Chlorination of natural organic matter: kinetics of chlorination and of THM formation.

The kinetics of the formation of trihalomethanes (THMs) and of chlorine consumption for the chlorination of natural organic matter with an excess of chlorine (50 microM > [Cl2]o >210 microM) was investigated. THM precursors could be divided into a fast and a slowly reacting fraction. Long term chlorine demand and the formation of THM could be described by second order kinetics. Rate constants were between 0.01 and 0.03 M(-1) s(-1) in the pH range 7-9 for surface waters and humic materials extracted from surface waters. A groundwater gave a higher rate constant of 0.124 M(-1) s(-1). Resorcinol-type structures were tested with respect to kinetics and yield of THM formation. They could possibly be responsible for the fast reacting THM precursors. which represent 15-30% of the THM precursors of natural waters. Additional classes of compounds that might contribute to the initial THM formation include readily enolizable compounds such as beta-diketones and beta-ketoacids. Experiments with phenol showed that slowly reacting THM precursors may consist of phenolic compounds. The influence of pretreatments (UV/visible irradiation, ozone and chlorine dioxide) on chlorine demand and THM formation from NOM was also studied: UV/visible irradiation does not alter THM formation but leads to a higher chlorine demand. Preoxidation with ozone leads to a lower THM formation with an unaltered chlorine demand and preoxidation with chlorine dioxide reduces THM formation and the chlorine demand.     

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.     

Carbohydrates as trihalomethanes precursors. Influence of pH and the presence of Cl(-) and Br(-) on trihalomethane formation potential

Upon chlorination carbohydrates can give trihalomethanes (THMs). In the present work, we have studied the influence of pH, chloride or bromide concentration on the formation of THMs from carbohydrates. We have observed that THMs are not formed at acidic pH, while basic pH values only increase slightly the THM content, although the consumption of chlorine increases up to 100% with respect to pH 8. The presence of chloride in ppm increases the THM formation from carbohydrates without influence of the chlorine consumption. In the same manner, the presence of bromide ions in ppb also increases remarkably the THMs formed upon chlorination of saccharides. Even more, we have observed that at bromide concentrations below 100ppb, complete incorporation of bromide in THMs occurs. Overall, the results obtained show that saccharides widely present in natural waters can give rise to significant THM concentrations in the disinfection process by chlorine.     

Enhanced coagulation using a magnetic ion exchange resin

The objective of this investigation was to examine the effectiveness of a magnetic ion exchange resin (MIEX) to enhance the coagulation of disinfection by-product precursors in nine surface waters, each representing a different element of the USEPA's 3 x 3 enhanced coagulation matrix. The effect of MIEX-pretreatment on the requisite alum dose needed for subsequent coagulation of turbidity was also evaluated. Enhanced coagulation with MIEX was found to be very effective for removing trihalomethane (THM) and haloacetic acid (HAA) precursors from the nine waters examined. THM and HAA formation potential was reduced by more than 60% in all of the waters studied; reductions approaching 90% were seen in the waters with the highest specific ultraviolet absorbance values. The residual total organic carbon concentration, ultraviolet absorbance, and THM and HAA formation potential were all substantially lower as a result of MIEX and alum treatment compared to alum coagulation alone. MIEX pre-treatment also lowered the coagulant demand of each of the waters substantially.     

Spatial and temporal evolution of trihalomethanes in three water distribution systems

Spatial and seasonal changes in trihalomethane (THM) concentrations were investigated in three distribution systems of Quebec (Canada) which are supplied by different surface waters and which use a variety of physicochemical treatment strategies. The investigation was based on an intensive 25-week sampling programme, undertaken at a time of year when the temperature of southern Quebec surface waters exceeds 4 degrees C (April-November). THMs and other water quality and operational parameters were monitored at points along the distribution system--between the treatment plant and the system extremities--which represented variable residence times of water. Results showed that THM concentrations vary significantly (from 1.5 to 2 times, depending on the utility) between finished waters as they leave the plant and water at the system extremities. When water temperature exceeds 15 degrees C, spatial THM variations are particularly high (from 2 to 4 times, depending on the utility). The development of multivariate regression models showed that water temperature was a better predictor of THM seasonal variability than chlorine dose, surrogates of natural organic matter and pH. Also, initial THM formation (in finished waters leaving the plant) was a good predictor of THM levels at distribution system extremities.     

