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Occurrence of nitrosamines and their precursors in North American drinking waters
Abstract
Eight N‐nitrosamines were measured at 37 water plants in the United States and Canada. Five tobacco‐specific nitrosamines (TSNAs) were measured in selected waters. N‐Nitrosodimethylamine (NDMA) was preferentially formed in chloraminated systems (maximum detention time: median 4.4 ng/L). A small amount was detected in some chlorinated systems (90th percentile <2.0 ng/L). After ozone (before chloramines), NDMA was sometimes detected (90th percentile 2.9 ng/L), suggesting that the ozone did not react with precursors to form NDMA. The chloramine plants that temporarily switched to chlorine typically produced less NDMA (Plant 29 reduced NDMA formation, on average, from 34 to 4 ng). More NDMA was produced during spring runoff, when there were elevated levels of ammonia and NDMA precursors in the source water. More NDMA was formed when there were higher levels of poly(diallyldimethylammonium chloride) (polyDADMAC) used. N‐Nitrosomorpholene was found to be a contaminant and not a disinfection byproduct; it did not increase during chloramination. TSNAs were produced during spring runoff; source water ammonia impacted the chlor(am)ine chemistry.
N-Nitrosamines, well-known human carcinogens, are widely considered to be formed through the disinfection of waters containing compounds with amine moieties. The formation mechanisms of nitrosamines during the disinfection of drinking water and wastewater have been previously reviewed in the literature. However, no study to date has reviewed the effects of inorganic ions on nitrosamines formation during disinfection. Inorganic ions are ubiquitous in the environment and are present at significant concentrations in water and wastewater. Their presence influences aqueous nitrosamines formation, depending on the type, concentration, and environmental conditions. In this review, we have critically reviewed nitrosamines’ precursors and occurrence, disinfection processes associated with nitrosamines’ formation/destruction, and the impact of inorganic ions on the formation or removal of nitrosamines during disinfection of water and wastewater. The disinfectants reviewed in the study were chlorine, chloramine, chlorine dioxide, ozone, and radicals generated through advanced oxidation processes (AOPs). N-Nitrosodimethylamine formation pathways, in the presence and absence of inorganic ions, were also reviewed to summarize our current understanding. Although chloramination has been associated with the formation of nitrosamines, many ozonation studies have also shown significant levels of nitrosamines formation. Pre-oxidation and AOPs have been reported as the most promising mitigation strategies for controlling nitrosamines formation, requiring prolonged exposure of precursors for effective mineralization.
As potable reuse guidelines and regulations continue to develop, the presence of N-nitrosamines is a primary concern because of their associated health concerns. In this study, bench-, pilot-, and full-scale tests were conducted to focus on the occurrence and treatment of N-nitrosomorpholine (NMOR) in United States (U.S.) potable reuse systems. Out of twelve U.S. wastewater effluents collected, ambient NMOR was detected in eleven (average = 20 ± 18 ng/L); in contrast, only two of the thirteen surface water and stormwater samples had NMOR. Across all of these samples maximum formation potential by chloramination produced an average increase of 3.6 ± 1.8 ng/L. This result underscores the need to understand the sources of NMOR as it is not likely a disinfection byproduct and it is not known to be commercially produced within the U.S. At the pilot-scale, three potable reuse systems were evaluated for ambient NMOR with oxidation (i.e., chlorination and ozonation), biofiltration, and granular activated carbon (GAC). Both pre-oxidation and biofiltration were ineffective at mitigating NMOR during long-term pilot plant operation (at least eight-months). GAC adsorbers were the only pilot-scale treatment to remove NMOR; however, complete breakthrough occurred rapidly from <2000 to 10,000 bed volumes. For comparison, a full-scale reverse osmosis (RO) potable reuse system was monitored for a year and confirmed that RO effectively removes NMOR. Systematic bench-scale UV-advanced oxidation experiments were undertaken to assess the mitigation potential for NMOR. At a fluence dose of 325 ± 10 mJ/cm² UV alone degraded 90% of the NMOR present. The addition of 5 mg/L hydrogen peroxide did not significantly decrease the UV dose required for one-log removal. These data illustrate that efficient NMOR removal from potable reuse systems is limited to RO or UV treatment.
Nitrosamine data reported from the first rounds of samples collected under the second Unregulated Contaminants Monitoring Rule (UCMR2) were reviewed to assess the frequency and magnitude of occurrence and the effect of disinfectant type and other treatment factors on reported nitrosamine concentrations. N-nitrosodimethylamine (NDMA) was detected in drinking water at concentrations above the UCMR2 minimum reporting level of 2 ng/L in 1 of every 10 samples, primarily in systems using chloramines. Other nitrosamines (i.e., N-nitrosodiethylamine [NDEA], N-nitrosopyrrol idine [NPYR], N-nitroso-di-n- butylamine [NDBA], and N-nitrosodimethylethylamine [NMEA]) were rarely detected. Followup survey results from 45 water systems generally followed expected trends based on the literature. NDMA occurrence was more frequent, and concentrations were higher in water systems having long contact times with chloramines and with no preoxidation step.
N-Nitrosodimethylamine (NDMA) is a member of a family of extremely potent carcinogens, the N-ni-trosamines. Until recently, concerns about NDMA mainly focused on the presence of NDMA in food, consumer products, and polluted air. However, current concern focuses on NDMA as a drinking water contaminant resulting from reactions occurring during chlorination or via direct industrial contamination. Because of the relatively high concentrations of NDMA formed during wastewater chlorination, the in-tentional and unintentional reuse of municipal wastewater is a particularly important area of concern. Al-though ultraviolet (UV) treatment can effectively remove NDMA, there is considerable interest in the de-velopment of less expensive alternative treatment technologies. These alternative technologies include approaches for removing organic nitrogen-containing NDMA precursors prior to chlorination and the use of sunlight photolysis, and in situ bioremediation to remove NDMA and its precursors.
The seasonal and diurnal patterns of N-nitrosomorpholine (NMOR) and its formation potential (NMOR FP) were examined with water samples taken from five outlets of four sewage treatment plants (STPs), seven main stream sites, and five tributary sites in the Yodo River basin. STPs were shown to be the main sources of downstream NMOR load. The highest NMOR levels were found in the discharge from one STP (26.4-171 ng/L). Continuous sequential samplings over a period of 24 h at this STP revealed that NMOR flux at the influent point fluctuated in both summer (0.4-3.2 g/h) and winter (0.3-5.4 g/h), while it was steady in the effluent. In addition, levels of NMOR remained stable during the biological treatment and disinfection processes. The present research demonstrated that NMOR could be formed from morpholine (MOR) in raw sewage treated by this STP, with a possible mechanism being formaldehyde-catalyzed nitrosation of MOR by nitrites, prior to raw sewage entering the STP. This implies that the NMOR detected here might not be a disinfection byproduct per se under low-chlorine disinfection (around 1.0 mg/L), but is primarily a contaminant that is difficult to remove during sewage treatment. NMOR attenuated significantly in the rivers in the daytime with production of MOR, but persisted during nights, which demonstrated the importance of monitoring NMOR levels in the water environment during periods of low UV intensity, especially nights.
