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This study investigated the effects of ferrate and ozone pre-oxidation on disinfection byproduct (DBP) formation from subsequent chlorination or chloramination. Two natural waters were treated at bench-scale under various scenarios (chlorine, chloramine, each with ferrate pre-oxidation, and each with pre-ozonation). The formation of brominated and iodinated DBPs in fortified natural waters was assessed. Results indicated ferrate and ozone pre-oxidation were comparable at molar equivalent doses for most DBPs. A net decrease in trihalomethanes (including iodinated forms), haloacetic acids (HAAs), dihaloacetonitrile, total organic chlorine, and total organic iodine was found with both pre-oxidants as compared to chlorination only. An increase in chloropicrin and minor changes in total organic bromine yield were caused by both pre-oxidants compared to chlorination only. However, ozone led to higher haloketone and chloropicrin formation potentials than ferrate. The relative performance of ferrate versus ozone for DBP precursor removal was affected by water quality (e.g., nature of organic matter and bromide concentration) and oxidant dose, and varied by DBP species. Ferrate and ozone pre-oxidation also decreased DBP formation from chloramination under most conditions. However, some increases in THM and dihaloacetonitrile formation potentials were observed at elevated bromide levels.

Halobenzoquinones (HBQs) are emerging disinfection by-products (DBPs) that are postulated drivers of bladder carcinogenicity. Prior assessments of 2,6-dichloro-1,4-benzoquinone (DCBQ) occurrence in drinking water distribution systems have revealed a gradual decline with increasing distance from points of entry. While this signals a degradation pathway, there is limited quantitative data on rate of that degradation. A systematic evaluation of DCBQ hydrolysis was performed, resulting in a rate law that is first order in both hydroxide [OH−] and [DCBQ]. The impact of temperature on that rate was characterized according to the Arrhenius relationship. Under the conditions tested (pH~7.2, T = 20°C) chloramine did not significantly impact DCBQ concentrations. However, DCBQ was rapidly degraded in solutions containing free available chlorine (FAC). Kinetic analysis showed non-integer order with respect to FAC. Further investigation led to a model that invoked reaction with dichlorine monoxide (Cl2O) as well as FAC.

The formation and occurrence of haloacetonitriles (HANs) in drinking water is of increasing concern because recent data have shown that they are the major contributors to DBP-associated toxicity of disinfected waters. Earlier research on HAN formation had established free amino acids as important HAN precursors due to their high reactivity with chlorine. However, free amino acids are unlikely to be the primary precursors for HANs in natural waters, mainly because the actual concentrations of these compounds are too low to sufficiently account for observed HAN formation. On the other hand, combined amino acids (i.e., peptides and proteins) are of much higher abundance even though it is unclear if they can contribute to HAN formation given that nearly all the amino nitrogen is tied up in peptide linkages. In order to clarify the reactivity of combined amino acids with chlorine to form HANs, dichloroacetonitrile (DCAN) formation kinetics was compared between free aspartic acid and two aspartyl-containing tetrapeptides (i.e., Asp-Asp-Asp-Asp and Arg-Gly-Asp-Ser). Results indicated that aspartyl residue could also lead to DCAN formation upon chlorination, whereas the rate of DCAN formation was much slower compared to that from free aspartic acid chlorination. Moreover, DCAN formation from the two model peptides was catalyzed by high pH. This is because chlorine-induced peptide backbone degradation is the key to DCAN formation from the chlorination of combined amino acids and this slow stepwise process is base-catalyzed. Perhaps most importantly, regardless of the precursors, DCAN was continuously formed but simultaneously degraded especially at alkaline pHs, leaving the corresponding N-chloro-2,2-dichloroacetamide (N-Cl-DCAM) and dichloroacetic acid (DCAA) as major end products. It was observed that over increasing chlorine exposure, there exists an important transition from initial organic precursors through metastable chlorination intermediates (e.g., DCAN and N-Cl-DCAM) and finally to stable end products (e.g., DCAA). By weighting DBP concentrations by their respective cytotoxic potencies, it is estimated that the aggregate cytotoxicity of chlorinated water would reach its maximum at relatively short chlorine contact times. In general, shorter water age and lower pH both resulted in higher levels of metastable intermediates (i.e., DCAN) and thus higher levels of aggregate calculated cytotoxicity. The resulting toxicity profile is different from the prevailing notion that supports current DBP regulations. Therefore, there is a risk that by placing regulatory limits and control strategies exclusively on regulated end products (e.g., HAAs), the overall toxicity of drinking water might be inadvertently elevated.

