Characterization of intracellular & extracellular algae organic matters (AOM) of Microcystic aeruginosa and formation of AOM-associated disinfection byproducts and odor & taste compounds

Algae organic matters (AOM), including intracellular organic matters (IOM) and extracellular organic matters (EOM), are causing numerous water quality issues, among which formation of disinfection byproducts (DBPs) and odor & taste (O&T) compounds are of particular concern. In this study, physiochemical properties of IOM and EOM of Microcystic aeruginosa under an exponential growth phase (2.01 × 10¹¹/L) were comprehensively characterized. Moreover, the yields of DBPs during AOM disinfection and O&T-causing compounds were quantified. Hydrophilic organic matters accounted for 86% and 63% of DOC in IOM and EOM, respectively. Molecular weight (MW) fractions of IOM in <1 kDa, 40-800 kDa, and >800 kDa were 27%, 42%, and 31% of DOC, respectively, while EOM primarily contained 1-100 kDa molecules. Besides, a low SUVA (0.84 L/mg m) and the specific fluorescence spectra suggested that AOM (especially IOM) was principally comprised of protein-like substances, instead of humic-like matters. The formation potentials of chloroform, chloroacetic acid, and nitrosodimethylamine were 21.46, 68.29 and 0.0096 μg/mg C for IOM, and 32.44, 54.58 and 0.0189 μg/mg C for EOM, respectively. Furthermore, the dominant O&T compound produced from EOM and IOM were 2-MIB (68.75 ng/mg C) and β-cyclocitral (367.59 ng/mg C), respectively. Of note, dimethyltrisulfide became the prevailing O & T compound following anaerobic cultivation.     

Reductive electrochemical remediation of emerging and regulated disinfection byproducts

Long-term exposure to low concentrations of disinfection byproducts (DBPs) in drinking water has been associated with increased human-health risks of bladder cancer and adverse reproductive outcomes. In this study, we investigated electrochemical reduction utilizing a resin-impregnated graphite cathode for the degradation of 17 DBPs (i.e. halomethanes, haloacetonitriles, halopropanones, chloral hydrate and trichloronitromethane) at low μg L⁻¹ concentration levels. The reduction experiments were potentiostatically controlled at cathode potentials −700, −800 and −900 mV vs Standard Hydrogen Electrode (SHE) during 24 h. At the lowest potential applied (i.e. −900 mV vs SHE), the disappearance of DBPs from the solution after 24 h of reduction was >70%, except for chloroform (32%), 1,1-dichloropropanone (48%), and chloral hydrate (31%). Due to the participation of several removal mechanisms (e.g. electrochemical reduction, adsorption, volatilization and/or hydrolysis) it was not possible to distinguish the removal efficiencies of electrochemical reduction of individual compounds. Adsorption of the more hydrophilic DBPs (i.e. haloacetonitriles, chloral hydrate, and 1,1-dichloropropanone) onto the electrode seems to be affected by the cathode polarization, as the removals observed in the open circuit experiments were significantly higher than the ones obtained in electrochemical reduction under the same conditions. The overall efficiency of reduction was estimated based on the analyses of the released Cl⁻, Br⁻ and I⁻ ions. Nearly complete C-I bond cleavage was achieved at all three potentials applied, and from the theoretically predicted release of I⁻ ions, calculated based on the removed DBPs, 86 ± 9 to 92 ± 1% was measured in the catholyte solution at −700 to −900 mV vs SHE. Debromination efficiencies obtained were 74 ± 3, 79 ± 6 and 68 ± 4% at −700, −800 and −900 mV vs SHE, while for C-Cl bond cleavage the obtained values were 69 ± 1, 72 ± 1 and 76 ± 4%, respectively. Nevertheless, dechlorination efficiencies are to be considered as approximate, since an increase in Cl⁻ concentration was observed in the open circuit experiments due to the hydrolysis of some of the chlorine-containing DBPs. Although the Coulombic efficiencies for DPBs dehalogenation were only 1.9 ± 0.3 (−900 mV vs SHE) -4.1 ± 0.2% (−700 mV vs SHE), relatively low energy consumption of the process was observed, estimated at 72 ± 2 Wh m⁻³ at −900 mV vs SHE for the concentration range of DBPs in this study (i.e. 65.3-129.7 μg L⁻¹). The study demonstrated that reductive electrochemical treatment has the potential to be a modern remediation technology for the removal of low concentrations of halogenated DBPs in water.     

