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.     

Comparison of NOM character in selected Australian and Norwegian drinking waters

Observations from many countries around the world during the past 10-20 years indicate increasing natural organic matter (NOM) concentration levels in water sources, due to issues such as global warming, changes in soil acidification, increased drought severity and more intensive rain events. In addition to the trend towards increasing NOM concentration, the character of NOM can vary with source and time (season). The great seasonal variability and the trend towards elevated NOM concentration levels impose challenges to the water industry and the water treatment facilities in terms of operational optimisation and proper process control. The aim of this investigation was to compare selected raw and conventionally treated drinking water sources from different hemispheres with regard to NOM character which may lead to better understanding of the impact of source water on water treatment. Results from the analyses of selected Norwegian and Australian water samples showed that Norwegian NOM exhibited greater humic nature, indicating a stronger bias of allochthonous versus autochthonous organic origin. Similarly, Norwegian source waters had higher average molecular weights than Australian waters. Following coagulation treatment, the organic character of the recalcitrant NOM in both countries was similar. Differences in organic character of these source waters after treatment were found to be related to treatment practice rather than origin of the source water. The characterisation techniques employed also enabled identification of the coagulation processes which were not necessarily optimised for dissolved organic carbon (DOC) removal. The reactivity with chlorine as well as trihalomethane formation potential (THMFP) of the treated waters showed differences in behaviour between Norwegian and Australian sources that appeared to be related to residual higher molecular weight organic material. By evaluation of changes in specific molecular weight regions and disinfection parameters before and after treatment, correlations were found that relate treatment strategy to chlorine demand and DBP formation.     

Natural organic matter and DBP formation potential in Alaskan water supplies

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

Characterization of natural organic matter in conventional water treatment processes for selection of treatment processes focused on DBPs control

Natural organic matter (NOM) from raw and process waters at a conventional water treatment plant was isolated into hydrophobic and hydrophilic fractions by physicochemical fractionation methods to investigate its characteristics. Formation potential of trihalomethanes (THMs) was highly influenced by the hydrophobic fraction, whereas haloacetic acids formation potential (HAAFP) depended more on the hydrophilic fraction. However the hydrophobic fraction was removed more than the hydrophilic fraction through conventional water treatment. Therefore residual hydrophilic NOM after conventional treatment needs to be removed to reduce HAAFP. Feasible additional processes are required to be evaluated by comparing preferential removal efficiency of hydrophilic NOM through pilot tests. The structural and chemical characteristics of hydrophobic NOM (i.e., humic substances (HS)) were further investigated to know how they are influenced by conventional treatment. The phenolic fraction in the hydrophobic NOM was mainly removed compared to the carboxylic fraction through water treatment, and a higher formation potential of THMs resulted from NOM with a higher phenolic content. The Fourier-transform infrared (FT-IR) and proton nuclear magnetic resonance ((1)H-NMR) employed for characterization of NOM through water treatment were insightful revealing that their results were quite close to each other. Decreases of ratio of UV absorbance at 253 and 203 nm, respectively (A(253)/A(203) ratio) and trihalomethane formation potential/dissolved organic carbon (THMFP/DOC) showed consistent trends; therefore, the A(253)/A(203) ratio may be a good indicator of tendency for the formation potential of disinfection by-products (DBPs).     

Long term case study of MIEX pre-treatment in drinking water; understanding NOM removal

Removal of natural organic matter (NOM) is a key requirement to improve drinking water quality. This study compared the removal of NOM with, and without, the patented magnetic ion exchange process for removal of dissolved organic carbon (MIEX DOC) as a pre-treatment to microfiltration or conventional coagulation treatment over a 2 year period. A range of techniques were used to characterise the NOM of the raw and treated waters. MIEX pre-treatment produced water with lower concentration of dissolved organic carbon (DOC) and lower specific UV absorbance (SUVA). The processes incorporating MIEX also produced more consistent water quality and were less affected by changes in the concentration and character of the raw water DOC. The very hydrophobic acid fraction (VHA) was the dominant NOM component in the raw water and was best removed by MIEX pre-treatment, regardless of the raw water VHA concentration. MIEX pre-treatment also produced water with lower weight average apparent molecular weight (AMW) and with the greatest reduction in complexity and range of NOM. A strong correlation was found between the VHA content and weight average AMW confirming that the VHA fraction was a major component of the NOM for both the raw water and treated waters.     