A source-to-tap evaluation of the origin and fate of chloramination N-nitrosodimethylamine (NDMA) precursors at 21 full-scale drinking water plants was conducted. Upstream wastewater discharges accounted for (on a median basis) ~16 ng/L NDMA formation potential (FP). A correlation between concentrations of the artificial sweetener sucralose (wastewater tracer) and NDMA FP was found within certain watersheds, with increased river flow decreasing sucralose and NDMA FP concentrations by diluting the wastewater discharges. The polymers polydiallyldimethylammonium chloride (polyDADMAC) and polyamine contributed (median) 6 and 14 ng/L of NDMA FP to coagulated water (which was pre-chloraminated in two cases), respectively. Biofiltration increased NDMA FP by (median) 6 ng/L; biofiltration tended to increase precursor loading rather than reduce it. Although wastewater and polymers are known sources of precursors, biofilters as a source of precursors was an important finding. Ozonation of raw or settled water was effective at destroying NDMA precursors (median 34%). As free chlorine exposure increased (from ≤3 min to >1 hr), NDMA formation in the chloraminated distribution system decreased (from median removal of 21% to 90% of the NDMA FP sampled prior to chlorination). For either oxidant, precursor abatement was typically higher at pH ~8-9 than at 7. Riverbank filtration, and powdered and granular activated carbon removed (median) 64, 47, and 64% of watershed-derived NDMA precursors, respectively. Each was able to remove NDMA FP better than that of the bulk total organic carbon. Granular activated carbon did not appear to be effective at removing polyDADMAC-derived precursors added during coagulation. The contribution of different watershed or in-plant sources to NDMA precursors varies by plant and over time and, depending upon precursor sources, different in-plant treatment strategies can effectively control NDMA formation.
Bench‐scale chloramination under uniform formation conditions was used to examine N‐nitrosodimethylamine (NDMA) formation in settled and (bio)filtered drinking water and treated wastewater. In this study, water temperature, pH, postchloramination time, and chlorine‐to‐nitrogen (Cl2/N) weight ratio were varied to investigate NDMA formation in various water types. Wastewater and certain polymers were investigated as sources of NDMA precursors. Nitrified biofilters were found to be another precursor source. NDMA formation in nitrified biofilter effluent and polymer‐impacted water was the highest at Cl2/N of 3–5; NDMA formation was the highest at Cl2/N of 5–7 in wastewater‐impacted waters. Other tests at Cl2/N of 4.75 evaluated the impact of pH and temperature, with a 3 min prechlorination, which can result in some precursor abatement. At pH 7, NDMA formation increased with increasing temperature, whereas at pH 8 and 9, low temperature sometimes yielded higher NDMA formation because of lower precursor abatement during prechlorination and, thus, higher NDMA formation during postchloramination.
Sucralose is an artificial sweetener and an indicator of wastewater impacts in drinking water. N-nitrosodimethyamine (NDMA) is a disinfection by-product with wastewater-derived precursors. In two studies conducted in the United States and Canada, data showed watershed and region-specific relationships between sucralose occurrence, stream flow, and NDMA formation potential (FP). In addition, other water supplies have been identified with high NDMA FP that were low in sucralose, which appeared to be impacted by other sources of precursors in the watershed during high-flow events (e.g., runoff). In these studies, seasonal and climatic effects were explored where changes in stream flow (e.g., storm events, droughts) and sucralose and NDMA FP have been well correlated in many watersheds. These studies demonstrate the usefulness of measuring sucralose, including the determination of site-specific correlations with NDMA FP and temporal variability, as well as determining the likely percentage of treated wastewater in the influent of drinking water treatment plants.
A comparison of loadings of N-nitrosamines and their precursors from different source water categories is needed to design effective source water blending strategies. Previous research using Formation Potential (FP) chloramination protocols (high dose and prolonged contact times) raised concerns about precursor loadings from various source water categories, but differences in the protocols employed rendered comparisons difficult. In this study, we applied Uniform Formation Condition (UFC) chloramination and ozonation protocols mimicking typical disinfection practice to compare loadings of ambient specific and total N-nitrosamines as well as chloramine-reactive and ozone-reactive precursors in 47 samples, including 6 pristine headwaters, 16 eutrophic waters, 4 agricultural runoff samples, 9 stormwater runoff samples, and 12 municipal wastewater effluents. N-Nitrosodimethylamine (NDMA) formation from UFC and FP chloramination protocols did not correlate, with NDMA FP often being significant in samples where no NDMA formed under UFC conditions. N-Nitrosamines and their precursors were negligible in pristine headwaters. Conventional, and to a lesser degree, nutrient removal wastewater effluents were the dominant source of NDMA and its chloramine- and ozone-reactive precursors. While wastewater effluents were dominant sources of TONO and their precursors, algal blooms, and to a lesser degree agricultural or stormwater runoff, could be important where they affect a major fraction of the water supply.
N-Nitrosamines (NAs) in drinking water have attracted considerable attention in recent years due to their high carcinogenicity, frequent occurrence, and their potential regulation. During the past three years, we have collected about 164 water samples of finished water, tap water, and source water from 23 provinces, 44 cities from large cities to small towns, and 155 sampling points all over China. The occurrence of NAs in the finished and tap water was much higher in China than that in the U.S. Nine NAs were measured and NDMA had the highest concentration. The occurrence of NDMA was in 33% of the finished waters of water treatment plants and in 41% of the tap waters. The average NDMA concentration in finished and tap waters was 11 and 13 ng/L, respectively. Formation potentials (FPs) of source waters were examined with an average NDMA FP of 66 ng/L. Large variations in NA occurrence were observed geographically in China and temporally in different seasons. The Yangtze River Delta area, one sub-area in East China, had the highest concentrations of NAs, where the average NDMA concentrations in the finished and tap water were 27 and 28.5 ng/L, respectively, and the average NDMA FP in the source water was 204 ng/L. NA control may be achieved by applying breakpoint free chlorination and/or advanced treatment of ozone - granular activated carbon process to remove the NA precursors before disinfection.
