Effect of permanganate oxidation and chlorination on the mutagenic activity and other quality parameters of artificially recharged ground water processed from humus-rich surface water

The effect of oxygen, chlorine, and potassium permanganate oxidation on the quality of drinking water processed from artificially recharged ground water was studied. Artificially recharged ground water contained only 45% of the organic material of the original lake water, but iron and manganese contents were high.Oxygen removed iron but not manganese. Potassium permanganate proved to be more effective than chlorine in removing manganese.The non-chlorinated waters were non-mutagenic but the level of the mutagenicity of all chlorinated artificially recharged ground waters were as high as in chlorinated drinking water processed from lake water. One exception was found, however. The mutagenicity of potassium permanganate oxidized, chlorinated, artificially recharged ground water was very low, only about 5% of the other waters.     

Influence of chlorination pH and chlorine dose on the formation of mutagenic activity and the strong bacterial mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-5(2H)-furanone (MX) in water

Samples from two Dutch raw water sources were chlorinated in the laboratory at different pH:s and chlorine doses, and were analysed for mutagenic activity and the mutagenic compound 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX). Chlorination produced mutagenic activity as well as MX in both waters. The formation of MX was favoured by acidic reaction conditions and high chlorine doses, but in waters treated with excess chlorine at pH 9, no MX was detected. The mutagenicity was approximately on the same level after chlorination of both water types but the MX concentration was significantly higher in the water containing mainly humic material.

MX was found to be quantitatively extracted from acidified waters by the XAD resin adsorption technique.     

Human pharmaceuticals, antioxidants, and plasticizers in wastewater treatment plant and water reclamation plant effluents.

The primary objective of this study was to determine the presence of unregulated organic chemicals in reclaimed water using complementary targeted and broad spectrum approaches. Eleven of 12 targeted human pharmaceuticals, antioxidants, and plasticizers, and 27 tentatively identified non-target organic chemicals, were present in secondary effluent entering tertiary treatment trains at a wastewater treatment plant and two water reclamation facilities. The removal of these compounds by three different tertiary treatment trains was investigated: coagulant-assisted granular media filtration (California Title-22 water, 22 CCR 60301-60357; Barclay [2006]), lime clarification/reverse osmosis (lime/ RO), and microfiltration-reverse osmosis (MF/RO). Carbamazepine, clofibric acid, gemfibrozil, ibuprofen, p-toluenesulfonamide, caffeine, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and N-butyl benzenesulfonamide (N-BBSA) were present at low to high nanogram-per-liter levels in Title 22 water. The lime/RO product waters contained lower concentrations of clofibric acid, ibuprofen, caffeine, BHA, and N-BBSA (<10 to 71 ng/L) than their Title 22 counterparts. The MF/RO treatment reduced concentrations to levels below their detection limits, although BHT was present in MF/RO product water from one facility. The presence of the target analytes in two surface waters used as raw drinking water sources and a recharged groundwater was also examined. Surface waters used as raw drinking water sources contained caffeine, BHA, BHT, and N-BBSA, while recharged groundwater contained BHT, BHA, and N-BBSA. Nontarget compounds in recharged groundwater appeared to be attenuated with increased residence time in the aquifer.     

Disinfection by-products in Finnish drinking waters

Disinfection by-products (DBPs) were measured in plant effluents of 35 Finnish waterworks, which utilized different treatment processes and raw water sources. DBPs were measured also from the distribution systems of three waterworks. Di- and trichloroacetic acids, and chloroform were the major DBPs found in treated water samples. The concentration of six haloacetic acids (HAA6) exceeded the concentrations of trihalomethanes (THMs). Chlorinated drinking waters (DWs) originating from surface waters contained the highest concentration of HAA6 and THMs: 108 and 26 microg/l, respectively. The lowest concentrations of DBPs were measured from ozonated and/or activated carbon filtrated and chloraminated DWs. Higher concentrations of HAA6, THMs, and adsorbable organic halogens were measured in summer compared to winter. The levels of chlorinated acetic acids, chloroform, and bromodichloromethane correlated positively with mutagenicity. Past mutagenicity levels of DWs were examined. A major reduction in the use of prechlorination, increased use of chloramine disinfection, and better removal of organic carbon were the most important reasons for the 69% decrease in mutagenicity from 1985 to 1994.     