Identification of potential nitrogenous organic precursors for C-, N-DBPs and characterization of their DBPs formation

Nitrosamines are a class of emerging disinfection by-products (DBPs), which are mainly formed when water is treated by chloramination. Nitrosamines are highly carcinogenic and are hence a major concern for drinking water supplies. Although dissolved organic nitrogen (DON) compounds such as dimethylamine (DMA) have been recognized as important precursors of nitrosamines, many of them have not been identified, especially those used in consumer products. In this study, nine representative nitrogenous organic compounds with different DON characteristics and structures were selected to react with free chlorine, chlorine dioxide and monochloramine, respectively, for their DBP formation characteristics (nitrosamines, trihalomethanes (THMs) and haloacetic acids (HAAs)). It was found that in addition to DMA, benzyldimethyltetradecylamine (benzalkonium chloride, BKC) and 3-(N,N-dimethyloctyl-ammonio)propanesulfonate (3-N,N-DAPSIS) inner salt were potent precursors for carbonated DBPs (C-DBPs) and nitrogenated DBPs (N-DBPs). The DBP formation potential (DBPFP) tests showed that 1 mM of BKC formed more than 2 × 10⁵ ng/L of N-nitrosodimethylamine (NDMA) when treated with monochloramine and high levels of C-DBPs (2713 ± 145 μg/L of THMs and 356 ± 5 μg/L of HAAs) when treated with chlorine. 3-N,N-DAPSIS was a less potent DBP precursor: 1 mM of 3-N,N-DAPSIS generated 1155 ± 7 ng/L of NDMA, 1351 ± 66 μg/L of THMs and 188 ± 1 μg/L of HAAs. DMA, 3-N,N-DAPSIS and BKC were examined for their DBPFPs at various pH and temperatures to determine the impact of pH and reaction temperature on DBP yields and their formation mechanisms. The results showed that DBP yields apparently increased with rising temperature. However, no consistent correlations were observed between DBPs yields and pH. Bromide shifted the DBP species into brominated DBPs, and this phenomenon was more apparent when BKC was treated with chloramine.     

Formation of organic chloramines during water disinfection - chlorination versus chloramination

Many of the available studies on formation of organic chloramines during chlorination or chloramination have involved model organic nitrogen compounds (e.g., amino acids), but not naturally occurring organic nitrogen in water. This study assessed organic chloramine formation during chlorination and chloramination of 16 natural organic matter (NOM) solutions and 16 surface waters which contained dissolved organic nitrogen (DON). Chlorination rapidly formed organic chloramines within 10 min, whereas chloramination formed organic chloramination much more slowly, reaching the maximum concentration between 2 and 120 h after the addition of monochloramine into the solutions containing DON. The average organic chloramine formation upon addition of free chlorine and monochloramine into the NOM solutions were 0.78 mg-Cl₂/mg-DON at 10 min and 0.16 mg-Cl₂/mg-DON at 24 h, respectively. Organic chloramine formation upon chlorination and chloramination increased as the dissolved organic carbon/dissolved organic nitrogen (DOC/DON) ratio decreased (i.e., DON contents increased). Chlorination of molecular weight (10,000 Da) fractionated water showed that molecular weight of DON would not impact the amount of organic chloramines produced. Comparison of three different disinfection schemes at water treatment plants (free chlorine, preformed monochloramine, and chlorine/ammonia additions) indicated organic chloramine formation could lead to a possible overestimation of disinfection capacity in many chloraminated water systems that add chlorine followed by an ammonia addition to form monochloramine.     

