Nitrification and biofilm growth within distribution systems remain major issues for drinking water treatment plants utilizing chloramine disinfection. Many chloraminated plants periodically switch to chlorine disinfection for several weeks to mitigate these issues, known as "chlorine burns". The evaluation of disinfection byproduct (DBP) formation during chlorine burns beyond regulated DBPs is scarce. Here, we quantified an extensive suite of 80 regulated and emerging, unregulated DBPs from 10 DBP classes in drinking water from two U.S. drinking water plants during chlorine burn and chloramination treatments. Total organic halogen (TOX), including total organic chlorine, total organic bromine, and total organic iodine, was also quantified, and mammalian cell cytotoxicity of whole water mixtures was assessed in chlorine burn waters for the first time. TOX and most DBPs increased in concentration during chlorine burns, and one emerging DBP, trichloroacetaldehyde, reached 99 μg/L. THMs and HAAs reached concentrations of 249 and 271 μg/L, respectively. Two highly cytotoxic nitrogenous DBP classes, haloacetamides and haloacetonitriles, increased during chlorine burns, reaching up to 14.2 and 19.3 μg/L, respectively. Cytotoxicity did not always increase from chloramine treatment to chlorine burn, but a 100% increase in cytotoxicity was observed for one plant. These data highlight that consumer DBP exposure during chlorine burns can be substantial.

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.

This study reveals key disinfection byproduct (DBP) toxicity drivers in drinking water across the United States. DBPs, which are ubiquitous in drinking water, form by the reaction of disinfectants, organic matter, bromide, and iodide and are generally present at 100-1000× higher concentrations than other contaminants. DBPs are linked to bladder cancer, miscarriage, and birth defects in human epidemiologic studies, but it is not known as to which DBPs are responsible. We report the most comprehensive investigation of drinking water toxicity to date, with measurements of extracted whole-water mammalian cell chronic cytotoxicity, over 70 regulated and priority unregulated DBPs, and total organic chlorine, bromine, and iodine, revealing a more complete picture of toxicity drivers. A variety of impacted waters were investigated, including those impacted by wastewater, agriculture, and seawater. The results revealed that unregulated haloacetonitriles, particularly dihaloacetonitriles, are important toxicity drivers. In seawater-impacted water treated with chloramine, toxicity was driven by iodinated DBPs, particularly iodoacetic acids. In chlorinated waters, the combined total organic chlorine and bromine was highly and significantly correlated with toxicity (r = 0.94, P < 0.01); in chloraminated waters, total organic iodine was highly and significantly correlated with toxicity (r = 0.80, P < 0.001). These results indicate that haloacetonitriles and iodoacetic acids should be prioritized in future research for potential regulation consideration.

This study investigated the transformation of a THM mixture and the change of toxicity risk in drinking water distribution systems for the first time.

In order to better understand the occurrence of disinfection byproducts (DBPs) in tap water and their real impacts on consumers, this study made a one-year long survey of the temporal variations of a series of DBPs before and after a point-of-use (POU) treatment facility installed in a building serving for ∼300 people. Water samples were collected every week at a fixed location and time for 1 year, and frequent samplings were carried out every 6 h a day for 1 month at selected seasons, which ultimately amounted to 322 samples. The results show that the concentrations of DBPs were higher in the summer than other seasons, with the lowest DBP levels being observed in spring. Within one week, higher levels of haloacetic acids (HAAs) were identified on weekdays than those on weekends. Diurnally, trihalomethanes, HAAs, and haloacetaldehydes were found to be higher at noon but lower in the evening. Consistent with other studies, the variations of most DBPs were somewhat positively related to the changes of temperature and organic matter, but negatively related to the quantity of free chlorine. With the use of a POU facility, which equips with two activated carbon cartridges and a boiler in sequence, most of DBPs were dramatically reduced, leading to 62-100% lower cytotoxicity for the measured DBPs. The study hence provides a real-water evidence about the DBP occurrences in a typical distribution system endpoint and the efficiency of a typical POU on mitigating DBP risks.