Degradation of DBPs' precursors in river water before and after slow sand filtration by photo-Fenton process at pH 5 in a solar CPC reactor

The generation of disinfection by-products during water treatment can be controlled by reducing the levels of precursor species prior to the chlorination step. The Natural Organic Matter (NOM) is the principal organic precursor and conventional removal of pollutants such as coagulation, flocculation and filtration do not guarantee the total NOM removal. In this study the degradation of NOM model compounds (dihydroxy-benzene) as well as the removal of NOM from river water via photo-Fenton process in a CPC solar photo-reactor is presented. The effect of solar activated photo-Fenton reagent at pH 5.0 before and after a slow sand filtration (SSF) in waters containing natural iron species is investigated and the details reported. The results showed that the total transformation of dihydroxy-benzene compounds along a mineralization higher than 80% was obtained. The mineralization of the organic compounds dissolved in natural water was higher than in Milli-Q water, suggesting that the aqueous organic and inorganic components (metals, humic acids and photoactive species) positively affect the photocatalytic process. When 1.0 mg/L of Fe³⁺ is added to the system, the photo-Fenton degradation was improved. Therefore the photo-Fenton reagent could be an interesting complement to other processes for NOM removal. Comparing the response of two rivers as media for the organic compounds degradation it was observed that the NOM photo-degradation rate depends of the water composition.     

Influence of the character of NOM on the ozonation of MIB and geosmin

Tastes and odours (T&Os) are a major concern in drinking water as they are not efficiently removed by conventional water treatment. Ozonation has been effective for their destruction in some studies. However, the natural organic matter (NOM) in waters can affect the ozonation process and subsequently affect the destruction of T&Os. Five NOM fractions were isolated and ozonated in synthetic waters. The fraction containing the more highly coloured, higher molecular weight compounds exhibited the highest ozone (O3) demand, whereas the low aromatic fraction exhibited the lowest O3 demand. The character of the NOM fractions influenced the ozonation of MIB and geosmin. The destruction of MIB and geosmin was significantly higher in the fraction with the highest colour and UV/visible absorbance at all O3 doses. The destruction of the compounds in the other fractions showed the same trends, increasing MIB and geosmin destruction with increasing UV/visible absorbing character of the NOM. MIB was also ozonated in two real waters. with results showing a competing effect between NOM concentration and NOM character. The O3 reaction time was shown to be important for the destruction of both compounds.     

Evaluation of biodegradability of NOM after ozonation

The major purpose of this study was to develop a simple procedure to describe the kinetics of biodegradation of natural organic matter (NOM) in drinking water and to use this procedure to evaluate changes in the concentration of biodegradable organic matter during ozonation and biotreatment. The proposed approach quantitatively describes the formation and removal of rapidly and slowly biodegradable fractions of NOM. This study showed that, depending on source water, ozonation of NOM may result in either minimal formation of biodegradable organic carbon (BDOC), or the formation of predominantly rapidly biodegradable NOM, or in the formation of both rapidly and slowly biodegradable NOM. The kinetic data obtained in this study suggest that while conventional biofiltration processes are capable of removing the rapidly biodegradable fraction, slowly biodegradable organic matter would remain in the filter effluent and may cause bacterial regrowth in the distribution system. An addition of a small amount of easily biodegradable carbon ("stimulated" biodegradation) to ozonated water appears to be effective for the removal of slowly biodegradable organic matter.     