Haloacetamides (HAMs) are a class of newly identified nitrogenous disinfection byproducts (N-DBPs) whose occurrence in drinking waters has recently been reported in several DBP surveys. As the most prominent HAM species, it is commonly acknowledged that 2,2-dichloroacetamide (DCAM) is mainly generated from dichloroacetonitrile (DCAN) hydrolysis because the concentrations of these two compounds are often well correlated. Instead of DCAM, a previously unreported N-DBP, N-chloro-2,2-dichloroacetamide (N-Cl-DCAM), was confirmed in this study as the actual DCAN degradation product in chlorinated drinking waters. It is suspected that N-Cl-DCAM has been erroneously identified as DCAM, because its nitrogen-bound chlorine is readily reduced by most commonly used quenching agents. This hypothesis is supported by kinetic studies that indicate almost instantaneous N-chlorination of DCAM even at low chlorine residuals. Therefore, it is unlikely that DCAM can persist as a long-lived DCAN decomposition product in systems using free chlorine as a residual disinfectant. Instead, chlorination of DCAM will lead to the formation of an equal amount of N-Cl-DCAM by forming a hydrogen bond between hypochlorite oxygen and amino hydrogen. Alternatively, N-Cl-DCAM can be produced directly from DCAN chlorination via nucleophilic addition of hypochlorite on the nitrile carbon. Due to its relatively low pKa value, N-Cl-DCAM tends to deprotonate under typical drinking water pH conditions, and the anionic form of N-Cl-DCAM was found to be very stable in the absence of chlorine. N-Cl-DCAM can, however, undergo acid-catalyzed decomposition to form the corresponding dichloroacetic acid (DCAA) when chlorine is present, although those acidic conditions that favor N-Cl-DCAM degradation are generally atypical for finished drinking waters. For these reasons, N-Cl-DCAM is predicted to have very long half-lives in most distribution systems that use free chlorine. Furthermore, an analytical method using ultra performance liquid chromatography (UPLC)/negative electrospray ionization (ESI-)/quadrupole time-of-flight mass spectrometry (qTOF) was developed for the detection of a family of seven N-chloro-haloacetamides (N-Cl-HAMs). Combined with solid phase extraction (SPE), the occurrence of N-Cl-DCAM and its two brominated analogues (i.e., N-chloro-2,2-bromochloroacetamide and N-chloro-2,2-dibromoacetamide) was quantitatively determined for the first time in 11 real tap water samples. The discovery of N-Cl-DCAM or, more broadly speaking, N-Cl-HAMs in chlorinated drinking waters is of significance because they are organic chloramines, a family of compounds that is perceived to be more toxicologically potent than halonitriles (e.g., DCAN) and haloamides (e.g., DCAM), and therefore they may pose greater risks to drinking water consumers given their widespread occurrence and high stability.

Lignin is the most abundant aromatic plant component in terrestrial ecosystems. This study was conducted to determine the contribution of lignin residues in natural water to the formation of disinfection byproducts (DBPs) in drinking water. We investigated the formation of different classes of DBPs from lignin model compounds, lignin polymers, and humic substances using two common disinfection techniques, chlorination and chloramination. The contributions of lignin to the overall formation of DBPs from these organic products were determined based on the observed abundances of individual lignin phenols and their DBP yields. Model lignin phenols generally produced higher trichloroacetic acid (TCAA) yields than chloroform and dichloroacetic acid (DCAA) during chlorination. Lignin phenols generally produced higher DBP yields but lower percentages of unknown total organic halogen compared to bulk humic substances and lignin polymers. The relative significance of lignin phenols as chlorination DBP precursors generally follows the order of TCAA > DCAA&chloroform. The relative significance of lignin phenols to DBP formation by chloramination follows the order: TCAA > DCAA&DCAN > chloroform. Overall, lignin phenols are more important as TCAA precursors than as chloroform and DCAA precursors.