Background: N-nitroso compounds (NOC) formed endogenously after nitrate/nitrite ingestion and disinfection by-products (DBPs) are suspected colorectal carcinogens, but epidemiologic evidence of these associations is limited. Objectives: We investigated the relationship between drinking water exposures and incident colorectal cancers in a cohort of postmenopausal women. Methods: Using historical nitrate-nitrogen (NO3-N) measurements and estimates of total trihalomethanes (TTHM), the sum of 5 or 6 haloacetic acids (HAAs), and individual DBPs in public water supplies (PWS), we computed average exposures and years of exposure above one-half the U.S. maximum contaminant level (> 1/2-MCL; > 5 mg/L NO3-N and >40 mu g/L TTHM). Nitrate/nitrite intakes from dietary sources were estimated using a food frequency questionnaire. We estimated hazard ratios (HR) and 95% confidence intervals (CI) from Cox regression models. We assessed NO3-N interactions with DBPs and with factors influencing endogenous NOC formation. Results: We identified 624 colon and 158 rectal cancers (1986-2010) among 15,910 women reporting PWS use > 10 years. Ingestion of NO3-N from drinking water was not associated with risk. Colon cancer risks were non-significantly associated with the average TTHM levels > 17.7 mu g/L (HRQ5vsQ1 = 1.13, CI = 0.89-1.44; p(trend) = 0.11) and were elevated for any duration of exposure > 1/2-MCL. Rectal cancer risks were associated with the highest TTHM levels (HRQ5vsQ1 = 1.71, CI = 1.00-2.92; p(trend) = 0.22) but not with years > 1/2-MCL. Bromodichloromethane (HRQ4vsQ1 = 1.89, CI = 1.17-3.00; p(trend) = 0.09) and trichloroacetic acid (HRQ4vsQ1 = 1.92, CI = 1.20-3.09; p(trend) = 0.18) levels were also associated with risk of rectal cancer. We found no evidence of interaction between TTHM and NO3-N on the risk of either cancer. Dietary analyses yielded a positive colon cancer association with red meat, but not with processed meat intake or estimated nitrate/nitrite from specific dietary sources. Conclusions: Our results suggest that exposure to TTHM in drinking water is associated with increased risk of rectal cancer. Positive findings for individual THMs and HAAs for both colon and rectal cancers require replication in other studies. We found no associations for nitrate overall or in subgroups with presumed higher NOC exposure.

N‑nitrosodimethylamine (NDMA) was detected in the source water of some Chinese drinking water treatment plants (DWTPs), which decreased in concentration along the treatment train. Volatilization, photolysis, and/or biodegradation were suspected of being capable of attenuating NDMA. In this study, the contribution of these mechanisms to NDMA removal was investigated by a field study in a conventional DWTP with aerated bio-pretreatment, as well as in laboratory-based experiments. The effluent of each unit process (i.e., aerated bio-pretreatment tank, horizontal sedimentation tank, sand filter) of this DWTP was sampled in the winter and summer, and the concentration of NDMA, its formation potential, and other water quality parameters were measured. NDMA removal by volatilization and biodegradation was simulated in batch experiments, and that by photolysis was calculated with parameters reported in the literature. The sampling results indicated that the aerated biofilm reactor of this DWTP removed 48% of the NDMA in August and 22% in December. According to modeling results, it could be well explained by photolysis (NDMA removal of 51% in summer and 25% in winter) and biotreatment (NDMA removal of 0.2-12% in summer and 0.1-6.1% in winter), with little contribution from aeration (NDMA removal of 0.8%). The sampling results indicated that the sedimentation tank removed 19% of NDMA in August and 9.2% in December. According to modeling results, it could be well explained by photolysis (NDMA removal of 16% in August and 9.4% in December), but little by volatilization. Thus, photolysis was shown to be the most important process for NDMA removal in this DWTP. Further investigation is needed to better understand NDMA removal during biotreatment.

including SPE cartridge, eluent type, eluent volume, and sample pH, were optimized. Under optimized conditions, the new method had method detection limits, method quantification limits, and precision ranging from 0.15 to 0.37 ng L-1, 0.50-0.95 ng L-1, and 5.8%-11%, respectively. The recoveries of the eight CPANs ranged from 92% to 102%. The concentrations of the eight CPANs in nine finished drinking waters were determined to be at concentrations ranging from 0.5 to 155 ng L-1. Seven CPANs were detectable in all samples. CPANs were detected at concentrations between 0.8 and 155 ng L-1 in chlorinated waters, and from 0.5 to 15 ng L-1 in chloraminated waters. Across all waters, the sum of all CPANs in chloraminated waters was 13% of that in chlorinated systems. (C) 2018 Elsevier Ltd. All rights reserved.