Effect of alum treatment on the trihalomethane formation and bacterial regrowth potential of natural and synthetic waters

Waters from five reservoirs and "synthetic waters", prepared using terrestrially derived dissolved organic matter (DOM) extracted from vegetation and reservoir catchment soils, were studied for their treatability with alum using a jar test procedure. DOM in drinking water is a precursor for the formation of trihalomethanes (THM) following chlorine disinfection and can also be a substrate for microbial growth in the drinking water distribution system. The trihalomethane formation potential (THMFP) represents an upper concentration limit on THMs formed by chlorination, while bacterial regrowth potential (BRP) is an indicator of the bioavailability of DOM. BRP and THMFP were measured before and after alum treatment and the results were related to the source of the DOM. It was found that freshly derived terrestrial DOM in synthetic water resulted in higher THMFP and BRP than DOM in reservoir waters. For the samples investigated, conventional alum treatment did not always reduce the THM precursor levels formed in laboratory tests below the NH&MRC (1996) guideline level of 250 microg/L nor produce microbially stable waters.     

Lake sediments as potential sources of trihalomethane precursors

Trihalomethanes (THMs) form when chlorine reacts with certain naturally-occurring organic molecules (THM precursors) during the disinfection of drinking water. THMs are believed to have significant carcinogenic and mutagenic properties. The elucidation of THM precursor sources is important because source management may lower costs and increase effectiveness of in-plant treatments. This study investigated the importance of lake and reservoir sediments as a THM precursor source.

Sediments collected from littoral and profundal areas of Lake Rockwell Reservoir (Portage County, Ohio) and from a nearby natural lake (East Twin Lake) were kept in the dark for 21 days at 20°C to estimate release rates of THM precursors. All sediments had significant THM precursor releases relative to non-sediment controls. Anaerobic conditions produced significantly less precursors than during an aerobic incubation. Littoral sediment precursor release rate (μg THMs/m²/day) was significantly greater than precursor release rates for lake and reservoir profundal sediments. The importance of sediment THM precursor release relative to other sources is discussed.     

Empirical rate equation for trihalomethane formation with chlorination of humic substances in water

Trihalomethane (THM) in drinking water is formed by chlorination of humic substances. In this study, the rates of THM formation in aqueous solution of humic acid were examined under various conditions. The following rate equation was obtained empirically. [THM] = k (pH − a)[TOC][Cl₂]₀^mtⁿ.

Here, [THM] is the concentration of total THM after t h, [TOC] and [Cl₂]₀ are the concentrations of total organic carbon and chlorine dose, k is the rate constant and a, m and n are parameters. The values of k, a, m and n for humic acid as reagent were obtained as 8.2 × 10⁻⁴ (l^mmg^−mh⁻ⁿ), 2.8, 0.25 and 0.36, respectively. The activation energy was obtained as 37 kJ mol⁻¹. Further, it was proved that the above equation could be applied to the rates of THM formation from precursors in actual river and lake waters.     

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.     

2. Comparison of the disinfection by-product formation potentials between a wastewater effluent and surface waters

In this study, the chemical reactivity with chlorine as measured by disinfection by-product formation potential (DBPFP) is compared among samples of a wastewater effluent and surface waters. Water samples that had higher anthropogenic impacts were found to have higher overall DBPFP due primarily to higher dissolve organic carbon (DOC) concentrations. Effluent-derived organic matter (EfOM), however, was found to be less reactive with chlorine on a per DOC concentration basis. Yet, EfOM had higher proportions of brominated DBP, which may be associated with greater health risks. In this research, pyrolysis-GC/MS was used to establish relationship between structural features of DOC and DBPFP. We show that there is a critical set of pyrolysis fragments that separates the waters based on the degree of anthropogenic influence. Even though no single chemical marker was found to be indicative of the formation potentials of different classes of DBP, combinations of chemical fragments were found to be associated with the formation potentials of total trihalomethane (THM), brominated THM, total haloacetic acid (HAA), and brominated HAA for this set of samples. In contrast to previous work, the phenolic signature of these samples was negatively correlated to DBPFP, whereas strong relationships were found between DBPFP and the organic nitrogen and halogenated signatures.     

A reactive species model for chlorine decay and THM formation under rechlorination conditions

Chlorine is typically used within drinking water distribution systems to maintain a disinfectant residual and minimize biological regrowth. Typical distribution system models describe the loss of disinfectant due to reactions within the water matrix as first order with respect to chlorine concentration, with the reactants in excess. Recent work, however, has investigated relatively simple dynamic models that include a second, hypothetical reactive species. This work extends these latter models to account for discontinuities associated with rechlorination events, such as those caused by booster chlorination and by mixing at distribution system junction nodes. Mathematical arguments show that the reactive species model will always represent chlorine decay better than, or as well as, a first-order model, under single dose or rechlorination conditions; this result is confirmed by experiments on five different natural waters, and is further shown that the reactive species model can be significantly better under some rechlorination conditions. Trihalomethane (THM) formation was also monitored, and results show that a linear relationship between total THM (TTHM) formation and chlorine demand is appropriate under both single dose and rechlorination conditions. This linear relationship was estimated using the modeled chlorine demand from a calibrated reactive species model, and using the measured chlorine demand, both of which adequately represented the TTHM formation.     