A comprehensive examination of nitrosamines was conducted in a water system, which included sewage treatment plants (STPs), river water, and seawater to understand their characteristic occurrence and fates in whole real water system. The concentrations of nitrosamines were highest in the STP influent (1440-29,100ng/L), followed by the river water (26.0-5180ng/L), the STP effluent (9.58-310ng/L), and seawater (44.2-155ng/L). The samples were especially affected by proximity to the industrial zone and the samples collected near industrial complex had much higher levels than others with different distribution patterns. In the STPs, nitrosamines were mostly eliminated during biological treatment processes (86.7-95.0%), while they were formed through chlorination processes (-59.6 to -27.7%), which is consistent with previous surveys. The primary clarifier showed insignificant elimination tendencies (5.6-28.2%). Although removal by ultraviolet light was effective (73.2-94.1%), more surveys may be needed because of conflicting results in other studies. Among water quality parameters, nitrosamines in waste water were linked with organic carbon and nitrogen levels.
Detention times in the distribution system of MWDSC were typically of the order of minutes to hours, except for in a covered finished water reservoir. As NDMA formation is slow, its concentration was found to increase in the reservoir. Moreover, NDMA levels increased in the distribution system of CSs. A hold study was used to demonstrate the impact of detention time on NDMA formation. In some of the CSs sampled, nitrification was occurring. In most cases, this did not appear to impact NDMA formation. However, in one location, there was substantially more nitrite and NDMA formation, where nitrosation may have contributed (in part) to the formation of NDMA. In one CS sampled, which blended MWDSC's surface water with their groundwater, the groundwater supply appeared to be a source of NMOR. The sampling conducted to date showed that detention time, possibly nitrification, and sources of other nitrosamines must be considered when comparing nitrosamine occurrence in CSs to that of the wholesaler. Also, there were seasonal variations in these impacts. This information is important in understanding the formation and control of nitrosamines in CSs. © 2012 American Water Works Association AWWA WQTC Conference Proceedings.
Utilities using chloramines need strategies to mitigate nitrosamine formation to meet potential future nitrosamine regulations. The ability to reduce NDMA formation under typical post-chloramination conditions of pretreatment with ultraviolet light from a low pressure mercury lamp (LPUV), free chlorine (HOCl), ozone (O3), and UV light from a medium pressure mercury lamp (MPUV) were compared at exposures relevant to drinking water treatment. The order of efficacy after application to waters impacted by upstream wastewater discharges was O3 > HOCl ≈ MPUV > LPUV. NDMA precursor abatement generally did not correlate well between oxidants, and waters exhibited different behaviors with respect to pH and temperature, suggesting a variety of source-dependent NDMA precursors. For wastewater-impacted waters, the observed pH dependence for precursor abatement suggested the important role of secondary or tertiary amine precursors. Although hydroxyl radicals did not appear to be important for NDMA precursor abatement during O3 or MPUV pretreatment, the efficacy of MPUV correlated strongly with dissolved organic carbon concentration (p = 0.01), suggesting alternative indirect photochemical pathways. The temperature dependences during pre- and post-disinfection indicated that NDMA formation is likely to increase during warm seasons for O3 pretreatment, decrease for HOCl pretreatment, and remain unchanged for MPUV treatment, although seasonal changes in source water quality may counteract the temperature effects. For two waters impacted by relatively high polyDADMAC coagulant doses, pretreatment with HOCl, O3, and MPUV increased NDMA formation during post-chloramination. For O3 pretreatment, hydroxyl radicals likely led to precursor formation from the polymer in the latter tests. MPUV treatment of polymer-impacted water increased subsequent NDMA formation through an indirect photochemical process. Many factors may mitigate the importance of this increased NDMA formation, including the low polyDADMAC doses typically applied, and simultaneous degradation of watershed-associated precursors.
Copyright © 2015 [The Author/The Authors]. Published by Elsevier Ltd.. All rights reserved.
A survey for N-nitrosodimethylamine (NDMA) and seven other nitrosamines in six UK drinking water supply systems was conducted. At the time of the study, there was no NDMA data for UK drinking waters, and the study remains one of few globally to report concentrations of the other seven nitrosamines in water supply systems. Five of the six water supply systems were selected as probable to have elevated nitrosamine concentrations because of the known source water characteristics and/or treatment practices; the sixth supply system had none of the suspected risk factors and was included as a control case. Sampling was conducted in five intervals and included samples collected from the source water, post-filter, post-disinfection and the distribution system. NDMA was measured barely above the method detection limit (0.9 ngl-1) in a few isolated samples in one distribution system; however, otherwise the majority of samples contained no detectable NDMA or other nitrosamines. An exception was that N-nitrosodibutylamine (NDBA) was consistently detected in one distribution system, up to a maximum concentration of 6.4 ngl-1. There were no identifiable relationships to link source water characteristics, the particular treatment processes or distribution system contact time with the observed nitrosamine concentrations.
The US Environmental Protection Agency's (USEPA's) final database for the second Unregulated Contaminant Monitoring Rule (UCMR2) was analyzed in depth for N-nitrosodimethylamine (NDMA) occurrence nationwide. Detectable levels of NDMA were found in 17% of samples and 25% of treatment plants. The other five listed nitrosamines were detected in fewer than 1% of samples. The strongest factor found positively associated with NDMA occurrence was chloramine use. Likewise, the use of surface waters was found to be linked to NDMA occurrence such that surface waters (even when decoupled from chloramine use) demonstrated elevated levels of NDMA more than groundwater sources did. No clear seasonal trends could be deciphered, but data supplied from utilities servicing fewer than 10,000 people provide evidence that smaller utilities have some of the most extreme NDMA levels and subsequently may have a difficult time meeting future NDMA regulations.
Nitrosamines are a class of toxic disinfection byproducts commonly associated with chloramination, of which several were included on the most recent U.S. EPA Contaminant Candidate List. Nitrosamine formation may be a significant barrier to ozonation in water reuse applications, particularly for direct or indirect potable reuse, since recent studies show direct formation during ozonation of natural water and treated wastewaters. Only a few studies have identified precursors which react with ozone to form N-nitrosodimethylamine (NDMA). In this study, several precursor compound solutions, prepared in ultrapure water and treated wastewater, were subjected to a 10 M excess of ozone. In parallel experiments, the precursor solutions in ultrapure water were exposed to gamma radiation to determine NDMA formation as a byproduct of reactions of precursor compounds with hydroxyl radicals. The results show six new NDMA precursor compounds that have not been previously reported in the literature, including compounds with hydrazone and carbamate moieties. Molar yields in deionized water were 61-78% for 3 precursors, 12-23% for 5 precursors and <4% for 2 precursors. Bromide concentration was important for three compounds (1,1-dimethylhydrazine, acetone dimethylhydrazone and dimethylsulfamide), but did not enhance NDMA formation for the other precursors. NDMA formation due to chloramination was minimal compared to formation due to ozonation, suggesting distinct groups of precursor compounds for these two oxidants. Hydroxyl radical reactions with the precursors will produce NDMA, but formation is much greater in the presence of molecular ozone. Also, hydroxyl radical scavenging during ozonation leads to increased NDMA formation. Molar conversion yields were higher for several precursors in wastewater as compared to deionized water, which could be due to catalyzed reactions with constituents found in wastewater or hydroxyl radical scavenging.