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.

Haloacetamides (HAMs), a group of nitrogenous disinfection byproducts (N-DBPs), can decompose to form corresponding intermediate products and other DBPs. The stability of ten different HAMs, including two chlorinated, five brominated, and three iodinated species was investigated with and without the presence of chlorine, chloramines, and reactive solutes such as quenching agents. The HAM basic hydrolysis and chlorination kinetics were well described by a second-order kinetics model, including first-order in HAM and hydroxide and first-order in HAM and hypochlorite, respectively, whereas the HAM neutral hydrolysis kinetic was first-order in HAM. Furthermore, HAMs decompose instantaneously when exposed to hypochlorite, which was almost two and nine orders of magnitude faster than HAM basic and neutral hydrolysis, respectively. In general, HAM hydrolysis and chlorination rates both increased with increasing pH and the number of halogens substituted on the methyl group. Moreover, chlorinated HAMs are more unstable than their brominated analogs, followed by the iodinated ones, due to the decrease in the electron-withdrawing inductive effect from chlorine to iodine atom. During hydrolysis, HAMs mainly directly decompose into the corresponding haloacetic acids (HAAs) via a nucleophilic reaction between the carbonyl carbon and hydroxide. For HAM chlorination reactions, hypochlorite reacts with HAMs to form the N-chloro-HAMs (N-Cl-HAMs) via Cl+ transfer from chlorine to the amide nitrogen. N-Cl-HAMs can further degrade to form HAAs via hypochlorous acid addition. In contrast, the reactions between chloramines and HAMs were found to be insignificant. Additionally, four common quenching agents, including sodium sulfite, sodium thiosulfate, ascorbic acid, and ammonium chloride, were demonstrated to expedite HAM degradation, whereas ammonium chloride was the least influential among the four. Taft linear free energy relationships were established for both HAM hydrolysis and chlorination reactions, based on which the hydrolysis and chlorination rate constants for three monohaloacetamides were estimated. The hydrolysis and chlorination rates of 13 HAMs decreased in the following order: TCAM > BDCAM > DBCAM > TBAM > DCAM > BCAM > DBAM > CIAM > BIAM > DIAM > MCAM > MBAM > MIAM (where C = chloro, B = bromo, I = iodo, T = tri, D = di, M = mono). Lastly, using the HAM kinetic model established in this study, HAM half-lifes in drinking water distribution systems can be predicted on the basis of pH and residual chlorine concentration.

Nitrate and nitrite are precursors of N-nitroso compounds (NOC), probable human carcinogens that cause pancreatic tumors in animals. Disinfection by-products (DBP) exposures have also been linked with digestive system cancers, but few studies have evaluated relationships with pancreatic cancer. We investigated the association of pancreatic cancer with these drinking water contaminants and dietary nitrate/nitrite in a cohort of postmenopausal women in Iowa (1986-2011). We used historical monitoring and treatment data to estimate levels of long-term average nitrate and total trihalomethanes (TTHM; the sum of the most prevalent DBP class) and the duration exceeding one-half the maximum contaminant level (>1/2 MCL; 5 mg/L nitrate-nitrogen, 40 mu g/L TTHM) among participants on public water supplies (PWS) >10 years. We estimated dietary nitrate and nitrite intakes using a food frequency questionnaire. We computed hazard ratios (HR) and 95% confidence intervals (CI) using Cox regression and evaluated nitrate interactions with smoking and vitamin C intake. We identified 313 cases among 34,242 women, including 152 with >10 years PWS use (N=15,710). Multivariable models of average nitrate showed no association with pancreatic cancer (HRp95 (vs. Q1)=1.16, 95% CI: 0.51-2.64). Associations with average TTHM levels were also null (HRQ4 (vs. Q1)=0.70, 95% CI:0.42-1.18). We observed no trend with increasing years of exposure to either contaminant at levels >1/2 MCL. Positive associations were suggested in the highest dietary nitrite intake from processed meat (HRp95 (vs. Q1)=1.66, 95% CI 1.00-2.75;p(trend)=0.05). We found no interactions of nitrate with known modifiers of endogenous NOC formation. Our results suggest that nitrite intake from processed meat may be a risk factor for pancreatic cancer.

