Comparison of the disinfection by-product formation potential of treated waters exposed to chlorine and monochloramine

The formation of disinfection by-products (DBPs) from chlorination and monochloramination of treated drinking waters was determined. Samples were collected after treatment at 11 water treatment works but before exposure to chlorine or monochloramine. Formation potential tests were carried out to determine the DBPs formed by chlorination and monochloramination. DBPs measured were trihalomethanes (THMs), haloacetic acids (HAAs), halonitromethanes (HNMs), haloacetonitriles (HANs), haloaldehydes (HAs), haloketones (HKs) and iodo-THMs (i-THMs). All waters had the potential to form significant levels of all the DBPs measured. Compared to chlorine, monochloramination generally resulted in lower concentrations of DBPs with the exception of 1,1-dichloropropanone. The concentrations of THMs correlated well with the HAAs formed. The impact of bromine on the speciation of the DBPs was determined. The literature findings that higher bromide levels lead to higher concentrations of brominated DBPS were confirmed.     

A comparison of the role of two blue-green algae in THM and HAA formation

The contribution of two blue-green algae species, Anabaena flos-aquae and Microcystis aeruginosa, to the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) was investigated. The experiments examined the formation potential of these disinfection by-products (DBPs) from both algae cells and extracellular organic matter (EOM) during four algal growth phases. Algal cells and EOM of Anabaena and Microcystis exhibited a high potential for DBP formation. Yields of total THMs (TTHM) and total HAAs (THAA) were closely related to the growth phase. Reactivity of EOM from Anabaena was slightly higher than corresponding cells, while the opposite result was found for Microcystis. Specific DBP yields (yield/unit C) of Anabaena were in the range of 2-11 μmol/mmol C for TTHM and 2-17 μmol/mmol C for THAA, while those of Microcystis were slightly higher. With regard to the distributions of individual THM and HAA compounds, differences were observed between the algae species and also between cells and EOM. The presence of bromide shifted the dominant compounds from HAAs to THMs.     

Controversies about the occurrence of chloral hydrate in drinking water

Besides trihalomethanes (THMs) and haloacetic acids (HAAs), chloral hydrate (CH) is the next most prevalent disinfection by-product (DBP) in drinking water, formed as a result of the reaction between chlorine and natural organic matter (NOM). Chloral hydrate (trichloroacetaldehyde) should be limited in drinking water because of its adverse health effect. The controversies concerning the appearance of CH in disinfected water found in literature are discussed in the present paper. According to some authors the CH yield during chlorination of water depends only on TOC. However, there are other data available that do not confirm this relationship. Another fact requiring clarification is the dependence of CH formation on pH. In the present study, CH formation is analysed in different types of water disinfected with different doses of chlorine. Formation of CH is correlated with the dose of Cl₂ and the contact time. The formation of chloral hydrate takes place as long as chlorine is available in the water. Total organic carbon (TOC) is not considered the main factor influencing the production of chloral hydrate in water treated with Cl₂ as the production depends also on the nature of NOM. Higher levels of CH are observed at alkaline conditions (pH > 7). A significant correlation (R² > 0.9) between the concentrations of chloral hydrate and chloroform has been observed. The preozonation increases significantly the chloral hydrate formation potential in the water treated. Biofiltration process does not remove all of CH precursors and its efficiency depends strongly on the contact time. Chloral hydrate was analyzed by gas chromatography with electron capture detector with the detection limit 0.1 μg L⁻¹.     

Disinfection and formation of disinfection by-products in a photoelectrocatalytic system

In this study, disinfection and formation of disinfection by-products (DBPs) were studied in a photoelectrocatalytic (PEC) treatment system. Disinfection performance of titanium dioxide (TiO₂) in the PEC system was determined through Escherichia coli (E. coli) inactivation. Humic acid (HA) was used as a model organic compound and its removal was monitored by total organic carbon (TOC) measurements using 410 nm (color) and 254 nm (UV₂₅₄) wavelengths. Trihalomethanes (THMs) were measured for the evaluation of DBPs formation during PEC treatment of chloride and HA mixture. It was found that unlike photocatalytic treatment, THMs might form in the PEC system. To investigate the effects of anions on the PEC treatment, chloride (Cl⁻), sulfate (SO₄²⁻), phosphoric acid (H₂PO₄⁻)/hydrogen phosphate (HPO₄²⁻) and bicarbonate (HCO₃⁻) ions were added separately to the HA and bacterial suspensions. Presence of H₂PO₄⁻/HPO₄²⁻ and HCO₃⁻ ions resulted in inhibitory effects on both HA degradation and E. coli inactivation, which were also examined in the photoanode. It was observed that the presence of HA had a strong inhibitory effect on the disinfection of E. coli.     