The presence of bacterial virus in groundwater and treated drinking water

Ten raw urban well water samples and twelve water samples collected from distribution lines after the well waters were treated were examined for bacteriological and coliphage/bacteriophage populations. The raw well waters were found to contain <1/100 ml total coliforms and fecal streptococci, but they all contained varying concentrations of coliphage and bacteriophage. The treated waters were all found to have <1 total coliforms and fecal streptococci per 100 ml with the exception of one treated water sample from Community C. However, even though the treated water samples contained free and total chlorine levels varying from 0.05 to 1.5 ppm, they were all found to contain usually greater amounts of coliphage and bacteriophage than the raw well waters.     

Occurrence and formation of trihalomethanes in marine aquaria studied using solid-phase microextraction gas chromatography-mass spectrometry

The occurrence and formation of chlorinated and brominated trihalomethanes (THMs) were studied in artificial saltwater and natural seawater marine aquaria as well as in groundwater and surface waters. A new headspace solid-phase microextraction method was used, which included gas chromatography-mass spectrometry and provided method detection limits of less than 0.1 microg/L, with a signal-to-noise ratio of 3 to 5. The results showed that disinfection by using either chlorine or ozone caused a significant formation of THMs in situ. Speciation of the THMs was a strong function of the water matrix, with initial bromide concentrations playing a pivotal role. These results provide a tool for understanding and monitoring the formation of key disinfection byproducts in marine aquaria that may cause respiratory, eye irritation, or other health concerns.     

Molecular size distribution of natural organic matter in raw and drinking waters.

The purpose of this study was to compare the molecular size distribution (MSD) of natural organic matter (NOM) in raw waters (RW) and drinking waters (DW), and to find out the differences between MSD after different water treatment processes. The MSD of NOM of 34 RW and DW of Finnish waterworks were determined with high-performance size-exclusion chromatography (HPSEC). Six distinct fractions were generally separated from water samples with the TSK G3000SW column, using sodium acetate at pH 7 as an eluent. Large and intermediate humic fractions were the most dominant fractions in surface waters (lakes and rivers), while in artificially recharged groundwaters and natural groundwaters intermediate and small fractions predominated. Water treatment processes removed the two largest fractions almost completely shifting the MSD towards smaller molecular size in DW. Granular activated carbon (GAC) filtration, ozonation, and their combination reduced all humic fractions compared to the conventional treatment. Humic fractions correlated with total organic carbon (TOC) content and chemical oxygen demand, this being especially true in RW. The results demonstrate that the HPSEC method can be applied for a qualitative and also for rough estimate quantitative analyzes of NOM directly from RW and DW samples without sample pretreatment.     

Nano-silver in drinking water and drinking water sources: stability and influences on disinfection by-product formation