Tracking natural organic matter (NOM) in a drinking water treatment plant using fluorescence excitation-emission matrices and PARAFAC

Natural organic matter (NOM) in water samples from a drinking water treatment train was characterized using fluorescence excitation emission matrices (F-EEMs) and parallel factor analysis (PARAFAC). A seven component PARAFAC model was developed and validated using 147 F-EEMs of water samples from two full-scale water treatment plants. It was found that the fluorescent components have spectral features similar to those previously extracted from F-EEMs of dissolved organic matter (DOM) from diverse aquatic environments. Five of these components are humic-like with a terrestrial, anthropogenic or marine origin, while two are protein-like with fluorescence spectra similar to those of tryptophan-like and tyrosine-like fluorophores. A correlation analysis was carried out for samples of one treatment plant between the maximum fluorescence intensities (F_max) of the seven PARAFAC components and NOM fractions (humics, building blocks, neutrals, biopolymers and low molecular weight acids) of the same sample obtained using liquid chromatography with organic carbon detection (LC-OCD). There were significant correlations (p < 0.01) between sample DOC concentration, UVA₂₅₄, and F_max for the seven PARAFAC components and DOC concentrations of the LC-OCD fractions. Three of the humic-like components showed slightly better predictions of DOC and humic fraction concentrations than UVA_254. Tryptophan-like and tyrosine-like components correlated positively with the biopolymer fraction. These results demonstrate that fluorescent components extracted from F-EEMs using PARAFAC could be related to previously defined NOM fractions and that they could provide an alternative tool for evaluating the removal of NOM fractions of interest during water treatment.     

The effect of ozonation on natural organic matter removal by alum coagulation

Natural organic matter (NOM) was extracted from a moderately colored, eutrophic surface water source (Forge Pond, Granby, MA), and fractionated into quasi-homogeneous fractions. Fulvic acid (FA) and hydrophilic neutrals (HN) were the two most abundant NOM fractions that were isolated. Adsorption affinity of the isolated NOM fractions on preformed aluminum hydroxide flocs increased with increase in specific organic charge of the fractions, except for the two most highly charged fractions, FA and hydrophilic acids (HAA), which showed less adsorption affinity than expected based on their specific organic charge. Prior ozonation of FA and HN fractions resulted in a decline and an increase, respectively, in their adsorption affinity on aluminum hydroxide surface. Prior ozonation of Forge Pond raw water resulted in a progressive decline in dissolved organic carbon (DOC) removal by alum coagulation with increase in ozone dose. It appeared that ozone applied to raw water reacted preferentially with the humic fraction of NOM, resulting in the detrimental effects of ozonation on subsequent NOM removal by alum coagulation being magnified. Forge Pond raw water was pre-coagulated to remove humic substances. Ozonation of the pre-coagulated water demonstrated the beneficial effects of ozonation on the removal of non-humic NOM through alum coagulation. A strategy for staged coagulation with intermediate ozonation was proposed for waters containing both humic and non-humic NOM for maximum DOC and specific UV absorbance at 254nm (SUVA) removal.     

Assimilable organic carbon in molecular weight fractions of natural organic matter

Assimilable organic carbon (AOC) in natural organic matter (NOM) has been measured in three Norwegian waters. The AOC measurement has been done on unfiltered and membrane-filtered (molecular weight (MW) cut-off of 1000 and 10,000) samples. While the colour in the waters is mainly related to the NOM with MW > 10,000, the AOC was mainly related to the NOM with MW < 1000. The fraction of the NOM with MW < 1000 corresponds to 16-38% of the total organic carbon (TOC), and 4-9% of the colour. This shows that a water treatment process removing the colour and a large part of the TOC in the water will not necessarily result in a reduction in the biofilm formation potential.     