Occurrence and formation of chloro- and bromo-benzoquinones during drinking water disinfection

Consumption of chlorinated drinking water has shown somewhat consistent association with increased risk of bladder cancer in a series of epidemiological studies, but plausible causative agents have not been identified. Halobenzoquinones (HBQs) have been recently predicted as putative disinfection byproducts (DBPs) that might be of toxicological relevance. This study reports the occurrence frequencies and concentrations of HBQs in plant effluents from nine drinking water treatment plants in the USA and Canada, where four common disinfection methods, chlorination, chloramination, chlorination with chloramination, and ozonation with chloramination, are used. In total, 16 water samples were collected and analyzed for eight HBQs: 2,6-dichloro-1,4-benzoquinone (2,6-DCBQ), 2,6-dibromo-1,4-benzoquinone (2,6-DBBQ), 2,6-dichloro-3-methyl-1,4-benzoquinone (2,6-DC-3-MBQ), 2,3,6-trichloro-1,4-benzoquinone (2,3,6-TriCBQ), 2,5-dibromo-1,4-benzoquinone (2,5-DBBQ), 2,3-dibromo-5,6-dimethyl-1,4-benzoquinone (2,3-DB-5,6-DM-BQ), tetrabromo-1,4-benzoquinone (TetraB-1,4-BQ), and tetrabromo-1,2-benzoquinone (TetraB-1,2-BQ). Of these, 2,6-DCBQ, 2,6-DBBQ, 2,6-DC-3-MBQ and 2,3,6-TriCBQ were detected in 16, 11, 6, and 3 of the 16 samples with the method detection limit (DL) of 1.0, 0.5, 0.9 and 1.5 ng/L, respectively, using a solid phase extraction and high performance liquid chromatography-tandem mass spectrometry method. The concentrations were in the ranges of 4.5-274.5 ng/L for 2,6-DCBQ, below DL to 37.9 ng/L for 2,6-DBBQ, below DL to 6.5 ng/L for 2,6-DC-3-MBQ, and below DL to 9.1 ng/L for 2,3,6-TriCBQ. These authentic samples show DCBQ and DBBQ as the most abundant and frequently detectable HBQs. In addition, laboratory controlled experiments were performed to examine the formation of HBQs and their subsequent stability toward hydrolysis when the disinfectants, chlorine, chloramine, or ozone followed by chloramines, reacted with phenol (a known precursor) under various conditions. The controlled reactions demonstrate that chlorination produces the highest amounts of DCBQ, while pre-ozonation increases the formation of DBBQ in the presence of bromide. At pH < 6.8, 2,6-DCBQ was observed to be stable, but it was easily hydrolyzed to form mostly 3-hydroxyl-2,6-DCBQ at pH 7.6 in drinking water.     

Effect of some parameters on the formation of chloroform during chloramination of aqueous solutions of resorcinol

The effects of various factors (N/Cl ratio used to prepare monochloramine, monochloramine doses, pH and contact time) on the monochloramine demand and on the chloroform yield during chloramination of resorcinol have been investigated. Chloramination experiments were carried out at 24 ± 1 °C, at pH values ranging from 6.5 to 12 using a bicarbonate/carbonate buffer and preformed monochloramine solutions prepared at pH 8.5 with N/Cl ratios ([NH₄Cl]₀/[Total free Cl₂]₀ ranging from 1.0 to 150 mol/mol). Kinetic experiments ([Resorcinol]₀ = 5 or 100 μM, [NH₂Cl]₀/[Resorcinol]₀ = 20 mol/mol, pH = 8.5 ± 0.1) showed a slow increase of the monochloramine consumption with reaction time. The monochloramine demands after reaction times of 7 days ([Resorcinol]₀ = 100 μM) and 14 days ([Resorcinol]₀ = 5 μM) were equal to 8.5 mol of NH₂Cl/mole of resorcinol and were higher than the chlorine demands (≈7.3 mol/mol). Chloroform yields from monochloramination of resorcinol were lower than 8% (<80 mmol of CHCl₃/mole of resorcinol) and were less than the yields obtained by chlorination (0.9-0.95 mol/mol). Chloroform productions increased with increasing monochloramine dose and reaction time and decreased with increasing pH values within the pH range 6.5-10. Chloroform formation markedly decreased when the N/Cl ratio increased from 1 to 1.5 mol/mol and was suppressed at N/Cl > 100 mol/mol. The data obtained in the present work suggest that free chlorine released from monochloramine hydrolysis plays a significant role on the formation of chloroform during chloramination of resorcinol at N/Cl ratios close to unity (1.0 < N/Cl < 1.5).     