Disinfection by-products from halogenation of aqueous solutions of terpenoids

We report the formation of trihalomethanes and other disinfection by-products from four polyfunctional terpenoids during simulated chlorination of natural waters. Complex suites of products were identified by closed loop stripping analysis (CLSA)/gas chromatography-mass spectrometry (GC-MS) from halogenation of β-carotene and retinol. β-Ionone appeared to be a key intermediate in the halogenation of β-carotene and retinol, reacting further under the reaction conditions to produce trans-β-ionone-5,6-epoxide and β-cyclocitral. Halogenation of the four terpenoids also produced trihalomethanes (THMs), most likely through haloform reaction on methyl ketone groups within many of the intermediates. Since halogenation of retinol produced a significant quantity of THMs at a slow reaction rate, retinol-based structures may possibly contribute to the slow reacting phase of THM formation in natural waters. Two polyhydroxyphenol model compounds were halogenated for comparison. The only products identified by CLSA/GC-MS from halogenation of 4′,5,7-trihydroxyflavanone and ellagic acid were THMs. 4′,5,7-Trihydroxyflavanone rapidly produced THMs, with an extremely high molar yield (94%) at pH 7. Terpenoids of the β-ionone and retinol type should be considered to be significant THM precursors, while 4′,5,7-trihydroxyflavanone has been shown to be an extremely significant THM precursor, potentially present within natural organic matter in water treatment processes and distribution systems.     

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.     

Oxidative elimination of cyanotoxins: comparison of ozone, chlorine, chlorine dioxide and permanganate

As the World Health Organization (WHO) progresses with provisional Drinking Water Guidelines of 1 microg/L for microcystin-LR and a proposed Guideline of 1 microg/L for cylindrospermopsin, efficient treatment strategies are needed to prevent cyanotoxins such as these from reaching consumers. A kinetic database has been compiled for the oxidative treatment of three cyanotoxins: microcystin-LR (MC-LR), cylindrospermopsin (CYN), and anatoxin-a (ANTX) with ozone, chlorine, chlorine dioxide and permanganate. This kinetic database contains rate constants not previously reported and determined in the present work (e.g. for permanganate oxidation of ANTX and chlorine dioxide oxidation of CYN and ANTX), together with previously published rate constants for the remaining oxidation processes. Second-order rate constants measured in pure aqueous solutions of these toxins could be used in a kinetic model to predict the toxin oxidation efficiency of ozone, chlorine, chlorine dioxide and permanganate when applied to natural waters. Oxidants were applied to water from a eutrophic Swiss lake (Lake Greifensee) in static-dose testing and dynamic time-resolved experiments to confirm predictions from the kinetic database, and to investigate the effects of a natural matrix on toxin oxidation and by-product formation. Overall, permanganate can effectively oxidize ANTX and MC-LR, while chlorine will oxidize CYN and MC-LR and ozone is capable of oxidizing all three toxins with the highest rate. The formation of trihalomethanes (THMs) in the treated water may be a restriction to the application of sufficiently high-chlorine doses.     

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.     

Formation of disinfection by-products after pre-oxidation with chlorine dioxide or ferrate

The effect of pre-oxidation with chlorine dioxide (ClO₂) or ferrate (Fe(VI)) on the formation of disinfection by-products (DBPs) during chlorination or chloramination was tested with natural waters from 12 sources (9 surface waters, 1 groundwater, and 2 wastewater effluents). DBPs investigated included trihalomethanes (THM), chloral hydrate (CH), haloketones (HK), haloacetonitriles (HAN) and trichloronitromethane (TCNM), chlorite and chlorate. Chlorite and chlorate were found in the ClO₂-treated waters. Application of 1 mg/L ClO₂ ahead of chlorination reduced the formation potential for THM by up to 45% and the formation of HK, HAN and TCNM in most of the samples. The CH formation results were mixed. The formation of CH and HK was enhanced with low doses of Fe(VI) (1 mg/L as Fe), but was greatly reduced at higher doses (20 mg/L Fe). Fe(VI) reduced the formation of THM, HAN and TCNM in most of the samples. Reduced potential for the formation of NDMA was observed in most of the samples after both ClO₂ and Fe(VI) pre-oxidation.     