Haloacetamides (HAMs), an emerging class of disinfection by-products, have received increasing attention due to their elevated cyto- and genotoxicity. However, only limited information is available regarding the iodinated analogues. This study investigated the formation and speciation of iodinated haloacetamides (I-HAMs) and their chlorinated/brominated analogues during the chloramination of bromide and/or iodide-containing waters and a model compound solution over various time periods. The rapid formation of diiodoacetamide (DIAM) was observed during chloramination of three simulated samples, whereas brominated (Br-HAMs) and chlorinated haloacetamides (Cl-HAMs) increased slowly with increasing reaction time. To further understand the differences in the formation of HAMs containing different halogens, experiments with the model compound asparagine in the presence/absence of iodide were conducted. Moreover, iodine utilisation factors and iodine incorporation factors were observed to increase significantly faster and were substantially higher than those of bromine. This implied that, compared with bromide, iodide has substantially greater potential to be transformed to the corresponding HAMs during chloramination, similar to that of other classes of DBPs. That is, I-HAMs formed faster than the other species investigated, including Cl-HAMs and Br-HAMs, in the early reaction stages (0-3 h). The effect of the bromide/iodide ratio (i.e., constant iodide, increasing bromide) on I-HAM formation was also examined. With increasing bromide/iodide ratio, the formation of Br-HAMs increased and dichloroacetamide decreased, but the formation of DIAM was largely unchanged. This was consistent with the constant level of iodide in spite of the increasing bromide. Chlorine and ammonia are applied separately during chloramination in water treatment, so the effect of pre-chlorination (before adding ammonia) on the formation and speciation of I-HAMs during in situ chloramination was also evaluated. Effective mitigation of DIAM formation with in situ chloramination was achieved, and the efficiency improved with increasing pre-chlorination time, where iodide was oxidised to iodate. The HAM associated cytotoxicity was calculated to determine the change in toxicity at different reaction times, bromide/iodide ratios, and pre-chlorination times. A similar trend as the formation of I-HAMs was observed, which increased rapidly in the first 3 h, but decreased somewhat subsequently. When the bromide/iodide ratio and pre-chlorination time was increased, the calculated toxicity of the HAMs increased (due to more formation of Br-HAMs and less Cl-HAMs) and decreased (due to less DIAM formation), respectively. (C) 2018 Elsevier Ltd. All rights reserved.

In the 1980s, a case–control epidemiologic study was conducted in Iowa (USA) to analyze the association between exposure to disinfection by-products (DBPs) and bladder cancer risk. Trihalomethanes (THMs), the most commonly measured and dominant class of DBPs in drinking water, served as a primary metric and surrogate for the full DBP mixture. Average THM exposure was calculated, based on rough estimates of past levels in Iowa. To reduce misclassification, a follow-up study was undertaken to improve estimates of past THM levels and to re-evaluate their association with cancer risk. In addition, the risk associated with haloacetic acids, another class of DBPs, was examined. In the original analysis, surface water treatment plants were assigned one of two possible THM levels depending on the point of chlorination. The re-assessment considered each utility treating surface or groundwater on a case-by-case basis. Multiple treatment/disinfection scenarios and water quality parameters were considered with actual DBP measurements to develop estimates of past levels. The highest annual average THM level in the re-analysis was 156μg/L compared to 74μg/L for the original analysis. This allowed the analysis of subjects exposed at higher levels (>96μg/L). The re-analysis established a new approach, based on case studies and an understanding of the water quality and operational parameters that impact DBP formation, for determining historical exposure.