The effect of inorganic precursors on disinfection byproduct formation during UV-chlorine/chloramine drinking water treatment

Ultraviolet (UV) disinfection is being increasingly used in drinking water treatment. It is important to understand how its application to different types of water may influence finished water quality, particularly as anthropogenic activity continues to impact the quality of source waters. The objective of this study was to evaluate the effect of inorganic precursors on the formation of regulated and unregulated disinfection byproducts (DBPs) during UV irradiation of surface waters when combined with chlorination or chloramination. Samples were collected from three drinking water utilities supplied by source waters with varying organic and inorganic precursor content. The filtered samples were treated in the laboratory with a range of UV doses delivered from low pressure (LP, UV output at 253.7 nm) and medium pressure (MP, polychromatic UV output 200-400 nm) mercury lamps followed by chlorination or chloramination, in the presence and absence of additional bromide and nitrate. The regulated trihalomethanes and haloacetic acids were not affected by UV pretreatment at disinfection doses (40-186 mJ/cm²). With higher doses (1000 mJ/cm²), trihalomethane formation was increased 30-40%. While most effects on DBPs were only observed with doses much higher than typically used for UV disinfection, there were some effects on unregulated DBPs at lower doses. In nitrate-spiked samples (1-10 mg N/L), chloropicrin formation doubled and increased three- to six-fold with 40 mJ/cm² MP UV followed by chloramination and chlorination, respectively. Bromopicrin formation was increased in samples containing bromide (0.5-1 mg/L) and nitrate (1-10 mg N/L) when pretreated with LP or MP UV (30-60% with 40 mJ/cm² LP UV and four- to ten-fold increase with 40 mJ/cm² MP UV, after subsequent chlorination). The formation of cyanogen chloride doubled and increased three-fold with MP UV doses of 186 and 1000 mJ/cm², respectively, when followed by chloramination in nitrate-spiked samples but remained below the World Health Organization guideline value of 70 μg/L in all cases. MP UV and high LP UV doses (1000 mJ/cm²) increased chloral hydrate formation after subsequent chlorination (20-40% increase for 40 mJ/cm² MP UV). These results indicate the importance of bench-testing DBP implications of UV applications in combination with post-disinfectants as part of the engineering assessment of a UV-chlorine/chloramine multi-barrier disinfection design for drinking water treatment.     

Comparison of disinfection byproduct formation from chlorine and alternative disinfectants

Seven diverse natural waters were collected and treated in the laboratory under five oxidation scenarios (chlorine, chloramine, both with and without preozonation, and chlorine dioxide). The impact of these disinfectants on the formation of disinfection byproducts was investigated. Results showed that preozonation decreased the formation of trihalomethanes (THMs), haloacetic acids (HAAs) and total organic halogen (TOX) for most waters during postchlorination. A net increase in THMs, HAAs and TOX was observed for a water of low humic content. Either decreases or increases were observed in dihaloacetic acids and unknown TOX (UTOX) as a result of preozonation when used with chloramination. Chloramines and chlorine dioxide produced a higher percentage of UTOX than free chlorine. They also formed more iodoform and total organic iodine (TOI) than free chlorine in the presence of iodide. Free chlorine produced a much higher level of total organic chlorine (TOCl) and bromine (TOBr) than chloramines and chlorine dioxide in the presence of bromide.     

Evaluation of bromine substitution factors of DBPs during chlorination and chloramination

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.     