This paper demonstrates that disinfection byproducts (DBP) concentration profiles in heated water were quite different from the DBP concentrations in the cold tap water. Chloroform concentrations in the heated water remained constant or even decreased slightly with increasing distribution system water age. The amount of dichloroacetic acid (DCAA) was much higher in the heated water than in the cold water; however, the maximum levels in heated water with different distribution system water ages did not differ substantially. The levels of trichloroacetic acid (TCAA) in the heated water were similar to the TCAA levels in the tap water, and a slight reduction was observed after the tap water was heated for 24 h. Regardless of water age, significant reductions of nonregulated DBPs were observed after the tap water was heated for 24 h. For tap water with lower water ages, there were significant increases in dichloroacetonitrile (DCAN), chloropicrin (CP), and 1,1-dichloropropane (1,1-DCP) after a short period of heating. Heating of the tap water with low pH led to a more significant increase of chloroform and a more significant short-term increase of DCAN. High pH accelerated the loss of the nonregulated DBPs in the heated water. The results indicated that as the chlorine doses increased, levels of chloroform and DCAA in the heated water increased significantly. However, for TCAA, the thermally induced increase in concentration was only notable for the chlorinated water with very high chlorine dose. Finally, heating may lead to higher DBP concentrations in chlorinated water with lower distribution system temperatures.

The objective of this study was to quantitatively evaluate the effect of pre-ozonation on the formation and speciation of disinfection byproducts (DBPs) from subsequent chlorination and chloramination. Laboratory experiments were conducted on six diverse natural waters with low to medium bromide concentrations. Four groups of DBPs were investigated in this study: trihalomethanes (THMs), trihaloacetic acids (THAAs), dihaloacetic acids (DHAAs), and dihaloacetonitriles (DHANs). The results showed that the relative destructions of chlorination DBP precursors by ozone generally follow the order of DHANs > THMs & THAAs > DHAAs. Pre-ozonation substantially increased the DHAA precursors in the waters with low specific ultraviolet absorbance values. Pre-ozonation shifted the formation of DBPs to more brominated species. The bromine substitution factors (BSF) of different chlorination DBPs typically increased by 1-8 percentage points after ozonation. Pre-ozonation reduced the yields of chloramination DHAAs and THMs and increased the BSFs of chloramination DHAAs by 1-6 percentage points.

The analysis of total organic halogen (TOX) in drinking water indicates that a substantial amount of the halogenated compounds cannot be accounted for by known specific disinfection by-products (DBPs). The primary aim of this research was to characterize the hydrophobicity and molecular size distribution of the unknown halogenated DBPs using XAD resins and ultrafiltration membranes. The impact of membrane rejection on the size analysis of unknown TOX was also investigated using chlorinated fulvic acid. Six finished waters from different locations and treatment processes were collected and fractionated into various hydrophobicity and molecular size groups. The results showed that most unknown TOX was in the size range between 0.5 kDa and 10 kDa, but it could have a wide spectrum of hydrophobicities. Simple ultrafiltration was not always reliable as a characterization tool, as it was shown to reject a significant fraction of DBPs with molecular weight (MW) lower than the membrane cutoffs. Flushing with deionized water was effective in removing these low MW compounds from the ultrafiltration cell. A significant reduction in the apparent size of unknown TOX resulted when low MW DBPs were flushed out of the cell (comparing with classic parallel ultrafiltration). Coagulation of fulvic acid also significantly reduced the apparent size of unknown TOX formed by chlorine.

Haloacetonitriles (HANs) are an important class of drinking water disinfection byproducts (DBPs) that are reactive and can undergo considerable transformation on time scales relevant to system distribution (i.e., from a few hours to a week or more). The stability of seven mono-, di-, and trihaloacetonitriles was examined under a variety of conditions including different pH levels and disinfectant doses that are typical of drinking water distribution systems. Results indicated that hydroxide, hypochlorite, and their protonated forms could react with HANs via nucleophilic attack on the nitrile carbon, forming the corresponding haloacetamides (HAMs) and haloacetic acids (HAAs) as major reaction intermediates and end products. Other stable intermediate products, such as the N-chloro-haloacetamides (N-chloro-HAMs), may form during the course of HAN chlorination. A scheme of pathways for the HAN reactions was proposed, and the rate constants for individual reactions were estimated. Under slightly basic conditions, hydroxide and hypochlorite are primary reactants and their associated second-order reaction rate constants were estimated to be 6 to 9 orders of magnitude higher than those of their protonated conjugates (i.e., neutral water and hypochlorous acid), which are much weaker but more predominant nucleophiles at neutral and acidic pHs. Developed using the estimated reaction rate constants, the linear free energy relationships (LFERs) summarized the nucleophilic nature of HAN reactions and demonstrated an activating effect of the electron withdrawing halogens on nitrile reactivity, leading to decreasing HAN stability with increasing degree of halogenation of the substituents, while subsequent shift from chlorine to bromine atoms has a contrary stabilizing effect on HANs. The chemical kinetic model together with the reaction rate constants that were determined in this work can be used for quantitative predictions of HAN concentrations depending on pH and free chlorine contact times (CTs), which can be applied as an informative tool by drinking water treatment and system management engineers to better control these emerging nitrogenous DBPs, and can also be significant in making regulatory decisions.