Nano-silver is increasingly used in consumer products from washing machines and refrigerators to devices marketed for the disinfection of drinking water or recreational water. The nano-silver in these products may be released, ending up in surface water bodies which may be used as drinking water sources. Little information is available about the stability of the nano-silver in sources of drinking water, its fate during drinking water disinfection processes, and its interaction with disinfection agents and disinfection by-products (DBPs). This study aims to investigate the stability of nano-silver in drinking water sources and in the finished drinking water when chlorine and chloramines are used for disinfection and to observe changes in the composition of DBPs formed when nano-silver is present in the source water. A dispersion of nano-silver particles (10 nm; PVP-coated) was used to spike untreated Ottawa River water, treated Ottawa River water, organic-free water, and a groundwater at concentrations of 5 mg/L. The diluted dispersions were kept under stirred and non-stirred conditions for up to 9 months and analyzed weekly using UV absorption to assess the stability of the nano-silver particles. In a separate experiment, Ottawa River water containing nano-silver particles (at 0.1 and 1 mg/L concentration, respectively) was disinfected by adding sodium hypochlorite (a chlorinating agent) in sufficient amounts to maintain a free chlorine residual of approximately 0.4 mg/L after 24 h. The disinfected drinking water was then quenched with ascorbic acid and analyzed for 34 neutral DBPs (trihalomethanes, haloacetonitriles, haloacetaldehydes, 1,1 dichloro-2-propanone, 1,1,1 trichloro-2-propanone, chloropicrin, and cyanogen chloride). The results were compared to the profile of DBPs obtained under the same conditions in the absence of nano-silver and in the presence of an equivalent concentration of Ag⁺ ions (as AgNO₃). The stability of the nano-silver dispersions in untreated Ottawa River water, with a dissolved organic carbon concentration of 6 mg/L, was significantly higher than the stability of the nano-silver dispersions in distilled, organic-free water. Nano-silver particles suspended in the groundwater agglomerated and were quickly and quantitatively removed from the solution. Our data confirm previous observations that natural dissolved organic matter stabilizes nano-silver particles, while the high-ionic strength of groundwater appears to favor their agglomeration and precipitation. As expected, nano-silver was not stable in Ottawa River water through the chlorination process, but survived for many days when added to the Ottawa River water after treatment with chlorine or chloramines. Stirring appeared to have minimal effect on nano-silver stability in untreated and treated Ottawa River water. The profile of DBPs formed in the presence of nAg differed significantly from the profile of DBPs formed in the absence of nAg only at the 1 mg/L nAg concentration. The differences observed consisted mainly in reduced formation of some brominated DBPs and a small increase in the formation of cyanogen chloride. The reduced formation of brominated congeners may be explained by the decrease in available bromide due to the presence of Ag⁺ ions. It should be noted that a concentration of 1 mg/L is significantly higher than nAg concentrations that would be expected to be present in surface waters, but these results could be significant for the disinfection of some wastewaters with comparably high nano-silver concentrations.     

Atrazine removal by ozonation processes in surface waters

Atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazinedyl-2,4-diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continuously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O3/H2O2 process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O3/H2O2 and O3/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.     

Powdered activated carbon coupled with enhanced coagulation for natural organic matter removal and disinfection by-product control: application in a Western Australian water treatment plant

The removal of organic precursors of disinfection by-products (DBPs), i.e. natural organic matter (NOM), prior to disinfection and distribution is considered as the most effective approach to minimise the formation of DBPs. This study investigated the impact of the addition of powdered activated carbon (PAC) to an enhanced coagulation treatment process at an existing water treatment plant on the efficiency of NOM removal, the disinfection behaviour of the treated water, and the water quality in the distribution system. This is the first comprehensive assessment of the efficacy of plant-scale application of PAC combined with enhanced coagulation on an Australian source water. As a result of the PAC addition, the removal of NOM improved by 70%, which led to a significant reduction (80-95%) in the formation of DBPs. The water quality in the distribution system also improved, indicated by lower concentrations of DBPs in the distribution system and better maintenance of disinfectant residual at the extremities of the distribution system. The efficacy of the PAC treatment for NOM removal was shown to be a function of the characteristics of the NOM and the quality of the source water, as well as the PAC dose. PAC treatment did not have the capacity to remove bromide ion, resulting in the formation of more brominated DBPs. Since brominated DBPs have been found to be more toxic than their chlorinated analogues, their preferential formation upon PAC addition must be considered, especially in source waters containing high concentrations of bromide.     

Atrazine removal by ozonation processes in surface waters

Abstract

Atrazine (6‐chloro‐N‐ethyl‐N'‐isopropyl‐1,3,5‐triazinedyl‐2,4‐diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O₃/H₂O₂ process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O₃/H₂O₂ and O₃/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.     