Rapid free chlorine decay in the presence of Cu(OH)2: chemistry and practical implications

A rapid reaction between free chlorine and the cupric hydroxide [Cu(OH)₂] solids commonly found on pipe walls in premise plumbing can convert free chlorine to chloride and rapidly age Cu(OH)₂ to tenorite (CuO). This reaction has important practical implications for maintaining free chlorine residuals in premise plumbing, commissioning of new copper pipe systems, and maintaining low levels of copper in potable water. The reaction stoichiometry between chlorine and Cu(OH)₂ is consistent with formation of CuO through a metastable Cu(III) intermediate, although definitive mechanistic understanding requires future research. Natural levels of silica in water (0-30 mg/L), orthophosphate, and higher pH interfere with the rate of this reaction.     

A comprehensive bulk chlorine decay model for simulating residuals in water distribution systems

Chlorine decay models provide efficient ways to develop disinfection strategies for water distribution systems, provided they account separately for bulk and wall decay, and accurately describe decay with a single set of coefficients. The augmented two-reactant (2RA) model is shown to be the simplest model to accurately describe effects of rechlorination dose/timing on bulk chlorine decay, in combination with effects of initial concentration and temperature over long periods. The two-reactant (2R) and variable reaction-coefficient (VRC) models provided predictions of comparable accuracy under higher and successive rechlorination doses at constant temperature. However, the 2RA model provides a more general basis for strategy development, as the VRC model cannot describe the effect of temperature variation. The minimal data-set required for 2RA calibration was similar for all cases considered. The 2RA model is readily applied by incorporation into system modelling software such as the multi-species extension (MSX) to EPANET software.     

Ozonation of drinking water: part II. Disinfection and by-product formation in presence of bromide,iodide or chlorine

Ozone is an excellent disinfectant and can even be used to inactivate microorganisms such as protozoa which are very resistant to conventional disinfectants. Proper rate constants for the inactivation of microorganisms are only available for six species (E. coli, Bacillus subtilis spores, Rotavirus, Giardia lamblia cysts, Giardia muris cysts, Cryptosporidium parvum oocysts). The apparent activation energy for the inactivation of bacteria is in the same order as most chemical reactions (35-50 kJ mol(-1)), whereas it is much higher for the inactivation of protozoa (80 kJ mol(-1)). This requires significantly higher ozone exposures at low temperatures to get a similar inactivation for protozoa. Even for the inactivation of resistant microorganisms, OH radicals only play a minor role. Numerous organic and inorganic ozonation disinfection/oxidation by-products have been identified. The by-product of main concern is bromate, which is formed in bromide-containing waters. A low drinking water standard of 10 microg l(-1) has been set for bromate. Therefore, disinfection and oxidation processes have to be evaluated to fulfil these criteria. In certain cases, when bromide concentrations are above about 50 microg l(-1), it may be necessary to use control measures to lower bromate formation (lowering of pH, ammonia addition). Iodate is the main by-product formed during ozonation of iodide-containing waters. The reactions involved are direct ozone oxidations. Iodate is considered non-problematic because it is transformed back to iodide endogenically. Chloride cannot be oxidized during ozonation processes under drinking water conditions. Chlorate is only formed if a preoxidation by chlorine and/or chlorine dioxide has occurred.     

Inactivation of particle-associated microorganisms in wastewater disinfection: modeling of ozone and chlorine reactive diffusive transport in polydispersed suspensions

Occlusion of microorganisms in wastewater particles often governs the overall performance of a disinfection system, and the associated health risks of post-disinfected effluents. Little is currently known on the penetration of chemical oxidants into particles developed in wastewater treatment. In this work, a reactive transport model that incorporates intra- and extra-particle chemical decay, radial intra-particle diffusion, mass transfer resistance at particle surfaces, and non-linear reaction kinetics within a competitive multi-particle size aqueous environment, was used to analyze the penetration of ozone and chlorine into wastewater particles. Individual characteristics from two secondary wastewater treatment facilities were used in model calibration. Simulations revealed that significant ozone transport within particles greater than 6 microm required large initial concentrations to exhaust the preferential reaction with aqueous soluble matter. Chlorinated samples exhibited apparently slower reactions and thus deeper penetration (22-40 microm). Chlorine penetration was less sensitive to variations in the extra-particle reaction and disinfectant concentration than ozone. Model simulations that considered elevated initial concentrations of chemical disinfectants revealed that complete inactivation of all particle size domains was not possible with current disinfection practices (e.g., contact times). Reduction in the health risks associated with wastewater particles requires treatment that efficiently balances particle removal (filtration) and particle inactivation (disinfection).     