Two natural waters were fortified with various levels of bromide or iodide ions (0-30 microM) and chlorinated in the laboratory to study the impact of bromide and iodide ions on the formation and speciation of disinfection byproducts. Trihalomethanes (THMs), haloacetic acids (HAAs), total organic halogen (TOX), and its halogen-specific fractions total organic chlorine (TOCl), bromine (TOBr), and iodine (TOI), were measured in this work. The molar yields of THMs and HAAs increased as the initial bromide concentration increased. No significant change in TOX concentration was found for varying bromide concentrations. However, TOX concentrations decreased substantially with increasing initial iodide concentrations. At higher levels of bromide, there was a decreasing level of unknown TOX and unknown TOCl but an increasing level of unknown TOBr. The extent of iodine substitution was much lower than that of bromine substitution when comparing identical initial concentrations because a substantial amount of iodide was oxidized to iodate by chlorine. The tendency toward iodate formation resulted in the unusual situation where higher chlorine doses actually caused reduced levels of iodinated organic byproducts. Quantitative assessment of the results of this study showed a good agreement with kinetic data in the literature.

Natural organic matter (NOM) is the major precursor to the formation of disinfection byproducts (DBPs) during drinking water treatment. Specific ultraviolet absorbance (SUVA) is a widely used surrogate parameter to characterize NOM and predict its DBP formation potential. The objective of this study was to determine the relationships between SUVA and different classes of DBPs formed by NOM fractions from different sources. Three natural waters with a wide SUVA range were fractionated into differing hydrophobicity and molecular weight groups using XAD-4 and XAD-8 resins and ultrafiltration membranes. Each NOM fraction was treated with chlorine and monochloramine under controlled laboratory conditions. Different classes of DBPs showed different relationships with SUVA. SUVA correlated strongly with trihaloacetic acids (THAAs) and unknown total organic halogen (UTOX) yields whereas weak correlations were observed between SUVA and trihalomethane (THM) and dihaloacetic acid (DHAA) yields during chlorination. These results reinforce the hypothesis that DHAAs and THAAs form through different precursors and reaction pathways. Strong correlation between SUVA and UTOX was also observed during chloramination. However, no significant relationship was observed between SUVA and chloramination THMs and DHAAs. Overall, SUVA is a good indicator for the formation of unknown DBPs. This indicates that UV absorbing compounds and aromatic carbon within NOM are the primary sources of precursors for unknown DBPs.

The quality of water entering a distribution system may differ substantially from the quality at the point of exposure to the consumer. This study investigated temporal variations in the levels of regulated and non-regulated disinfection byproducts (DBPs) in cold and hot tap water in a home on a medium-sized municipal water system. In addition, samples were collected directly from the water plant with some being held in accordance with a simulated distribution system (SDS) test protocol. The location for this work was a system in western Massachusetts, USA that uses free chlorine as a final disinfectant. Very little short term variability of DBPs at the point of entry (POE) was observed. The concentration of DBPs in the time-variable SDS test was similar to concentrations in the cold water tap. For most DBPs, the concentrations continued to increase as the cold water tap sample was held for the time-variable SDS incubation period. However, the impact of heating on DBP levels was compound specific. For example, the concentrations of trihalomethanes (THMs), dichloroacetic acid (DCAA) and chloropicrin (CP) were substantially higher in the hot water tap than in the cold water time-variable SDS samples. In contrast, the concentration of trichloroacetic acid (TCAA) was lower in the heated hot tap water, but about equal to that observed in the cold tap water. The situation was more pronounced for dichloroacetonitrile (DCAN), bromodichloroacetic acid (BDCAA), bromochloroacetic acid (BCAA) and 1,1,1-trichloropropanone (TCP), which all showed lower concentrations in the hot water then in either of the cold water samples (instantaneous or time-variable SDS). The latter was viewed as a clear indication of thermally-induced decomposition. The ratio of unknown total organic halide (UTOX) to TOX was substantially lower in the hot tap water as the THM to TOX ratio became correspondingly larger. The results of this study show that DBP exposure in the home is not well represented by concentrations measured in cold water taps where most compliance monitoring is done.