Occurrence and suitability of pharmaceuticals and personal care products as molecular markers for raw wastewater contamination in surface water and groundwater

This study aimed to provide the first and comprehensive data on the occurrence of 17 target pharmaceuticals and personal care products (PPCPs) in urban water environment in Singapore. Meanwhile, this study also verified the suitability of these PPCPs as specific markers of raw wastewater contamination in receiving water bodies in highly urbanized areas where both surface water and groundwater are not impacted by the discharge of treated wastewater effluents. Analytical results of wastewater showed that among 17 target PPCPs examined, only 5 PPCPs were detected in 100 % of raw wastewater samples, including acetaminophen (ACT), carbamazepine (CBZ), caffeine (CF), diethyltoluamide (DEET), and salicylic acid (SA). Similarly, these PPCPs were found in most surface water and groundwater. Interestingly, the three PPCPs (ACT, CBZ, and SA) were only detected in surface water and groundwater in the sampling sites close to relatively older sewer systems, while they were absent in background samples that were collected from the catchment with no known wastewater sources. This suggests that ACT, CBZ, and SA can be used as specific molecular markers of raw wastewater in surface water and groundwater. This study also confirmed that CF and DEET were not really associated with wastewater sources, thus cannot serve well as specific molecular markers of wastewater contamination in receiving water bodies. To the best knowledge of the authors, the use of ACT and SA as specific molecular markers of raw wastewater contamination in urban surface waters and groundwater was first reported. Further studies on the use of ACT, CBZ, and SA along with other chemical/microbial markers are recommended to identify and differentiate contamination sources of surface waters/groundwater.     

Comparison of drinking water mutagenicity with leaching of polycyclic aromatic hydrocarbons from water distribution pipes

The primary objectives of this study were to examine the changes in concentration of six polycyclic aromatic hydrocarbons (PAH) and the possibility of changes in mutagenic potential of treated waters as a result of their passage through commonly used distribution pipes. With the exception of the finished water taken at one treatment plant in which the total concentration of the six PAH was 138.5 parts per trillion (ppt), the total initial concentration in all other treated water ranged from 0 to 13.4 ppt. The corresponding total PAH concentration in water after passage through the distribution pipes varied from 0 to 61.6 ppt. This demonstrated that PAH concentration in water can increase as a result of their passage through coated distribution pipes. Mutagenic activity was also detected in many of the treated water samples, however, the levels of this activity did not correlate with either the transit of water through the distribution system or the levels of PAH in the water. There was some evidence to indicate that the water treatment process itself may have contributed to the mutagenicity observed in the finished water.     

Spatial and temporal distribution of the leaching of surface applied tracers from an irrigated monolith of a loamy vineyard soil

Fresh water scarcity is an increasing problem worldwide. Strategies to alleviate water scarcity include the use of low-quality water for irrigation. The risk of groundwater contamination by pollutants in this water is affected by soil heterogeneity and preferential flow. These risk factors can be assessed by measuring the spatio-temporal redistribution of uniformly applied water and solutes. We placed a soil monolith (height 29 cm) from an Australian vineyard on a 100-cell multi-compartment sampler (MCS). At this vineyard, treated wastewater is used in response to the severe shortage of water in the summer. We studied the leaching risk associated with heterogeneous or preferential flow by irrigating the soil column with 24 applications to simulate one year. We applied simulated rainfall as well as wastewater (which contained chloride) during summer while relying on rainfall only in winter. We compared the chloride leaching with the leaching of bromide, which was applied during one of the applications as a pulse. During the entire simulated year, leaching of solutes from the monolith was measured. The results indicate that the assumption of uniform flow would underestimate the risk for the fresh groundwater reserves: 25 % of the solutes are transported though 6 % of the soil’s cross-section. The spatial distribution of drainage and solute leaching varied little during the experiment. Consequently, the mass flux density pattern of the bromide pulse was comparable to that of the repeatedly applied chloride. However, the MCS data suggested lateral ‘escape’ from chloride to non-mobile areas, which means in the long run, considerable quantities of these solutes can build up in areas that do not receive irrigation water.     