Preliminary laboratory investigation of disinfection by-product precursor removal using an advanced oxidation process

Natural organic matter (NOM) is ubiquitous in surface and ground waters throughout the world. During drinking water treatment, the NOM that remains in treated water can react with chlorine to form disinfection by‐products. It has been shown that titanium dioxide photocatalysis can achieve over 96% reduction in ultraviolet (UV)₂₅₄ absorbing species such as hydrophobic NOM and over 81% reduction in dissolved organic carbon (DOC). However, an additional filtration stage is required to recover the suspended catalyst before it is suitable for municipal drinking water application. To overcome this problem, we have used immobilised catalysts prepared using chemical sol–gels, and their performance has been assessed during bench‐scale experiments. An immobilised catalyst enables in situ regeneration using UV light and subsequent reuse of the catalyst. In this research, titanium dioxide sol–gels have been used to coat substrates at a laboratory scale. Results showed that the various coatings prepared had different removal efficiencies for both DOC and UV₂₅₄ absorbance. Maximum removals were 1.336 g/m² and 89%, respectively.     

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.     

Probing reactivity of dissolved organic matter for disinfection by-product formation using XAD-8 resin adsorption and ultrafiltration fractionation

The disinfection by-product (DBP) reactivity (yield and speciation upon reaction with chlorine) of dissolved organic matter (DOM) isolated from two surface waters was investigated. The source waters, each having significantly different specific ultraviolet absorbance (SUVA254), molecular weight (MW) distribution and polarity, were fractionated using XAD-8 resin adsorption and ultrafiltration (UF), with good DOM mass balance closures (based on dissolved organic carbon). It was found that such fractionation preserved both the SUVA and the reactivity of the source waters, as demonstrated by statistically similar DBP formation and speciation from chlorinated source water and source waters reconstituted from XAD-8 or UF fractions. In addition, there was no evidence of synergistic effects among DOM components when reacting with chlorine. Consistent trends between DBP yields and MW were not found. Hydrophobic fractions of DOM (isolated by XAD-8) were the most reactive DOM components; however, hydrophilic components also showed appreciable DBP yields, contributing up to 50% of total DBP formation. In contrast, strong and unique correlations were observed between the SUVA of individual fractions and their trihalomethane (THM) and haloacetic acid (HAA9) yields, confirming that the aromaticity of DOM components is more directly related to reactivity than other physicochemical properties. The finding of a single correlation independent of the fractionation process employed is notable because XAD-8 adsorption and UF fractionate DOM by significantly different mechanisms. These results confirm that SUVA is a distributed parameter that reflects DOM heterogeneity. Therefore, the SUVA distribution within natural water represents an important property that can be used as a reliable predictor of DBP formation. Finally, bromine appears to be more effectively incorporated into low UV-absorbing (i.e., low SUVA), low MW and hydrophilic DOM fractions.     

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

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

Removal of THM precursors by coagulation or ion exchange

The removal of natural organic matter (NOM) from drinking water supplies can be achieved by different processes, among them coagulation and adsorption. Synthetic waters made from concentrates of humic substances from reservoir and river waters were tested in the laboratory for ease of removal of NOM by coagulation with cationic organic polymers and with alum, and by adsorption on anion exchangers. For polymers such as high molecular weight polydiallyldimethylammonium chloride (polyDADMAC) and cationic polyacrylamides of high charge, performance was nearly as effective as alum, with colour removals 86–100% of those obtained for alum. Ion exchange using the best commercially available resins designed for this purpose, a gel polystyrene and a macroporous acrylic resin, was more effective than alum treatment for two of the natural waters studied, but inferior for a third. The resins were overall superior to cationic polymers.

The NOM was separated into four fractions based on hydrophobic and hydrophilic properties. Alum was not as effective as ion exchange for the elimination of individual ionic NOM fractions. It was better than cationic polymers for removal of humic and fulvic acids, although polyDADMAC was as good for one water. For the removal of charged compounds alum then polyDADMAC were the best performers for that water. Unequivocal evidence was obtained that coagulants remove material that is not adsorbed by resins, and vice versa. A combination of coagulation with a cationic polymer and adsorption by an anion exchanger removed essentially all of the NOM. The preference of the coagulants was for the larger, more hydrophobic molecules, and of resins for smaller highly charged hydrophilic molecules. Each fraction had trihalomethane formation potentials in the range 11–24 μg/mg, except for one water that was more reactive. Hence, the actual amount of each fraction in the original water becomes a crucial factor.     