Dichloroacetonitrile (DCAN) is an important example of a reactive disinfection by-product for which a large body of occurrence data exists. Although it is known to undergo base-catalysed hydrolysis, DCAN9s peculiar dependence on reaction time, chlorine dose and pH has never been fully reconciled with expectations based on its presumed precursor (i.e. amino acid residues). The purpose of this research was to improve existing models for DCAN degradation and to use this information for interpretation of DCAN concentration profiles. Laboratory studies were performed using buffered solutions of DCAN, natural organic matter (NOM) and treated drinking waters, both with and without free residual chlorine. DCAN concentrations were measured as a function of reaction time. Results indicate a decomposition scheme encompassing three pathways of hydrolysis: attack by hydroxide, hypochlorite and water. Any one of the three pathways may predominate in drinking water systems, depending on the pH and chlorine residual. The resulting chemical kinetic model was used to show that the DCAN formed (and subsequently decomposed) was often many times the actual measured DCAN concentration. DCAN formation was found to agree with expectations based on the underlying chemistry of chlorine attack on proteinaceous material.

A general framework for modeling the bulk chlorine decay that accommodates effects of pH, temperature in water distribution system and in-home heating profiles is developed. With a single set of readily interpreted parameters, and various fictive concentrations of reactive constituents in the water, chlorine decay for the different water systems could be simultaneously modeled. Differential Evolution is employed to estimate the parameters stochastically. By using Bayesian Information Criterion, it is shown that a model consisting of two reactive species is preferred over models that consist of one or three reactive species. The flexibility and power of the framework is demonstrated with a case study of both types of effects.

The formation of halogenated solvent artifacts was investigated in common analytical solvents exposed to free chlorine, chloramines, and free bromine. Three brominated solvent artifacts [3-bromo-3-methyl-2-butanol (BMB), 1-bromo-2-methyl-2-propanol, and bromoacetone] were identified by gas chromatographyjmass spectrometry in methyl tert-butyl ether or pentane exposed to free bromine. These same three compounds have been previously reported as new disinfection byproducts in ozonated waters high in bromide. A number of chlorinated artifacts, which were reported as novel chloramination byproducts in another previous study, were also identified in diethyl ether exposed to free chlorine and chloramines

Bromine substitution factor (BSF) was used to quantify the effects of disinfectant dose, reaction time, pH, and temperature on the bromine substitution of disinfection byproducts (DBPs) during chlorination and chloramination. The BSF is defined as the ratio of the bromine incorporated into a given class of DBPs to the total concentration of chlorine and bromine in that class. Four classes of DBPs were evaluated: trihalomethanes (THMs), dihaloacetonitriles (DHANs), dihaloacetic acids (DHAAs) and trihaloacetic acids (THAAs). The results showed that the BSFs of the four classes of DBPs generally decreased with increasing reaction time and temperature during chlorination at neutral pH. The BSFs peaked at a low chlorine dose (1 mg/L) and decreased when the chlorine dose further increased. The BSFs of chlorination DBPs at neutral pH are in the order of DHAN > THM & DHAA > THAA. DHAAs formed by chloramines exhibited distinctly different bromine substitution patterns compared to chlorination DHAAs. Brominated DBP formation was generally less affected by the pH change compared to chlorinated DBP formation.

A simple gas chromatographic method was developed for the determination of cyanogen chloride and cyanogen bromide in drinking waters. Saturated headspace is injected directly onto a capillary column and the analytes are quantified by electron capture detection. Method detection limits are 0.04 and 0.2 μg/l for CNCl and CNBr, respectively. Effects of temperature and salt addition on analyte response were investigated. Other tests were conducted to determine the effects of sulfite and free chlorine on analyte stability. A concluding set of experiments showed the relationship between bromide concentration and cyanogen halide speciation.