Temporal variability of groundwater chemistry in shallow and deep aquifers of Araihazar, Bangladesh

Samples were collected every 2-4 weeks from a set of 37 monitoring wells over a period of 2-3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5-91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to +/-90%. In wells tapping the deeper aquifers >30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by (3)H/(3)He and (14)C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged <5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 microg/L (range: <5 to 648 microg/L; n=118) and 272 microg/L (range: 10 to 485 microg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with >5 years (3)H/(3)He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanisms of mobilization.     

Novel insights in Al-MCM-41 precursor as adsorbent for regulated haloacetic acids and nitrate from water

High concentration of NO ₃ ^? in groundwater has raised concern over possible contamination of drinking water supplies. In addition, the formation of haloacetic acids (HAAs) as by-products during disinfection with chlorine-based agents is still a relevant issue, since HAAs pose serious health hazard. In this work, we investigated the affinity of a precursor of Al-MCM-41 (a mesostructured hexagonal aluminosilicate containing the template surfactant) towards nitrate and HAAs, for its possible application in the removal of these pollutants from natural and drinking waters. Additionally, adsorption kinetics and isotherms were studied. The adsorbent was synthesized using cetyltrimethylammonium bromide as surfactant and characterized by physico?Cchemical techniques. Simulated drinking water was spiked with the EPA-regulated HAAs (monochloroacetic (MCAA), monobromoacetic (MBAA), dichloroacetic (DCAA), dibromoacetic (DBAA), and trichloroacetic (TCAA) acids) and placed in contact with the adsorbent. The effect of matrix composition was studied. Adsorption kinetic studies were performed testing three kinetics models. For the adsorption studies, three adsorption isotherm approaches have been tested to experimental data. The pollutant recoveries were evaluated by suppressed ion chromatography. The affinity of the adsorbent was TCAA = DBAA = DCAA > MBAA > MCAA with DCAA, DBAA, and TCAA completely removed. A removal as high as 77?% was achieved for 13?mg/L nitrate. The adsorption isotherms of NO ₃ ^? and monochloroacetic acid can be modeled by the Freundlich equation, while their adsorption kinetics follow a pseudo-second-order rate mechanism. The adsorbent exhibited high affinity towards HAAs in simulated drinking water even at relevant matrix concentrations, suggesting its potential application for water remediation technologies.     

Modeling the formation of chlorination by-products in river waters with different quality

Water chlorination results in formation of a variety of organic compounds, known as chlorination by-products (CBPs), mainly trihalomethanes (THMs) and haloacetic acids (HAAs). Factors affecting their concentrations have been found to be organic matter content of water, 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 river waters from Lesvos island, Greece, with different water quality regarding bromide concentration and organic matter content. The factors studied were pH, time and chlorine dose. The determination of CBPs 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 trihalomethanes and total HAAs based on the use of pH, reaction time and chlorine dose. The developed models, although providing satisfactory estimations of the concentrations of the CBPs, showed lower correlation coefficients than the multiple regression models developed for THMs only during previous study. It seems that the different water quality characteristics of the two river waters in the present study is responsible for this phenomenon. The results indicate that under these conditions the formation of THMs and HAAs in water has a more stochastic character, which is difficult to be described by the conventional regression techniques.     