Tobacco-specific nitrosamines (TSNAs) exist in environmental waters, however, it is unknown whether TSNAs can be produced during water disinfection. Here we report on the investigation and evidence of TSNAs as a new class of disinfection byproducts (DBPs). Using five common TSNAs, including (methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) as the targets, we first developed a solid phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) method capable of rapidly determining these TSNAs as low as 0.02 ng/L in treated water. Using this highly sensitive method, we investigated the occurrence and formation potential (FP) (precursor test conducted in the presence of chloramines) of TSNAs in treated water from two wastewater treatment plants (WWTPs) and seven drinking water treatment plants (DWTPs). NNAL was detected in the FP samples, but not in the samples before the FP test, confirming NNAL as a DBP. NNK was detected in the treated wastewater before the FP test, but its concentration increased significantly after chloramination in two of three tests. Thus NNK could be a DBP and/or a contaminant in wastewater. Moreover, these TSNAs were detected in FP tests of wastewater-impacted DWTP plant influents in 9 of 11 samples. However, TSNAs were not detected at full-scale DWTPs, except for at one DWTP with high ammonia where breakpoint chlorination was not achieved. The concentration of the sum of five TSNAs (0.3 ng/L) was 100-fold lower than NDMA, suggesting that TSNAs have a minor contribution to total nitrosamines in water. We examined several factors in the treatment process and found that chlorine or ozone may destroy TSNA precursors and GAC treatment may remove the precursors. Further research is warranted into the efficiency of these processes at different DWTPs using sources of varying water quality.
The survey design, implementation, and responses of water utilities and comparison of estimates of the use of chloramines from the economic analysis with survey response estimates, are discussed. The primary aim of the survey was to determine the percentage of utilities currently using chloramines and those adapting to it in the near future. It was found that 29% of community water systems currently use chloramines for secondary disinfection, and another 3% are in the process of converting to chloramines. Economic analysis of estimates of the use of chloramines were higher for both the current and future practice than the survey respondents indicated, while for groundwater systems, it was lower one.
Unintentional, indirect wastewater reuse often occurs as wastewater treatment plant (WWTP) discharges contaminate receiving waters serving as drinking-water supplies. A survey was conducted at 23 WWTPs that utilized a range of treatment technologies. Samples were analyzed for typical wastewater and drinking-water constituents, chemical characteristics of the dissolved organic matter (DOM), and disinfection byproduct (DBP) precursors present in the effluent organic matter (EfOM). This was the first large-scale assessment of the critical water quality parameters that affect the formation of potential carcinogens during drinking water treatment relative to the discharge of upstream WWTPs. This study considered a large and wide range of variables, including emerging contaminants rarely studied at WWTPs and never before in one study. This paper emphasizes the profound impact of nitrification on many measures of effluent water quality, from the obvious wastewater parameters (e.g., ammonia, biochemical oxygen demand) to the ones specific to downstream drinking water treatment plants (e.g., formation potentials for a diverse group of DBPs of health concern). Complete nitrification reduced the concentration of biodegradable dissolved organic carbon (BDOC) and changed the ratio of BDOC/
This review summarizes major findings over the last decade related to nitrosamines in drinking water, with a particular focus on N-nitrosodimethylamine (NDMA), because it is among the most widely detected nitrosamines in drinking waters. The reaction of inorganic dichloramine with amine precursors is likely the dominant mechanism responsible for NDMA formation in drinking waters. Even when occurrence surveys found NDMA formation in chlorinated drinking waters, it is unclear whether chloramination resulted from ammonia in the source waters. NDMA formation has been associated with the use of quaternary amine-based coagulants and anion exchange resins, and wastewater-impaired source waters. Specific NDMA precursors in wastewater-impacted source waters may include tertiary amine-containing pharmaceuticals or other quaternary amine-containing constituents of personal care products. Options for nitrosamine control include physical removal of precursors by activated carbon or precursor deactivation by application of oxidants, particularly ozone or chlorine, upstream of chloramination. Although NDMA has been the most prevalent nitrosamine detected in worldwide occurrence surveys, it may account for only ∼5% of all nitrosamines in chloraminated drinking waters. Other significant contributors to total nitrosamines are poorly characterized. However, high levels of certain low molecular weight nitrosamines have been detected in certain Chinese waters suspected to be impaired by industrial effluents. The review concludes by identifying research needs that should be addressed over the next decade.
Since the 1974 discovery of trihalomethanes as disinfection by-products (DBPs) in drinking water, the regulatory and public health focus has been primarily directed at halogenated compounds, even though it is well established that chlorination and chloramination also produce non-halogenated DBPs. Specific halogenated DBPs that could reasonably explain the correlation of some adverse health outcomes with consumption of disinfected drinking water in a number of epidemiologic studies have yet to be identified. We therefore explored an emerging class of non-halogenated DBPs, N-nitrosamines, which warrant consideration given public health concerns regarding possible correlations of bladder cancer with exposure to chlorinated drinking water. We developed a dual media (Ambersorb® 572 and LiChrolut® EN), off-line, solid-phase extraction method that utilized a modified commercially-available extraction manifold combined with our previous GC–MS ammonia positive chemical ionization (PCI) quantitative method for analyzing N-nitrosamines in drinking water. We surveyed 20 Alberta municipal drinking-water distribution systems for the presence of N-nitrosodimethylamine (NDMA) and seven other N-nitrosamine species. Analytical results revealed the occurrence of NDMA (up to 100 ng/L) as well as two other N-nitrosamines (N-nitrosopyrrolidine and N-nitrosomorpholine) within select Alberta drinking water supplies.Key words: Alberta, chloramination, disinfection by-products, distribution system, drinking water, N-nitrosamines, NDMA, public health, survey.