Ten aquatic humic and fulvic acids were isolated and studied with respect to their reaction with chlorine. Yields of TOX, chloroform, trichloroacetic acid, dichloroacetic acid, dichloroacetonitrile, and 1,1,1-trichloropropanone were measured at pH 7 and 12. Humic acids produced higher concentrations than their corresponding fulvic acids of all byproducts except 1,1,1-trichloropropanone. Chlorine consumption and byproduct formation were related to fundamental chemical characteristics of the humic materials. A statistical model was proposed for activated aromatic content based on {sup 13}C NMR and base titration data. The values estimated from this model were found to be well correlated with chlorine consumption. Specific by-product formation was related to UV absorbance, nitrogen content, or the activated aromatic content.

Concentration profiles of combined residual chlorine (CRC) are measured in a small stream just below a municipal wastewater outfall. Loss of CRC is found to be due primarily to volatilization. Vertical and longitudinal concentration profiles are successfully modeled with a 2‐dimensional diffusive transport model, not incorporating a stagnant film. To calibrate this model, a Henry's Law constant for CRC is determined in the laboratory. The model proves superior in the case studied to the classical two‐film model for the prediction of depth‐integrated combined residual chlorine. The diffusive transport model is nearly identical to the two‐film model under conditions of imposed gas‐phase limitation. However, the two‐film theory predicts liquid‐phase limitation for the data in this study, and as a result, significant differences exist between the two sets of model predictions. Field data clearly indicates gas‐phase limitation, which was predicted by the 2‐dimensional diffusive transport model.

The objective of the research described in this article was to partially bridge the gap between formation potentials in model systems, e.g., humic substances, and by-product concentrations likely to be encountered in finished waters. The chlorination by-products chosen for study were trihalomethanes, total organic halide, trichloroacetic acid, dichloroacetic acid, trichloroacetone, and dichloroacetonitrile. By-product formation from colored raw waters was found to be similar to that observed for aquatic humic and fulvic acids. Alum coagulation of a moderately colored surface water resulted in the removal of 50-90 percent of all by-product precursors tested. Almost from the first report of trihalomethanes (THMs) in finished drinking water, the presence of this group of compounds has been attributed to reactions between chlorine and humic materials.1-2 Support for this hypothesis comes from observed similarities in the rates of THM formation (e.g., Stevens et al3) and yields for natural waters and isolated aquatic humic substances. The fact that humic substances are the major organic components of colored waters45 is another strong argument in support of this idea. Humic materials have similarly been linked to the formation of total organic halide (TOX) in drinking waters.68

Total organic halide (TOX) analyzers are commonly used to measure the amount of dissolved halogenated organic byproducts in disinfected waters. Because of the lack of information on the identity of disinfection byproducts, rigorous testing of the dissolved organic halide (DOX) procedure for method bias is not always possible. This note presents the results of a brief study comparing two commercial TOX analyzers with neutron activation. The purpose was to determine if differential bias exists between the two analyzers, and to determine analyte recovery of adsorbed disinfection byproducts. Disinfection byproducts of aquatic fulvic acid were prepared using the following disinfectants: chlorine, bromine, and monochloramine. Analysis of these samples indicated that the two commercial TOX analyzers gave similar results. Neutron activation analysis suggested that organic chlorine recovery from the activated carbon adsorbent was complete, however results with organic bromine recovery were inconclusive. A...

Natural organic matter (NOM) from five water sources was fractionated using XAD resins and ultrafiltration membranes into different groups based on hydrophobicity and molecular weight (MW), respectively. The disinfection byproduct formation from each fraction during chlorination and chloramination was studied. In tests using chlorination, hydrophobic and high MW (e.g., >0.5 kDa) precursors produced more unknown total organic halogen (UTOX) than corresponding hydrophilic and low MW (e.g.

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.

The objective of this research was to determine the optimum total organic halogen (TOX) protocol for use with ion chromatographic (IC) detection to analyze total organic chlorine (TOCl), bromine (TOBr), and iodine (TOI) in drinking water simultaneously. Two commercial analyzers (one using a pure O2 carrier and one using O2/CO2 mixture) and three commercially available activated carbons (two coconut-based and one bituminous coal-based) were examined in this study. Results showed that the pyrolytic analyzer using pure O2 and off-line IC combined with a standard TOX carbon (coconut-based) achieved the most complete recovery of TOCl, TOBr and TOI for both model compounds and real samples. There was no obvious difference between the two analyzers when used in microcoulometric detection mode. The TOX method is moderately sensitive to nitrate rinse volume. The monohaloacetic acids were partly washed out during sample preparation. This problem was solved by a modified nitrate rinsing solution.