Mutagenicity of anaerobic fenitrothion metabolites after aerobic biodegradation

Previous studies have revealed that the mutagenicity of fenitrothion increases during anaerobic biodegradation, suggesting that this insecticide's mutagenicity could effectively increase after it pollutes anaerobic environments such as lake sediments. To investigate possible changes to the mutagenicity of fenitrothion under aerobic conditions after it had already been increased by anaerobic biodegradation, batch incubation cultures were maintained under aerobic conditions. The mutagenicity, which had increased during anaerobic biodegradation, decreased under aerobic conditions with aerobic or facultative bacteria, but did not disappear completely in 22 days. In contrast, it did not change under aerobic conditions without bacteria or under continued anaerobic conditions. These observations suggest that the mutagenicity of anaerobically metabolized fenitrothion would not necessarily decrease after it arrives in an aerobic environment: this would depend on the presence of suitable bacteria. Therefore, fenitrothion-derived mutagenic compounds may pollute the water environment, including our drinking water sources, after accidental pollution of aerobic waters. Although amino-fenitrothion generated during anaerobic biodegradation of fenitrothion was the principal mutagen, non-trivial contributions of other, unidentified metabolites to the mutagenicity were also observed.     

Formation of halogenated acetaldehydes, and occurrence in Canadian drinking water

Controlled laboratory chlorination of acetaldehyde (ACD) under typical drinking water conditions (pH 6.7, 7.6 and 8.8, and temperature 4 degrees C and 21 degrees C) revealed that the formation of chloral hydrate (CH), the most common halogenated acetaldehyde (HAs), increased with contact time (0-10 days). However, at increased pH and temperature, CH reached maximum levels and subsequently broke down partially to chloroform and other unidentified compounds. After 10 days contact time, a maximum of 63% (molar) of the initial ACD consumed were converted into CH or chloroform (TCM). Various surveys of drinking water systems indicated that ACD is not the only precursor of CH. A suite of aldehydes (including ACD), and chlorinated disinfection by-products (including TCM and CH) were found in most distribution systems. The levels of bromide in source water impacted speciation of HAs. In addition to CH, brominated and other mixed (Cl/Br) acetaldehydes were detected in most samples; the speciation of HAs and THMs followed comparable trends. Similar to chloroform for trihalomethanes, CH contributed from as low as 5% to up to 60% of the total HAs. The bromine incorporation factors (BIF) in THMs and HAs were shown to increase with increasing bromide ion concentrations in the source water. Brominated THMs are more readily formed than their HA analogues; in fact, BIF values for THMs were 2-3 times higher than for the HAs. It was found that HAs may be as high as THMs in some drinking waters. As a result, the determination of the other target HAs, in addition to CH, is necessary for a better assessment of the pool of disinfection by-products in drinking water.     

Occurrence of THMs and HAAs in experimental chlorinated waters of the Quebec City area (Canada)

Haloacetic acids (HAAs) and trihalomethanes (THMs) were generated in bench-scale chlorination experiments using treated waters (prior to final chlorination) of the three major drinking water utilities of the Quebec City area. The purpose was to investigate the formation and occurrence of these chlorination by-products (CBPs) on a seasonal basis. Data for HAAs, THMs and other physico-chemical parameters were produced through a six-month sampling program with variable conditions of water quality, water temperature, applied chlorine dose and reaction time. In waters from the three utilities, chloroform (THM specie), dichloroacetic and trichloroacetic acid (HAA species) were the most prevalent compounds due to the low concentrations of bromide in the utilities' raw waters. Significant differences in CBP occurrence were noted between the three utilities' chlorinated waters, mainly due to the type of disinfectant applied to raw water. The use of pre-ozonation, as opposed to pre-chlorination (or direct chlorination) in one of the utilities appears to be the major factor contributing to that utility's potential for compliance with current THM and future HAA standards. Seasonal variations in THMs and HAAs were mainly associated with variations in organic precursors and to changes in water temperature (two parameters which vary widely on a seasonal basis in surface waters of southern Quebec), with CBP occurrence at its highest in spring. Statistical correlations between HAAs and THMs were moderate and only temperature appeared to affect the preponderance of one CBP or the other. Finally, a regression analysis was carried out aimed at associating each CBP to water quality and the experimental parameters. Thanks to their predictive ability, multivariate models seem to be the tools with the best potential for decision-making purposes.