Absorbance spectroscopy-based examination of effects of coagulation on the reactivity of fractions of natural organic matter with varying apparent molecular weights

Absorbance spectra of fractions of natural organic matter (NOM) with varying apparent molecular weights (AMWs) were examined in this study. Size exclusion chromatography (SEC) was employed to obtain AMW distributions for three Australian water sources which represented low- and high-dissolved organic carbon (DOC) surface waters and a source with highly degraded NOM. These waters were coagulated with alum and other coagulants. Effects of coagulation on AMW distributions were quantified based on an absorbance slope index (ASI) calculated using NOM absorbance measured at 220, 230, 254 and 272 nm. This index can be calculated for any AMW fraction of NOM. Similarly to SUVA₂₅₄, ASI values decrease consistently in coagulated waters and are correlated with trihalomethane yields. Comparison of ASI indexes in different water sources indicates the presence of both common trends and differences indicative of NOM site-specificity.     

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

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

Formation of chlorination by-products in waters with low SUVA--correlations with SUVA and differential UV spectroscopy

The formation of THMs and HAAs after chlorination of bulk water fractions of low-SUVA (specific UV absorbance) surface waters was investigated, and the applicability of SUVA and differential UV spectroscopy for monitoring THMs and HAAs in such waters was evaluated. Samples from two reservoirs were fractionated employing XAD-8, XAD-4, MIEX resin and granular activated carbon adsorption. A total of 83 bulk water NOM fractions (i.e., the remaining solutions after contact with the adsorbent or resin at various doses) were obtained and chlorinated. The majority of NOM in both waters was found to have average molecular weights <2000 Da and SUVA values <2L/mg Cm, indicating that NOM in the tested waters contained dominantly lower molecular weight fractions and low aromaticity. SUVA did not correlate well with the formation and speciation of THMs and HAAs, suggesting that SUVA does not capture the reactive sites on NOM moieties responsible for DBP formation in low-SUVA waters. Similarly, no correlations were found among THMs/HAAs formations and differential UV spectroscopy, indicating the formation of DBPs independent of destruction in UV-absorbing sites. In all fractions, concentrations of THMs were higher than those of HAAs. Chlorinated DBP species were dominant over brominated ones due to low bromide concentrations. The results overall suggested that low- or non-UV-absorbing NOM moieties play important roles in the formation of DBPs in waters with low SUVA, low DOC and low bromide levels.     

Impact of recycling filter backwash water on organic removal in coagulation-sedimentation processes

The overall purpose of this research was to examine the impacts of filter backwash water (FBWW) and membrane backwash water (MBWW) recycles on water quality in coagulation-sedimentation processes. Specifically, the impact of recycling 5 or 10% by volume of FBWW and MBWW with surface water on the removal of natural organic matter (NOM) was evaluated at bench-scale using a standard jar-test apparatus and measurement of specific water quality parameters including total organic carbon (TOC), dissolved organic carbon (DOC), UV254, turbidity, total aluminum and zeta potential. The results of jar test conducted on a source water with a specific UV absorbance (SUVA) value within the range of 2-4 mg/L m showed a significantly higher removal of DOC from the raw water that was blended with 5 and 10% by volume of FBWW as compared to control trials where backwash water was not added. Increasing rates of MBWW that did not contain destabilized hydroxide precipitates did not significantly change DOC concentrations in the settled water samples as compared to the control trials. For source waters that are characterized as having low turbidity with medium SUVA values, these results could hold particular significance for plants that have reached treatment ceilings in terms of dissolved NOM removal using conventional coagulation designs.