DNA damage induction by two halogenated acetaldehydes, byproducts of water disinfection

Drinking water contains disinfection byproducts, generated by the interaction of chlorine (or other disinfecting chemicals) with organic matter, anthropogenic contaminants, and bromide/iodide naturally present in most source waters. One class of these chemicals is the halogenated acetaldehydes (HAs), identified in high quantities when ozone is used as primary or secondary disinfectant. In this study, an analysis of the genotoxic potential of two HAs, namely tribromoacetaldehyde (TBA) and chloral hydrate (CH) has been conducted in human cells (TK6 cultured cells and peripheral blood lymphocytes). The comet assay was used to 1) measure the induction of single and double-strand DNA breaks, 2) evaluate the capacity of inducing oxidative DNA damage, and 3) determine the DNA repair kinetics of the induced primary genetic damage. In addition, chromosome damage, as a measure of fixed damage, was evaluated by means of the micronucleus test. The results of the comet assay show that both compounds are clearly genotoxic, inducing high levels of DNA breaks, TBA being more effective than CH. According to the comet results, both HAs produce high levels of oxidized bases, and the induced DNA damage is rapidly repaired over time. Contrarily, the results obtained in the micronucleus test, which measures the capacity of genotoxic agents to induce clastogenic and aneugenic effects, are negative for the two HAs tested, either using TK6 cells or human peripheral blood lymphocytes. This would indicate that the primary damage induced by the two HAs is not fixed as chromosome damage, possibly due to an efficient repair or the death of damaged cells, which is an important point in terms of risk assessment of DBPs exposure.     

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

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

The influence of disinfection on aquatic biodegradable organic carbon formation

The aim of this paper was to assess the extent of biodegradable dissolved organic carbon formation upon disinfection of water with chlorine dioxide. Wide diversity of natural waters has been subjected to reactions with various amounts of ClO₂. For comparison examined waters have also been treated with ozone and chlorine. The application of chlorine dioxide and ozone significantly changed the molecular weight distribution of aquatic organic matter. As a result significant amounts of biodegradable carboxylic acids and aldehydes were generated. The formic, acetic, oxalic and ketomalonic acids as well as formaldehyde, acetaldehyde, glyoxal, methylglyoxal were identified. The productivity of aldehydes calculated for all examined waters and disinfectants amounted 12.7-47.7 μg mg⁻¹ DOC in the case of ozonation, 1.3-8.1 μg mg⁻¹ DOC after chlorination and 1.7-9.4 μg mg⁻¹ DOC for ClO₂ treatment. The highest total concentration of carboxylic acids was determined after the ozonation processes. In this case the organic acids' formation potential was in the range 10.8-62.8 μg mg⁻¹ DOC. Relatively high formation potential (5.3-17.9 μg mg⁻¹ DOC) was determined after the oxidation with ClO₂ as well. In the case of chlorination, the productivity of organic acids was low and did not exceed 3.4 μg mg⁻¹ DOC. The relatively high correlation between BDOC formation and carboxylic acids' formation potential was observed. Thus, carboxylic acids' formation potential may be used as a measure of water potential to form BDOC.     

Formation of halogenated organic byproducts during medium-pressure UV and chlorine coexposure of model compounds, NOM and bromide

When chlorine is applied before or during UV disinfection of bromide-containing water, interactions between chlorine, bromide and UV light are inevitable. Formation of halogenated organic byproducts was studied during medium-pressure UV (MPUV) and chlorine coexposure of phenol, nitrobenzene and benzoic acid and maleic acid, chosen to represent electron-donating aromatics, electron-withdrawing aromatics, and aliphatic structures in natural organic matter (NOM), respectively. All were evaluated in the presence and absence of bromide. MPUV and chlorine coexposure of phenol produced less total organic halogen (TOX, a collective parameter for halogenated organic byproducts) than chlorination in the dark, and more haloacetic acids instead of halophenols. Increases in TOX were found in the coexposure of nitrobenzene and benzoic acid, but maleic acid was rather inert during coexposure. The presence of bromide increased the formation of brominated TOX but did not significantly affect total TOX formation, in spite of the fact that it reduced hydroxyl radical levels. MPUV and chlorine coexposure of NOM gave a higher differential UV absorbance of NOM and a larger shift to lower molecular weight compounds than chlorination in the dark. However, TOX formation with NOM remained similar to that observed from dark chlorination.     

