen (DON) compounds such as dimethylamine (DMA) have been recognized as important precursors of nitrosamines, many of them have not been identified, especially those used in consumer products. In this study, nine representative nitrogenous organic compounds with different DON characteristics and structures were selected to react with free chlorine, chlorine dioxide and monochloramine, respectively, for their DBP formation characteristics (nitrosamines, trihalomethanes (THMs) and haloacetic acids (HAAs)). It was found that in addition to DMA, benzyldimethyltetradecylamine (benzalkonium chloride, BKC) and 3-(N,N-dimethyloctyl-ammonio)propanesulfonate (3-N,N-DAPSIS) inner salt were potent precursors for carbonated DBPs (C-DBPs) and nitrogenated DBPs (N-DBPs). The DBP formation potential (DBPFP) tests showed that 1 mM of BKC formed more than 2 × 10⁵ ng/L of N-nitrosodimethylamine (NDMA) when treated with monochloramine and high levels of C-DBPs (2713 ± 145 μg/L of THMs and 356 ± 5 μg/L of HAAs) when treated with chlorine. 3-N,N-DAPSIS was a less potent DBP precursor: 1 mM of 3-N,N-DAPSIS generated 1155 ± 7 ng/L of NDMA, 1351 ± 66 μg/L of THMs and 188 ± 1 μg/L of HAAs. DMA, 3-N,N-DAPSIS and BKC were examined for their DBPFPs at various pH and temperatures to determine the impact of pH and reaction temperature on DBP yields and their formation mechanisms. The results showed that DBP yields apparently increased with rising temperature. However, no consistent correlations were observed between DBPs yields and pH. Bromide shifted the DBP species into brominated DBPs, and this phenomenon was more apparent when BKC was treated with chloramine.     

Differential vs. absolute UV absorbance approaches in studying NOM reactivity in DBPs formation: Comparison and applicability

Differential absorbance at wavelengths near 272 nm (−ΔA₂₇₂) has been used to track the halogenation of NOM, but its performance for different drinking water sources before and after water treatment processes has not been thoroughly ascertained. In this study, the behavior of −ΔA₂₇₂ during the halogenation process was determined to be strongly correlated with DBPs' concentrations regardless of the NOM properties. However, chlorination of different NOM samples resulted in different patterns when DBP concentrations were plotted vs. −ΔA₂₇₂. In order to quantify the reactivity of NOM in DBPs formation an alternative index, denoted as −ΔA₂₇₂(t = 2 h), that is the differential absorbance at 272 nm obtained at 2 h of reaction time and pH 7.0, was proposed. This parameter was strongly correlated with DBPs' concentrations regardless of the major chlorination conditions (chlorine dose, water temperature) and NOM properties (raw, treated and fractionated samples). Its performance was found better than that of other widely used surrogate parameters (i.e. DOC, SUVA₂₅₄, A₂₅₄, A₂₇₂) and it presents several options for field applications.     

臭氧/高锰酸盐复合预氧化控制氯化消毒副产物前质

研究了高锰酸盐与臭氧单独或复合预氧化对消毒副产物前质--三卤甲烷生成势（THMFP）和卤乙酸生成势（HAAFP）的去除效果.试验结果表明,高锰酸盐单独预氧化对消毒副产物前质的去除率可达20%以上,而臭氧预氧化的去除率仅约为10%.复合氧化比单一氧化更能有效去除消毒副产物前质,但受投加方式的影响,在试验务件下,以两种氧化剂同时投加的效果为最佳.复合氧化去除消毒副产物前质的机理包括：高锰酸盐与臭氧的协同氧化作用、锰的中间态产物对臭氧的催化作用以及高锰酸盐的强化混凝作用.     

Optimization of Coagulation and Ozonation Processes for Disinfection by–Products Formation Potential Reduction

Optimization of coagulation and ozonation processes for removal of disinfection by–products (DBP) formation potential in raw water was conducted by a pilot scale system. Proper poly–aluminum–chloride–sulfates (PACS), pre–ozone and post–ozone dosages are required for improving the removal performance of DBP formation potential to guarantee the safety of drinking water. Considering the treatment performances and economic costs, the optimum PACS, pre–ozone and post–ozone dosages for treating raw water with high organic concentration should be around 8.9 mg/L Al₂O₃, 0.5 and 2.5 mg/L, respectively. The combined drinking water treatment system of pre–ozonation, coagulation/sedimentation, sand filtration, post–ozonation, granular activated carbon filtration and disinfection is a promising process to reduce DBP formation potential from raw water in southern China. Under the optimum conditions, this combined system removed total trihalomethanes and haloacetic acids formation potential 50.16 and 69.10%, respectively.     

Formation of carbonaceous and nitrogenous disinfection by-products from the chlorination of Microcystis aeruginosa

Formation of carbonaceous disinfection by-products (C-DBPs), including trihalomethanes (THMs), haloacetic acids (HAAs), haloketones (HKs), chloral hydrate (CH), and nitrogenous disinfection by-products (N-DBPs), including haloacetonitriles (HANs) and trichloronitromethane (TCNM) from chlorination of Microcystis aeruginosa, a blue-green algae, under different conditions was investigated. Factors evaluated include contact time, chlorine dosages, pH, temperature, ammonia concentrations and algae growth stages. Increased reaction time, chlorine dosage and temperature improved the formation of the relatively stable C-DBPs (e.g., THM, HAA, and CH) and TCNM. Formation of dichloroacetonitrile (DCAN) followed an increasing and then decreasing pattern with prolonged reaction time and increased chlorine dosages. pH affected DBP formation differently, with THM increasing, HKs decreasing, and other DBPs having maximum concentrations at certain pH values. The addition of ammonia significantly reduced the formation of most DBPs, but TCNM formation was not affected and 1,1-dichloropropanone (1,1-DCP) formation was higher with the addition of ammonia. Most DBPs increased as the growth period of algal cells increased. Chlorination of algal cells of higher organic nitrogen content generated higher concentrations of N-DBPs (e.g., HANs and TCNM) and CH, comparable DCAA concentration but much lower concentrations of other C-DBPs (e.g., THM, TCAA and HKs) than did natural organic matter (NOM).