Anion exchange resins are important tools for the removal of harmful anionic contaminants from drinking water, but their use has been linked to the presence of carcinogenic nitrosamines in treated drinking water. In bench-scale batch and column experiments, anion exchange resins from a large, representative group were investigated as sources of the nitrosamines N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosodi-n-propylamine (NDPA) and N-nitrosodi-n-butylamine (NDBA) and their precursors. Several resins were found to release high levels (up to >2000 ng/L, orders of magnitude above drinking water regulatory levels) of nitrosamines upon initial rinsing with lab-grade water, with levels subsiding within 50-100 bed volumes of rinsing. Resins released similarly high levels of nitrosamine precursors, with spikes in precursor release triggered by regeneration of resins with sodium chloride or by interruptions in flow resulting in prolonged contact times. Free chlorine or preformed monochloramine in feed water led to the production of nitrosamines. Resins released different nitrosamines and precursors depending on their functional groups, with some resins releasing as many as three different nitrosamines and their precursors. These findings have significant implications for the pretreatment and appropriate use of anion exchange resins by drinking water utilities and for the production of anion exchange resins by manufacturers.
A U.S.-wide occurrence survey conducted as part of the Unregulated Contaminant Monitoring Rule 2 found that N-nitrosodimethylamine (NDMA) was present in 34% of chloraminated drinking water samples, but was the most prevalent of the 6 N-nitrosamines evaluated using U.S. EPA Method 521. If the U.S. EPA considers limiting exposures to N-nitrosamines as a group, a critical question is whether NDMA is the most prevalent N-nitrosamine, or whether significant concentrations occur for N-nitrosamines other than those captured by EPA Method 521. A total N-nitrosamine assay was developed and applied to 36 drinking water plant effluents or distribution system samples from 11 utilities, including 9 utilities that practiced chloramination for secondary disinfection. Concurrent application of EPA Method 521 indicated that NDMA was the most prevalent of the Method 521 N-nitrosamines, yet accounted for ~5% of the total N-nitrosamine pool on a median basis. Among 8 plant influent waters, NDMA was detected once, while total N-nitrosamines were detected in 5 samples, suggesting the importance of source water protection. Similar to NDMA, total N-nitrosamine concentrations in source waters increased after chloramination. Chloramines were applied to model organic precursors for pristine natural organic matter, algal exudate, wastewater effluent and polyDADMAC quaternary amine-based coagulation polymers. While high yields of NDMA were restricted to the wastewater effluent and polyDADMAC, high yields of total N-nitrosamines were observed from the algal exudate, the wastewater effluent and polyDADMAC. The results suggest that N-nitrosamines as a class may be more prevalent than suggested by occurrence surveys conducted using EPA Method 521.
The spatiotemporal presence of eight N-nitrosamines in the water of seven supply systems in Quebec considered to be susceptible to these emerging disinfection by-products was evaluated. This is the first study on the presence of N-nitrosamines in drinking water utilities in Quebec. Seven sampling campaigns were carried out at several sampling points in each of the systems over a period of 1 year. The results show that N-nitrosamines, primarily N-nitrosodimethylamine (NDMA), were not commonly detected in the water of the facilities under study (10 % of samples). The concentrations measured were lower than those reported in recent North American studies. None of the 195 samples taken exceeded the Ontario standard of 9 ng/L for NDMA (maximum value observed of 3.3 ng/L). N-nitrosomethylethylamine and N-nitrosopiperidine were detected once, with concentrations of 3.7 and 6.0 ng/L, respectively. Chloramination was identified as being the main risk factor regarding the presence of N-nitrosamines, but water quality and some operating parameters, in particular disinfectant residual, also seem to be related to their presence. NDMA concentrations at the end of the distribution systems were generally higher than water leaving the plant. No seasonal trends were observed for the formation of N-nitrosamines in the investigated supply systems. Finally, an association between the presence of N-nitrosamines and the levels of trihalomethanes and haloacetic acids was observed in some facilities.
Activated carbon (AC) has been shown to remove precursors of halogenated disinfection byproducts. Granular and powdered activated carbon (GAC, PAC) were investigated for their potential to adsorb N-nitrosodimethylamine (NDMA) precursors from blends of river water and effluent from a wastewater treatment plant (WWTP). At bench scale, waters were exposed to lignite or bituminous AC, either as PAC in bottle point experiments or as GAC in rapid small-scale column tests (RSSCTs). NDMA formation potential (FP) was used as a surrogate for precursor removal. NDMA FP was reduced by 37, 59, and 91% with 3, 8, and 75 mg/L of one PAC, respectively, with a 4-hr contact time. In RSSCTs and in full-scale GAC contactors, NDMA FP removal always exceeded that of the bulk dissolved organic carbon (DOC) and UV absorbance at 254 nm. For example, whereas DOC breakthrough exceeded 90% of its influent concentration after 10,000 bed volumes of operation in an RSSCT, NDMA FP was less than 40% of influent concentration after the same bed life of the GAC. At full or pilot scale, high NDMA FP reduction ranging from >60 to >90% was achieved across GAC contactors, dependent upon the GAC bed life and/or use of a pre-oxidant (chlorine or ozone). In all experiments, NDMA formation was not reduced to zero, which suggests that although some precursors are strongly sorbed, others are not. This is among the first studies to show that AC is capable of adsorbing NDMA precursors, but further research is needed to better understand NDMA precursor chemical properties (e.g., hydrophobicity, molecular size) and evaluate how best to incorporate this finding into full-scale designs and practice.
A kinetic model of the reacting aqueous chlorine-ammonia system is proposed which describes equally well the rapid "breakpoint" oxidation of ammonia, where the applied chlorine dose (Cl2) to ammonia-nitrogen molar ratio (Cl/N) is greater than approximately 1.6; the slow oxidation of ammonia in aqueous chloramine solutions (Cl/N < 1); and the transition region of 1 < Cl/N < 1.6, where rapid initial decay results in chloramine species residuals. Calculated time-dependent concentrations of the chlorine species, determined by numerical solution of the rate expressions, compare favorably to measured values, determined during experiments performed over ranges of initial pH (6-8) and Cl/N (0.25-2.0) conditions. The experimentally measured species include free chlorine (HOCl + OCl-), monochloramine (NH2Cl), and dichloramine (NHCl2). In addition, the model appropriately considers the catalysis of certain key reactions by several commonly encountered inorganics, such as bicarbonate and phosphate species.