Trihalomethane formation by chlorination of ammonium- and bromide-containing groundwater in water supplies of Hanoi, Vietnam

The occurrence and the fate of trihalomethanes (THMs) in the water supply system of Hanoi City, Vietnam was investigated from 1998 to 2001. The chlorination efficiency, THM speciation, and, THM formation potential (THMFP) was determined in the water works and in tap water. With regard to THM formation, three types of groundwater resources were identified: (I) high bromide, (II) low bromide, and (III) high bromide combined with high ammonia and high dissolved organic carbon (DOC) concentrations. Under typical treatment conditions (total chlorine residual 0.5-0.8 mg/L), the total THM formation was always below WHO, EU, and USEPA drinking water standards and decreased in the order type I > type II > type III, although the THMFP was > 400 micrograms/L for type III water. The speciation showed > 80% of bromo-THMs in type I water due to the noticeable high bromide level (< or = 140 micrograms/L). In type II water, the bromo-THMs still accounted for some 40% although the bromide concentration is significantly lower (< or = 30 micrograms/L). In contrast, only traces of bromo-THMs were formed (approximately 5%) in type III water, despite bromide levels were high (< or = 240 micrograms/L). This observation could be explained by competition kinetics of chlorine reacting with ammonia and bromide. Based on chlorine exposure (CT) estimations, it was concluded that the current chlorination practice for type I and II waters is sufficient for > or = 2-log inactivation of Giardia lamblia cysts. However, in type III water the applied chlorine is masked as chloramine with a much lower disinfection efficiency. In addition to high levels of ammonia, type III groundwater is also contaminated by arsenic that is not satisfactory removed during treatment. N-nitrosodimethylamine, a potential carcinogen suspected to be formed during chloramination processes, was below the detection limit of 0.02 microgram/L in type III water.     

Multiple linear regression modeling of disinfection by-products formation in Istanbul drinking water reservoirs

Oxidation of raw water with chlorine results in formation of trihalomethanes (THM) and haloacetic acids (HAA). Factors affecting their concentrations have been found to be organic matter type and concentration, pH, temperature, chlorine dose, contact time and bromide concentration, but the mechanisms of their formation are still under investigation. Within this scope, chlorination experiments have been conducted with water reservoirs from Terkos, Buyukcekmece and Omerli lakes, Istanbul, with different water quality regarding bromide concentration and organic matter content. The factors studied were pH, contact time, chlorine dose, and specific ultraviolet absorbance (SUVA). The determination of disinfection by-products (DBP) was carried out by gas chromatography techniques. Statistical analysis of the results was focused on the development of multiple regression models for predicting the concentrations of total THM and total HAA based on the use of pH, contact time, chlorine dose, and SUVA. The developed models provided satisfactory estimations of the concentrations of the DBP and the model regression coefficients of THM and HAA are 0.88 and 0.61, respectively. Further, the Durbin-Watson values confirm the reliability of the two models. The results indicate that under these experimental conditions which indicate the variations of pH, chlorine dosages, contact time, and SUVA values, the formation of THM and HAA in water can be described by the multiple linear regression technique.     

Chlorine demand-based predictive modeling of THM formation in water distribution networks

The potential carcinogenicity of trihalomethanes (THMs) has led to increasingly stricter regulation of drinking water supplies. This has led to the need to manage better the chemical and microbiological risk balance in chlorinated supplies. The use of empirical equations to predict THM concentrations in water quality models is challenging and expensive due to the numerous temporally and spatially dependent uncertainties involved. In this paper, the benefits of a simple predictive method using a THM productivity parameter based on chlorine consumed by bulk free chlorine reactions are explored using extensive field data from a water distribution system in the Midlands region of the UK. It is concluded that the productivity parameter provides an appropriate, relatively robust, yet straightforward alternative to the use of an empirical equation based on regression analyses to predict THM concentrations in distribution, and that the method has the potential to help distribution system water quality model calibration.     

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.     

Disinfection by-products and their precursors in a water treatment plant in North China: Seasonal changes and fraction analysis

A one-year-long monitoring project was conducted to assay the concentrations of THMs, HAAs and their formation potential along the conventional process in a water treatment plant in North China. Subsequent investigations of organic matter fractionation and the contribution of the algae to the precursor were also conducted to trace the source of the DBPs. The results showed that the concentration of DBPs and their formation potential varied with the seasons. The highest concentrations of THMs and the highest HAAs formation potential, each almost 500 microg/L, were detected in autumn and the lowest were in spring, no more than 100 microg/L. Both organic matter and algae were found to be important DBP precursors. The hydrophobic acid fraction in dissolved organic matter has the highest formation potential for both THM and HAA. Algae contribute about 20% to 50% of the total formation potential during an algal bloom. The efficiency of each unit process for DBPs and precursors was also assayed. Unfortunately, the conventional drinking water treatment process is limited in its efficiency for precursor removal. The pre-chlorination and filtration process had a negative effect on DBP or precursor removal.     