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.

Background: N-nitroso compounds formed endogenously after nitrate/nitrite ingestion are animal renal carcinogens. Previous epidemiologic studies of drinking water nitrate did not evaluate other potentially toxic water contaminants, including the suspected renal carcinogen chloroform.Methods: In a cohort of postmenopausal women in Iowa (19862010), we used historical measurements to estimate long-term average concentrations of nitrate-nitrogen (NO3-N) and disinfection by-products (DBP) in public water supplies. For NO3-N and the regulated DBP (total trihalomethanes [THM] and the sum of five haloacetic acids [HAA5]), we estimated the number of years of exposure above one-half the current maximum contaminant level (>1/2-MCL NO3-N; > 5 mg/L). Dietary intakes were assessed via food frequency questionnaire. We estimated hazard ratios (HRs) and 95% confidence intervals (CIs) with Cox models, and evaluated interactions with factors influencing N-nitroso compound formation.Results: We identified 125 incident kidney cancers among 15,577 women reporting using water from public supplies > 10 years. In multivariable models, risk was higher in the 95th percentile of average NO3-N (HRp95vsQ1 = 2.3; CI: 1.2, 4.3; P-trend = 0.33) and for any years of exposure >1/2-MCL; adjustment for total THM did not materially change these associations. There were no independent relationships with total THM, individual THMs chloroform and bromodichloromethane, or with haloacetic acids. Dietary analyses yielded associations with high nitrite intake from processed meats but not nitrate or nitrite overall. We found no interactions.Conclusions: Relatively high nitrate levels in public water supplies were associated with increased risk of renal cancer. Our results also suggest that nitrite from processed meat is a renal cancer risk factor.

Unpleasant odors in drinking water can have a negative effect on consumer confidence. In fact, consumers often perceive that if their water smells bad, then it must be bad and unsafe to drink. Compliance for odor aesthetics of drinking water in the United States is based on a secondary standard using the threshold odor number (TON) method, a dilution‐to‐threshold test. However, this test has been subject to criticism in the drinking water community for being a poor measure of consumer acceptance. As a result, many utilities have turned to flavor profile analysis (FPA) to better predict consumer acceptance. However, FPA requires a trained panel, and TON remains the recommended procedure for regulatory compliance. The Metropolitan Water District of Southern California, in collaboration with Tufts University, developed a new, robust odor testing method called total intensity of odor, which offers a valid alternative for compliance purposes.

Chloramines are often used instead of free chlorine as a residual disinfectant in order to limit formation of regulated halogen‐substituted disinfection by‐products that form more readily in the presence of free chlorine. However, the use of chloramines can form carcinogenic nitrosamines. Some polymers, particularly polyDADMAC, contribute nitrosamine precursors (as confirmed in this research). Alternative polymers produced from natural products evaluated in bench and pilot testing produced clarification and filtration performance as good as or better than that with polyDADMAC or other currently used polymers while contributing little or no nitrosamine precursors. However, there was indication of high biological growth in filters that were not chlorinated. Replacing readily biodegradable acetic acid with a mineral acid (e.g., hydrochloric acid) during synthesis of chitosan might reduce the potential for biological activity with this polymer. Performance variations in different source waters suggest that site‐specific determination of the best polymer type, dose, and application point should be completed before using any polymer.

This special focus issue of Journal AWWA presents papers from the United States and abroad that discuss current research on nitrosamines. This month's guest editor discusses how drinking water utilities have cost‐effectively optimized their treatment and disinfection processes to control a variety of micropollutants to meet state and federal regulations, operational requirements, and aesthetic issues. However, the discovery of new pollutants presents challenges to the drinking water industry. An emerging class of disinfection by‐products (DBPs) of health and regulatory concern are nitrosamines (e.g., N‐nitrosodimethylamine [NDMA]). NDMA is preferentially formed by chloramines, where chloramines have been increasingly used to control the formation of the regulated DBPs trihalomethanes and haloacetic acids.