An overview is given of existing trace analytical methods for the determination of seven popular artificial sweeteners [acesulfame (ACE), aspartame, cyclamate (CYC), neotame, neohesperidine dihydrochalcone, saccharin (SAC), and sucralose (SUC)] from aqueous environmental samples. Liquid chromatography-electrospray ionization tandem mass spectrometry and liquid chromatography-electrospray ionization high-resolution mass spectrometry are the methods most widely applied, either directly or after solid-phase extraction. Limits of detection and limits of quantification down to the low nanogram per liter range can be achieved. ACE, CYC, SAC, and SUC were detected in wastewater treatment plants in high microgram per liter concentrations. Per capita loads of individual sweeteners can vary within a wide range depending on their use in different countries. Whereas CYC and SAC are usually degraded by more than 90% during wastewater treatment, ACE and SUC pass through wastewater treatment plants mainly unchanged. This suggests their use as virtually perfect markers for the study of the impact of wastewater on source waters and drinking waters. In finished water of drinking water treatment plants using surface-water-influenced source water, ACE and SUC were detected in concentrations up to 7 and 2.4 μg/L, respectively. ACE was identified as a precursor of oxidation byproducts during ozonation, resulting in an aldehyde intermediate and acetic acid. Although the concentrations of ACE and SUC are among the highest measured for anthropogenic trace pollutants found in surface water, groundwater, and drinking water, the levels are at least three orders of magnitude lower than organoleptic threshold values. However, ecotoxicology studies are scarce and have focused on SUC. Thus, further research is needed both on identification of transformation products and on the ecotoxicological impact of artificial sweeteners and their transformation products.
Chloramines in drinking water may form N-nitrosodimethylamine (NDMA). Various primary disinfectants can deactivate NDMA precursors prior to chloramination. However, they promote the formation of other byproducts. This study compared the reduction in NDMA formation due to chlorine, ozone, chlorine dioxide, and UV over oxidant exposures relevant to Giardia control coupled with postchloramination under conditions relevant to drinking water practice. Ten waters impacted by treated wastewater, poly(diallyldimethylammonium chloride) (polyDADMAC) polymer, or anion exchange resin were examined. Ozone reduced NDMA formation by 50% at exposures as low as 0.4 mg×min/L. A similar reduction in NDMA formation by chlorination required ∼60 mg×min/L exposure. However, for some waters, chlorination actually increased NDMA formation at lower exposures. Chlorine dioxide typically had limited efficacy regarding NDMA precursor destruction; moreover, it increased NDMA formation in some cases. UV decreased NDMA formation by ∼30% at fluences >500 mJ/cm(2), levels relevant to advanced oxidation. For the selected pretreatment oxidant exposures, concentrations of regulated trihalomethanes, haloacetic acids, bromate, and chlorite typically remained below current regulatory levels. Chloropicrin and trichloroacetaldehyde formation were increased by preozonation or medium pressure UV followed by postchloramination. Among preoxidants, ozone achieved the greatest reduction in NDMA formation at the lowest oxidant exposure associated with each disinfectant. Accordingly, preozonation may inhibit NDMA formation with minimal risk of promotion of other byproducts. Bromide >500 μg/L generally increased NDMA formation during chloramination. Higher temperatures increased NDMA precursor destruction by preoxidants but also increased NDMA formation during postchloramination. The net effect of these opposing trends on NDMA formation was water-specific.
The artificial sweetener sucralose has recently been shown to be a widespread of contaminant of wastewater, surface water, and groundwater. In order to understand its occurrence in drinking water systems, water samples from 19 United States (U.S.) drinking water treatment plants (DWTPs) serving more than 28 million people were analyzed for sucralose using liquid chromatography tandem mass spectrometry (LC-MS/MS). Sucralose was found to be present in source water of 15 out of 19 DWTPs (47-2900 ng/L), finished water of 13 out of 17 DWTPs (49-2400 ng/L) and distribution system water of 8 out of the 12 DWTPs (48-2400 ng/L) tested. Sucralose was only found to be present in source waters with known wastewater influence and/or recreational usage, and displayed low removal (12% average) in the DWTPs where finished water was sampled. Further, in the subset of DWTPs with distribution system water sampled, the compound was found to persist regardless of the presence of residual chlorine or chloramines. In order to understand intra-DWTP consistency, sucralose was monitored at one drinking water treatment plant over an 11 month period from March 2010 through January 2011, and averaged 440 ng/L in the source water and 350 ng/L in the finished water. The results of this study confirm that sucralose will function well as an indicator compound for anthropogenic influence on source, finished drinking and distribution system (i.e., tap) water, as well as an indicator compound for the presence of other recalcitrant compounds in finished drinking water in the U.S.
Urban watersheds are susceptible to numerous pollutant sources and the identification of source-specific indicators can provide a beneficial tool in the identification and control of input loads, often times needed for a water body to achieve designated beneficial uses. Differentiation of wastewater flows from other urban wet weather flows is needed in order to more adequately address such environmental concerns as water body nutrient impairment and potable source water contamination. Anthropogenic compounds previously suggested as potential wastewater indicators include caffeine, carbamazepine, N,N-diethyl-meta-toluamide (DEET), gemfibrozil, primidone, sulfamethoxazole, and TCEP. This paper compares the suitability of a variety of anthropogenic compounds to sucralose, an artificial sweetener, as wastewater indicators by examining occurrence data for 85 trace organic compounds in samples of wastewater effluents, source waters with known wastewater point source inputs, and sources without known wastewater point source inputs. The findings statistically demonstrate the superior performance of sucralose as a potential indicator of domestic wastewater input in the U.S. While several compounds were detected in all of the wastewater effluent samples, only sucralose was consistently detected in the source waters with known wastewater discharges, absent in the sources without wastewater influence, and consistently present in septic samples. All of the other compounds were prone to either false negatives or false positives in the environment.
The worldwide detection of pharmaceuticals and personal care products (PPCPs) in the aquatic environment and drinking water has been a cause for concern in recent years. The possibility for concurrent formation of nitrosamine DBPs (disinfection by-products) during chloramine disinfection has become another significant concern for delivered drinking water quality because of their potent carcinogenicity. This study demonstrates that a group of PPCPs containing amine groups can serve as nitrosamine precursors during chloramine disinfection. Molar yields higher than 1% are observed for eight pharmaceuticals, with ranitidine showing the strongest potential to form N-nitrosodimethylamine (NDMA). The molar conversion increases with the Cl(2):N mass ratio, suggesting that dichloramine is relevant to the formation of NDMA from these precursors. Although the trace level of PPCPs in the environment suggests that they may not account for the majority of nitrosamine precursors during the disinfection process, this study demonstrates a connection between the transformation of PPCPs and the formation of nitrosamines during chloramine disinfection. This both expands the pool of potential nitrosamine precursors, and provides a possible link between the presence of trace levels of certain PPCPs in drinking water sources and potential adverse health effects.