Bench-scale testing of a magnetic ion exchange resin for removal of disinfection by-product precursors

The objective of this research was to compare enhanced coagulation with anion exchange for removal of disinfection by-product (DBP) precursors (i.e. natural organic matter (NOM) and bromide). Treatment with a magnetic ion exchange resin (MIEX((R))) was the primary focus of this study. Raw waters from four utilities in California were evaluated. The waters had low turbidity, low to moderate organic carbon concentrations, a wide range of alkalinities, and moderate to high bromide ion concentrations. The treated waters were compared based on removal of ultraviolet (UV) absorbance, dissolved organic carbon (DOC), trihalomethane formation potential (THMFP), and haloacetic acid formation potential (HAAFP). The results indicated that treatment with MIEX is more effective than coagulation at removing UV-absorbing substances and DOC. Treatment with MIEX and treatment with MIEX followed by coagulation yielded similar results, suggesting that coagulation of MIEX-treated water does not provide additional removal of organic carbon. MIEX treatment reduced the THMFP and HAAFP in all waters, and did so to a greater extent than coagulation. Treatment with MIEX was most effective in raw waters having a high specific UV absorbance and a low anionic strength. Following MIEX treatment, subsequent chlorination resulted in a shift to the more brominated THM and HAA species as compared to chlorination of the raw water. MIEX also removed bromide to varying degrees, depending on the raw water alkalinity and initial bromide ion concentration.     

Volatile halogenated hydrocarbons in Belgian drinking waters

A comparative study was carried out to determine levels of volatile halogenated hydrocarbons, especially trihalomethanes (THM) in different Belgian drinking waters, prepared from both ground and surface waters. In addition to examining raw and treated water leaving the production plants, changes in haloform concentration during transport in the distribution system were also studied. Only a slight decrease of haloform concentration after decompression in water towers and reservoirs occurred and was rapidly compensated by on going chlorination by residual free chlorine.Despite of the very different conditions used for chlorination in the plants studied, a fairly clear relation was found between total THM content in the finished waters and TOC-values of the raw waters, indicating that the primary organic load was the determining factor for haloform formation.     

Multi-route trihalomethane exposure in households using municipal tap water treated with chlorine or ozone-chlorine

In Korea, data for multi-route trihalomethane (THM) exposure in households using municipal tap water treated with ozone-chlorine or chlorine are unavailable or very limited. Accordingly, the present study was designed to obtain those data by measurements of the THM concentrations in the tap water and indoor and outdoor air in the two types of households, along with an estimation of THM exposure from water ingestion, showering, and the inhalation of indoor air. Chloroform was the most abundant THM in all three media, yet no bromoform was detected in any sample. Similar to previous findings, the winter chloroform concentration in tap water treated with chlorine (22.1 microg/l, median) was significantly higher than that in the tap water treated with ozone-chlorine (16.8 microg/l, median). However, the summer water chloroform concentrations and summer and winter water concentrations of the other two THMs (bromodichloromethane and dibromochloromethane) exhibited no significant difference between the chlorine and ozone-chlorine-treated water. It was suggested that the effects of the water parameters including biochemical oxygen demand of raw water entering water treatment plants should be considered when evaluating the advantage of ozone-chlorine disinfection for THM formation over chlorine disinfection. The indoor air THM concentration trend was also consistent with the water concentration trend. The indoor to outdoor air concentration ratios were comparable with previous studies. The THM exposure estimates from water ingestion, showering, and the inhalation of apartment indoor air when not in the shower suggested that, for residents living in the surveyed households, their exposure to THMs in the home was mostly associated with their household water uses. The THM exposure estimates from tap water ingestion were similar to those from showering.     

Trihalomethanes formation in point of use surface water disinfection with chlorine or chlorine dioxide tablets

In remote or underdeveloped areas, natural disaster emergencies and armed conflict zones, point‐of‐use surface water disinfection with chlorine tablets provides microbiologically safe water, but disinfection by‐products such as trihalomethanes (THMs) are formed. While the health risks from THMs are much less than the risks from consuming microbiologically unsafe water, it is nonetheless desirable to understand and minimise THM formation. We show that THM concentrations in surface water samples from the Northern British Isles disinfected with chlorine tablets increased with contact time, in some cases to significantly exceed EU, US EPA and WHO drinking water guidance values after more than an hour. More stagnant water from ponds and lochs had higher THM formation than river water. Doubling the chlorine tablet dose slightly enhanced THM formation, and passing water through coffee filter paper reduced it. Chlorine dioxide tablets produced minimal amounts of THMs.