Disinfection by-product formation following chlorination of drinking water: Artificial neural network models and changes in speciation with treatment

Artificial neural network (ANN) models were developed to predict disinfection by-product (DBP) formation during municipal drinking water treatment using the Information Collection Rule Treatment Studies database complied by the United States Environmental Protection Agency. The formation of trihalomethanes (THMs), haloacetic acids (HAAs), and total organic halide (TOX) upon chlorination of untreated water, and after conventional treatment, granular activated carbon treatment, and nanofiltration were quantified using ANNs. Highly accurate predictions of DBP concentrations were possible using physically meaningful water quality parameters as ANN inputs including dissolved organic carbon (DOC) concentration, ultraviolet absorbance at 254 nm and one cm path length (UV₂₅₄), bromide ion concentration (Br⁻), chlorine dose, chlorination pH, contact time, and reaction temperature. This highlights the ability of ANNs to closely capture the highly complex and non-linear relationships underlying DBP formation. Accurate simulations suggest the potential use of ANNs for process control and optimization, comparison of treatment alternatives for DBP control prior to piloting, and even to reduce the number of experiments to evaluate water quality variations when operating conditions are changed. Changes in THM and HAA speciation and bromine substitution patterns following treatment are also discussed.     

Performance and biofilm activity of nitrifying biofilters removing trihalomethanes

Nitrifying biofilters seeded with three different mixed-culture sources removed trichloromethane (TCM) and dibromochloromethane (DBCM) with removals reaching 18% for TCM and 75% for DBCM. In addition, resuspended biofilm removed TCM, bromodichloromethane (BDCM), DBCM, and tribromomethane (TBM) in backwash batch kinetic tests, demonstrating that the biofilters contained organisms capable of biotransforming the four regulated trihalomethanes (THMs) commonly found in treated drinking water. Upon the initial and subsequent increased TCM addition, total ammonia nitrogen (TOTNH₃) removal decreased and then reestablished, indicating an adjustment by the biofilm bacteria. In addition, changes in DBCM removal indicated a change in activity related to DBCM. The backwash batch kinetic tests provided a useful tool to evaluate the biofilm’s bacteria. Based on these experiments, the biofilters contained bacteria with similar THM removal kinetics to those seen in previous batch kinetic experiments. Overall, performance or selection does not seem based specifically on nutrients, source water, or source cultures and most likely results from THM product toxicity, and the use of GAC media appeared to offer benefits over anthracite for biofilter stability and long-term performance, although the reasons for this advantage are not apparent based on research to date.     

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.     

A comparison of disinfection by-products found in chlorinated and chloraminated drinking waters in Scotland

Seven water treatment works were selected to compare disinfection by-products (DBPs) formed when using chlorination and chloramination. DBPs measured included trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), trihalonitromethane, iodinated THMs and nitrosamines. Generally treatment works that used chloramination were able to meet the European THM regulatory limit of 100 μg L⁻¹ whereas the chlorinated works found it significantly more difficult. There were no significant differences in the levels of nitrogenous DBPs between the treatment works using chlorination or chloramination with the exception of the nitrosamine N-nitrosodimethylamine (NDMA) which was present at one treatment works in one season.     

A new approximate solution for chlorine concentration decay in pipes

Biswas et al. (1993. A model for chlorine concentration decay in pipes. Water Res. 27(12), 1715-1724) presented an analytical solution of a two-dimensional (2-D) steady-state chlorine transport equation in a pipe under the turbulent condition and employed fractional error function and regression technique to develop an approximate solution. However, their approximate solution may not give a good result if the wall decay parameter is large. This paper provides a more accurate approximate solution of the 2-D steady-state chlorine transport equation under the turbulent condition. This new approximate solution has advantages of easy evaluation and good accuracy when compared with the approximate solution given by Biswas et al. (1993). In addition, this paper also develops a methodology that combines simulated annealing (SA) with this new approximate solution to determine the wall decay parameter. Two cases are chosen to demonstrate the application of the present approximate solution and methodology. The first case is to use this new approximate solution in simulating chlorine decay in pipes with the experiment-observed data given by Rossman (2006. The effect of advanced treatment on chlorine decay in metallic pipes. Water Res. 40(13), 2493-2502), while the second case presents the determination of the wall consumption at the end of the pipe network.     