Formation, adsorption and separation of high molecular weight disinfection byproducts resulting from chlorination of aquatic humic substances

A significant portion of the unidentified disinfection byproducts (DBPs) in chlorinated drinking water can be attributed to high molecular weight (MW)-chlorinated DBPs (above 500 Da) that may have adverse health effects. In this work, issues on the formation, adsorption and separation of high MW-chlorinated DBPs were investigated by introducing radioactive (36)Cl into humic substance samples. The results show that the amount of high MW-chlorinated DBPs during chlorination decreased with the increase of contact time from 1 to 120 h, increased with the increase of pH from 5.5 to 9.5, and was less in the ultrafiltered samples from Suwannee River fulvic acid than from Suwannee River humic acid. The high MW-chlorinated DBPs were found to be effectively adsorbed by activated carbon and be possibly reduced to Cl(-) by activated carbon, but not to be readily desorbed from the activated carbon. Those high MW-chlorinated DBPs were demonstrated to be incapable of resolution into discrete peaks by any of the three liquid chromatography columns studied. The significant implications of these results are discussed.     

Factors affecting formation of haloacetonitriles, haloketones, chloropicrin and cyanogen halides during chloramination

Effects of contact time, monochloramine doses, monochloramine application modes, pH, temperature and bromide ion concentrations on formation of disinfection by-products (DBPs), including haloacetonitriles, haloketones, chloropicrin, cyanogen halides and trihalomethanes, during chloramination were investigated using model solutions containing 5 mg/L (as DOC) Suwannee River natural organic matter (NOM). Chloramine speciation and some DBPs were measured using membrane introduction mass Spectrometer (MIMS). Longer reaction times led to continued formation over time for dichloroacetonitrile (DCAN), 1,1-dichloro-2-propanone (1,1-DCP) and chloroform. Cyanogen chloride (CNCl) formation occurred over time, but after reaching a peak concentration CNCl concentrations decreased over longer time periods. Linear relationships were observed between the formation of DCAN, 1,1-DCP, CNCl or chloroform and the dosage of monochloramine. Chloramination modes (addition of preformed monochloramine or variable sequential additions of free chlorine and ammonium salts) exhibited the largest impact on chloroform formation but displayed little effect on the formation of DCAN, 1,1-DCP and CNCl. Over the range in pH from 4 to 9 profound differences in DBP formation were observed; pH values between 5 and 6 resulted in the highest DBP concentrations. An increase in temperature enhanced the formation of chloroform but did not affect DCAN, 1,1-DCP and CNCl formation. Chloropicrin concentrations were always low (around detection limits) under all conditions. Increasing the concentrations of bromide ions enhanced the formation of bromine-substituted DBPs.     

Influence of nitrogen source on NDMA formation during chlorination of diuron

N-Nitrosodimethylamine (NDMA) is formed during chlorination of water containing the herbicide diuron (N′-(3,4-dichlorophenyl)-N,N-dimethylurea) but formation is greatly enhanced in the presence of ammonia (chloramination). Groundwater impacted by agricultural runoff may contain diuron and relatively high total nitrogen concentrations; this study examines the impact of the nitrogen form (ammonium, nitrite or nitrate) on NDMA formation during chlorination of such waters. NDMA formation during chlorination of diuron increased in the order nitrite < nitrate < ammonium for a given chlorine, nitrogen, and diuron dose. Formation of dichloramine seemed to fully explain enhanced NDMA formation in the presence of ammonium. Nitrate unexpectedly enhanced nitrosation of diuron derivatives to form NDMA compared to the cases of no added nitrogen or nitrite addition. Nitrite addition is less effective because it consumes more chlorine and produces intermediates that react rapidly with diuron and its aromatic byproducts. Differences between surface water and groundwater in nitrogen forms and concentrations and disinfection approaches suggest strategies to reduce NDMA formation should vary with drinking water source.     

Formation of aldehydes upon ClO2 disinfection

Carbonyl compounds are considered to be the most common ozonation by-products. Apart from well-known chlorites and chlorates, chlorine dioxide (ClO(2)) also generates organic by-products. The goal of this paper is an investigation into the influence of disinfection with ClO(2) on the aldehydes formation. Three types of waters were disinfected with different doses of ClO(2) at the various pH values. The results of size exclusion chromatography show that the reaction of ClO(2) with humic fraction of natural organic matter proceeds mainly on an aromatic part of the molecules. The results obtained indicate that the level of carbonyls concentration can significantly increase with the time of ClO(2) reaction with carbonyl precursors in treated water. There is no noticeable correlation between quantity of aldehydes and pH value of disinfected water. The range of "productivity" of aldehydes in water treated with chlorine dioxide is similar to the range estimated for the carbonyls formed upon ozonation.     