Effluents from wastewater treatment plants (WWTPs) contain disinfection byproducts (DBPs) of health concern when the water is utilized downstream as a potable water supply. The pattern of DBP formation was strongly affected by whether or not the WWTP achieved good nitrification. Chlorine addition to poorly nitrified effluents formed low levels of halogenated DBPs, except for (in some cases) dihalogenated acetic acids, but often substantial amounts of N-nitrosodimethyamine (NDMA). Chlorination of well-nitrified effluent typically resulted in substantial formation of halogenated DBPs but much less NDMA. For example, on a median basis after chlorine addition, the well-nitrified effluents had 57 microg/L of trihalomethanes [THMs] and 3 ng/L of NDMA, while the poorly nitrified effluents had 2 microg/L of THMs and 11 ng/L of NDMA. DBPs with amino acid precursors (haloacetonitriles, haloacetaldehydes) formed at substantial levels after chlorination of well-nitrified effluent. The formation of halogenated DBPs but not that of NDMA correlated with the formation of THMs in WWTP effluents disinfected with free chlorine. However, THM formation did not correlate with the formation of other DBPs in effluents disinfected with chloramines. Because of the relatively high levels of bromide in treated wastewater, bromine incorporation was observed in various classes of DBPs.
Recent studies indicated that water treatment polymers such as poly(epichlorohydrin dimethylamine) (polyamine) and poly(diallyldimethylammonium chloride) (polyDADMAC) may form N-nitrosodimethylamine (NDMA) when in contact with chloramine water disinfectants. To minimize such potential risk and improve the polymer products, the mechanisms of how the polymers behave as NDMA precursors need to be elucidated. Direct chloramination of polymers and intermediate monomers in reagent water was conducted to probe the predominant mechanisms. The impact of polymer properties including polymer purity, polymer molecular weight and structure, residual dimethylamine (DMA), and other intermediate compounds involved in polymer synthesis, and reaction conditions such as pH, oxidant dose, and contact time on the NDMA formation potential (NDMA-FP) was investigated. Polymer degradation after reaction with chloramines was monitored at the molecular level using FT-IR and Raman spectroscopy. Overall, polyamines have greater NDMA-FP than polyDADMAC, and the NDMA formation from both polymers is strongly related to polymer degradation and DMA release during chloramination. Polyamines' tertiary amine chain ends play a major role in their NDMA-FP, while polyDADMACs' NDMA-FP is related to degradation of the quaternary ammonium ring group.
A nationwide survey of N-nitrosodimethylamine (NDMA) in both raw and finished water samples from drinking water treatment plants (DWTPs) in Japan was conducted. NDMA was analyzed by solid-phase extraction (SPE) followed by ultra performance liquid chromatography (UPLC) coupled with tandem mass spectrometry (MS/MS). NDMA was detected in 15 of 31 raw water samples collected in the summer at concentrations up to 2.6 ng/L, and in 9 of 28 raw water samples collected in winter at concentrations up to 4.3 ng/L. The NDMA concentrations were higher in raw water samples collected from treatment plants with catchment areas that have high population densities. The NDMA concentrations were higher in river water samples collected from the east and west of Japan than in those collected from other areas. NDMA was detected in 10 of 31 finished samples collected in summer at reduced concentrations of up to 2.2 ng/L, while 5 of 28 finished samples collected in winter showed NDMA concentrations up to 10 ng/L. The highest NDMA levels were detected in finished water samples collected from the Yodo River basin DWTP, which uses ozonation. Furthermore, evaluation of the process water produced at six advanced water treatment plants was conducted. Influent from the Yodo River indicated that the NDMA concentration increased during ozonation to as high as 20 ng/L, and then decreased with subsequent biological activated carbon treatment. To our knowledge, this is the first nationwide evaluation of NDMA concentrations in water conducted in Japan to date.
Strong base anion-exchange resins represent an important option for water utilities and homeowners to address growing concerns with nitrate, arsenate, and perchlorate contamination of source waters. Most commercially available anion-exchange resins employ quaternary amine functional groups. Previous research has provided contradictory evidence regarding whether these resins serve as sources of nitrosamines, considered as highly carcinogenic nitrogenous disinfection byproducts (N-DBPs), even without disinfectants. For three common varieties of commercial anion-exchange resins, we evaluated the importance of releases of nitrosamines, and two other N-DBPs (dimethylnitramine and chloropicrin), when the resins were subjected to typical column flow conditions with and without free chlorine or chloramine application upstream or downstream of the columns. In the absence of disinfectants, fresh trimethylamine- and tributylamine-based type 1 and dimethylethanolamine-based type 2 anion-exchange resins usually released 2-10 ng/L nitrosamines, likely due to shedding of manufacturing impurities, with excursions of up to 20 ng/L following regeneration. However, the lack of significant nitrosamine release in a full-scale anion-exchange treatment system after multiple regeneration cycles indicates that releases may eventually subside. Resins also shed organic precursors that might contribute to nitrosamine formation within distribution systems when chloramines are applied downstream. With free chlorine or chloramine application upstream, nitrosamine concentrations were more significant, at 20-100 ng/L for the type 1 resins and approximately 400 ng/L for the type 2 resin. However, chloropicrin formation was lowest for the type 2 resin. Dimethylnitramine formation was significant with free chlorine application upstream but negligible with chloramines. Although no N-DBPs were detected in cation-exchange-based consumer point-of-use devices exposed to chlorinated or chloraminated waters, our results indicate that inclusion of anion-exchange resins in these devices, as in laboratory deionized water systems, would likely be problematic.
The tumorigenic activities and DNA methylating abilities in F344 rats of the tobacco specific nitrosamine 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and the structurally related nitrosamine N-nitrosodimethylamine (NDMA) were compared. Groups of 30 male rats were given 60 s.c. injections of 0.0055 mmol/kg of either NNK or NDMA over a 20-week period (total dose, 0.33 mmol/kg). The experiment was terminated after 104 weeks. The numbers of rats with tumors were as follows for NNK and NDMA, respectively: liver, 10 and 6; lung 13 and 0; and nasal cavity, 6 and 1. NNK was significantly more tumorigenic than was NDMA toward the lung (P less than 0.01) and nasal cavity (P less than 0.05). Groups of rats were treated with a single s.c. injection of 0.39 mmol/kg or 0.055 mmol/kg of NNK or NDMA and the levels of 7-methylguanine and O6-methylguanine were measured in liver, lung, and nasal mucosa 1-48 h after treatment. In liver and lung, levels of 7-methylguanine and O6-methylguanine in DNA were 3-22 times (P less than 0.001) greater in NDMA treated rats than in NNK treated rats. Levels of methylation induced by NDMA and NNK in the nasal mucosa were similar. The results of this study demonstrate that NNK is a more potent tumorigen than NDMA in the F344 rat and suggest that DNA methylation alone does not account for its strong tumorigenicity in rat lung and nasal mucosa.