The formation of halogen-specific TOX from chlorination and chloramination of natural organic matter isolates

The formation of disinfection by-products (DBPs) is a public health concern. An important way to evaluate the presence of DBPs is in terms of the total organic halogen (TOX), which can be further specified into total organic chlorine (TOCl), bromine (TOBr), and iodine (TOI). The formation and distribution of halogen-specific TOX during chlorination and chloramination of natural organic matter (NOM) isolates in the presence of bromide and iodide ions were studied. As expected, chloramination produced significantly less TOX than chlorination. TOCl was the dominant species formed in both chlorination and chloramination. TOI was always produced in chloramination, but not in chlorination when high chlorine dose was used, due to the limited presence of HOI in chlorination as a result of the oxidation of iodide to iodate in the presence of excess chlorine. The formation of TOI during chloramination increased as the initial iodide ion concentration increased, with a maximum of ∼60% of the initial iodide ion becoming incorporated into NOM. Iodine incorporation in NOM was consistently higher than bromine incorporation, demonstrating that the competitive reactions between bromine and iodine species in chloramination favoured the formation of HOI and thus TOI, rather than TOBr. Correlations between the aromatic character of the NOM isolates (SUVA₂₅₄ and % aromatic C) and the concentrations of overall TOX and halogen-specific TOX in chloramination were observed. This indicates that the aromatic moieties in NOM, as indicated by SUVA₂₅₄ and % aromatic C, play an important role in the formation of overall TOX and halogen-specific TOX in chloramination. THMs comprised only a fraction of TOX, up to 7% in chloramination and up to 47% in chlorination. Although chloramine produces less TOX than chlorine, it formed proportionally more non-THM DBPs than chlorine. These non-THM DBPs are mostly unknown, corresponding to unknown health risks. Considering the higher potential for formation of iodinated DBPs and unknown DBPs associated with the use of chloramine, water utilities need to carefully balance the risks and benefits of using chloramine as an alternative disinfectant to chlorine in order to satisfy guideline values for THMs.     

Effects of UV 254 irradiation on residual chlorine and DBPs in chlorination of model organic-N precursors in swimming pools

Ultraviolet (UV) irradiation is commonly applied as a secondary disinfection process in chlorinated pools. UV-based systems have been reported to yield improvements in swimming pool water and air chemistry, but to date these observations have been largely anecdotal. The objectives of this investigation were to evaluate the effects of UV irradiation on chlorination of important organic-N precursors in swimming pools.Creatinine, L-arginine, L-histidine, glycine, and urea, which comprise the majority of the organic-N in human sweat and urine, were selected as precursors for use in conducting batch experiments to examine the time-course behavior of several DBPs and residual chlorine, with and without UV₂₅₄ irradiation. In addition, water samples from two natatoria were subjected to monochromatic UV irradiation at wavelengths of 222 nm and 254 nm to evaluate changes of liquid-phase chemistry. UV₂₅₄ irradiation promoted formation and/or decay of several chlorinated N-DBPs and also increased the rate of free chlorine consumption. UV exposure resulted in loss of inorganic chloramines (e.g., NCl₃) from solution. Dichloromethylamine (CH₃NCl₂) formation from creatinine was promoted by UV exposure, when free chlorine was present in solution; however, when free chlorine was depleted, CH₃NCl₂ photodecay was observed. Dichoroacetonitrile (CNCHCl₂) formation (from L-histidine and L-arginine) was promoted by UV₂₅₄ irradiation, as long as free chlorine was present in solution. Likewise, UV exposure was observed to amplify cyanogen chloride (CNCl) formation from chlorination of L-histidine, L-arginine, and glycine, up to the point of free chlorine depletion. The results from experiments involving UV irradiation of chlorinated swimming pool water were qualitatively consistent with the results of model experiments involving UV/chlorination of precursors in terms of the behavior of residual chlorine and DBPs measured in this study.The results indicate that UV₂₅₄ irradiation promotes several reactions that are involved in the formation and/or destruction of chlorinated N-DBPs in pool settings. Enhancement of DBP formation was consistent with a mechanism whereby a rate-limiting step in DBP formation was promoted by UV exposure. Promotion of these reactions also resulted in increases of free chlorine consumption rates.