THM, HAA and CNCl formation from UV irradiation and chlor(am)ination of selected organic waters

The formation of disinfection by-products (DBPs), including chloroform, dichloroacetic acid (DCAA), trichloroacetic acid (TCAA), and cyanogen chloride (CNCl) after sequential exposure of four organic waters to UV irradiation via either low- or medium-pressure lamps and free chlorine (or preformed monochloramine) under practical conditions was simulated. Statistically significant changes in the DBP formation from chlorination due to the additional UV irradiation are commonly observed under testing conditions, although some of these changes are not practically significant. The impacts from UV exposure were found to be most significant in chloroform formation (up to 40 microg/L) among the four tested DBPs. Organics from rivers were more sensitive to UV alteration than was the organic drawn from soil. This difference could not be explained by the specific UV absorbance (SUVA) values. In most cases, irradiation with the medium-pressure UV lamp gave similar or slightly larger changes in DBP yields, compared with the corresponding trials using the low-pressure lamp. Different application sequences could significantly change the relative quantities of DBPs but no general trend was identified. Case-specific evaluation of the formation of chloroform and CNCl is necessary.     

Formation of nitrosodimethylamine (NDMA) during chlorine disinfection of wastewater effluents prior to use in irrigation systems

The probable human carcinogen nitrosodimethylamine (NDMA) is produced when wastewater effluent is disinfected with chlorine. In systems where wastewater effluent is used for landscape or crop irrigation, relatively high chlorine doses (i.e., up to 2,000,mg-min/L) are often used to ensure adequate disinfection and to minimize biofouling in the irrigation system. To assess the formation of NDMA in such systems, samples were collected from several locations in full-scale wastewater treatment systems and their associated irrigation systems. Up to 460 ng/L of NDMA was produced in full-scale systems in which chloramines were formed when wastewater effluent was disinfected with chlorine in the presence of ammonia. Less than 20 ng/L of NDMA was produced in systems that used free chlorine (i.e., HOCl/OCl(-)) for disinfection in the absence of ammonia. The production of NDMA in ammonia-containing systems was correlated with the concentration of NDMA precursors in the wastewater effluent and the overall dose of chlorine applied. Much of the NDMA formation occurred in chlorine contact basins or in storage basins where water that contained chloramines was held after disinfection. When landscape or crop irrigation is practiced with ammonia-containing wastewater effluent, NDMA production can be controlled by use of lower chlorine doses or by application of alternative disinfectants.     

Modeling dichloroacetic acid formation from the reaction of monochloramine with natural organic matter

A kinetic model was developed to predict dichloroacetic acid (DCAA) formation in chloraminated systems. Equations describing DCAA formation were incorporated into an established comprehensive monochloramine-natural organic matter (NOM) reaction model. DCAA formation was theorized to be proportional to the amount of NOM oxidized by monochloramine and described by a single dimensionless DCAA formation coefficient, theta(DCAA) (M(DCAA)/M(DOC(ox)). The applicability of the model to describe DCAA formation in the presence of six different NOM sources was evaluated. DCAA formation could be described by considering a single NOM source-specific value for theta(DCAA) over a wide range of experimental conditions (i.e., pH, NOM, free ammonia, and monochloramine concentrations). DCAA formation appears to be directly proportional to the amount of active chlorine (monochloramine and free chlorine) that reacted with the NOM under these experimental conditions. Values of theta(DCAA) for all six NOM sources, determined by nonlinear regression analysis, varied from 6.51 x 10(-3) to 1.15 x 10(-2) and were linearly correlated with specific ultraviolet absorbance at 280 nm (SUVA(280)). The ability to model monochloramine loss and DCAA formation in the presence of NOM provides insight into disinfection by-product (DBP) formation pathways under chloramination conditions. The subsequent model and correlations to SUVA has the potential to aid the water treatment industry as a tool in developing strategies that minimize DBP formation while maintaining the microbial integrity of the water distribution system.