Exposure to disinfection byproducts in drinking water has been associated with an increased risk of bladder cancer. We pooled the primary data from 6 case-control studies of bladder cancer that used trihalomethanes as a marker of disinfection byproducts.
Two studies were included from the United States and one each from Canada, France, Italy, and Finland. Inclusion criteria were availability of detailed data on trihalomethane exposure and individual water consumption. The analysis included 2806 cases and 5254 controls, all of whom had measures of known exposure for at least 70% of the exposure window of 40 years before the interview. Cumulative exposure to trihalomethanes was estimated by combining individual year-by-year average trihalomethane level and daily tap water consumption.
There was an adjusted odds ratio (OR) of 1.24 in men exposed to an average of more than 1 microg/L (ppb) trihalomethanes compared with those who had lower or no exposure (95% confidence interval [CI] = 1.09-1.41). Estimated relative risks increased with increasing exposure, with an OR of 1.44 (1.20-1.73) for exposure higher than 50 microg/L (ppb). Similar results were found with other indices of trihalomethane exposure. Among women, trihalomethane exposure was not associated with bladder cancer risk (0.95; 0.76-1.20).
These findings strengthen the hypothesis that the risk of bladder cancer is increased with long-term exposure to disinfection byproducts at levels currently observed in many industrialized countries.
The formation of the potent carcinogen, N-nitrosodimethylamine (NDMA), during chlorine disinfection has caused significant concern among drinking water and wastewater recycling utilities practicing intentional or unintentional chloramination. Previous research modeled NDMA formation as arising from a reaction between monochloramine and organic nitrogen precursors, such as dimethylamine, via an unsymmetrical dimethylhydrazine (UDMH) intermediate. Contrary to the importance of monochloramine indicated by previous studies, hypochlorite formed an order of magnitude more NDMA than monochloramine when applied to a secondary municipal wastewater effluent containing excess ammonia. Experiments involving variation of the order that each reagent (i.e., hypochlorite, ammonium chloride, and dimethylamine) was added to solution suggest two factors that may be more important for NDMA formation than the presence of monochloramine: (i) the chlorination state of organic nitrogen precursors and (ii) the partial formation of dichloramine. Although dichloramine formation was most influenced by the pH conditions under which inorganic chloramine formation was performed, mixing effects related to the order of reagent addition may be important at full-scale plants. Chloramination strategies are suggested that may reduce NDMA formation by nearly an order of magnitude.
Nitrosamine formation during chloramination previously has been linked to a reaction between monochloramine and organic nitrogen precursors via unsymmetrical dialkylhydrazine intermediates. Our results demonstrate the critical importance of dichloramine and dissolved oxygen. We propose a new nitrosamine formation pathway in which dichloramine reacts with secondary amine precursors to form chlorinated unsymmetrical dialkylhydrazine intermediates. Oxidation of these intermediates by dissolved oxygen to form nitrosamines competes with their oxidation by chloramines. Even when preformed monochloramine was applied, our model explained nearly all N-nitrosodimethylamine formation from the traces of dichloramine formed via monochloramine disproportionation. We suggest that, in contrast to unsymmetrical dialkylhydrazines, the weak, nonpolar nature of the N-Cl linkage in chlorinated unsymmetrical dialkylhydrazine intermediates enables incorporation of dissolved oxygen to form nitrosamines. With the improved understanding of the nitrosamine formation pathway, strategies are suggested that could significantly reduce nitrosamine formation during chloramination.
N-Nitrosodimethylamine (NDMA), a member of a group of probable human carcinogens, has been detected as a disinfection byproduct (DBP) in drinking water supplies in Canada and the United States. To comprehensively investigate the occurrence of possible nitrosamines in drinking water supplies, a liquid chromatography-tandem mass spectrometry technique was developed to detect both thermally stable and unstable nitrosamines. This technique consisted of solid-phase extraction (SPE), liquid chromatography (LC) separation, and tandem quadrupole linear ion trap mass spectrometry (MS/MS) detection. It enabled the determination of sub-ng/L levels of nine nitrosamines. Isotope-labeled N-nitrosodimethylamine-d6 (NDMA-d6) was used as the surrogate standard for determining recovery, and N-nitrosodi-n-propylamine-dl4 (NDPA-dl4) was used as the internal standard for quantification. The method detection limits were estimated to be 0.1-10.6 ng/L, and the average recoveries were 41-111% for the nine nitrosamines; of these, NDMA, N-nitrosopyrrolidine (NPyr), N-nitrosopiperidine (NPip), and N-nitrosodiphenylamine (NDPhA) were identified and quantified in drinking water samples collected from four locations within the same distribution system. In general, the concentrations of these four nitrosamines in this distribution system increased with increasing distance from the water treatment plant, indicating that the amount of formation was greater than the amount of decomposition within this time frame. The identification of NPip and NDPhA in drinking water systems and the distribution profiles of these nitrosamines have not been reported previously. These nitrosamines are toxic, and their presence as DBPs in drinking water may have toxicological relevance.
Use of Toxicological and Chemical Models to Prioritize DBP
- R J D A Bull
- V Reckhow
- O M Rotello
- Bull
- Kim
Guidelines for Canadian drinking water quality: Guideline technical document: N-Nitrosodimethylamine (NDMA)
- Health Canada
Unregulated contaminant monitoring rule 2
- Usepa
Contaminant candidate list 3-CCL
- Usepa
Integrated Risk Information System (IRIS): N-Nitrosodimethylamine CASRN 62-75-9
- Usepa
Method 521: Determination of nitrosamines in drinking water by solid phase extraction and capillary column gas chromatography with large volume injection and chemical ionization tandem mass spectrometry (MS/MS)
- J. W. Munch
- M. V. Bassett
Occurrence and management of NDMA and other nitrogenous disinfection by‐products in Australian drinking and recycled waters (WQRA project 1018 milestone 5 report)
- G. Newcombe
- J. Morran
- J. Culbert
- N. Slyman
- J. Leach
- C. Kapralos
Development of a bench‐scale test to predict the formation of nitrosamines
- S. W. Krasner
- C. F. T. Lee
- W. A. Mitch
- U. Gunten