Beita-Sandí W, Karanfil T. Removal of both N-nitrosodimethylamine and trihalomethanes precursors in a single treatment using ion exchange resins. Water Res. 2017 Jul 14;124:20-28. doi: 10.1016/j.watres.2017.07.028.
Drinking water utilities are relying more than ever on water sources impacted by wastewater effluents. Disinfection/oxidation of these waters during water treatment may lead to the formation of several disinfection by-products, including the probable human carcinogen N-nitrosodimethylamine (NDMA) and the regulated trihalomethanes (THMs). In this study, the potential of ion exchange resins to control both NDMA and THMs precursors in a single treatment is presented. Two ion exchange resins were examined, a cation exchange resin (Plus) to target NDMA precursors and an anion exchange resin (MIEX) for THMs precursors control. We applied the resins, individually and combined, in the treatment of surface and wastewater effluent samples. The treatment with both resins removed simultaneously NDMA (43-85%) and THMs (39-65%) precursors. However, no removal of NDMA precursors was observed in the surface water with low initial NDMA FP (14 ng/L). The removals of NDMA FP and THMs FP with Plus and MIEX resins applied alone were (49-90%) and (41-69%), respectively. These results suggest no interaction between the resins, and thus the feasibility of effectively controlling NDMA and THMs precursors concomitantly. Additionally, the effects of the wastewater impact and the natural attenuation of precursors were studied. The results showed that neither the wastewater content nor the attenuation of the precursor affected the removals of NDMA and THMs precursors. Finally, experiments using a wastewater effluent sample showed that an increase in the calcium concentration resulted in a reduction in the removal of NDMA precursors of about 50%.
Chen WH, Wang CY, Huang TH. Formation and fates of nitrosamines and their formation potentials from a surface water source to drinking water treatment plants in Southern Taiwan. Chemosphere. 2016 Jul 29;161:546-554. doi: 10.1016/j.chemosphere.2016.07.027.
Nitrosamines are toxic and emerging disinfection byproducts. In this study, three drinking water treatment plants (DWTPs) in southern Taiwan treating the same source water in Gaoping River with comparable technologies were selected. The objective was to evaluate the formation and fates of six nitrosamines and their formation potentials (FPs) from a surface water source to drinking water. Albeit decreased further downstream in the river, four nitrosamine-FPs were observed in the source water due to anthropogenic pollution in the upstream areas. In the DWTPs, nitrosamines were formed and NDMA was the main species. While high organic carbon concentrations indicated elevated nitrosamine-FPs in the source water, NDMA formation in the DWTPs was more positively associated with reductions of water parameters that quantify organic matters with double bonded ring structures. Although precursor removal via pre-oxidation is a viable approach to limit nitrosamine formation during post-disinfection, this study clearly indicates that a great portion of NDMA in treated water has been formed in the 1st oxidation step of drinking water treatment. The pre-oxidation simulations in the lab demonstrated the impact of pre-chlorination on nitrosamine formation. Given the limited removal in conventional treatment processes, avoiding nitrosamine-FPs in sources and/or nitrosamine formation during pre-oxidation become important issues to control the threats of nitrosamines in drinking water. Under current circumstance in which pre-oxidation is widely used to optimize the treatment effectiveness in many DWTPs, its adverse effect by forming nitrosamines needs to be carefully minimized and using technologies other than pre-chlorination (e.g., pre-ozonation) may be considered.
Wang W, Yu J, An W, Yang M. Occurrence and profiling of multiple nitrosamines in source water and drinking water of China. The Science of the Total Environment. 2016 Feb 17;551-552:489-495. doi: 10.1016/j.scitotenv.2016.01.175.
The occurrence of multiple nitrosamines was investigated in 54 drinking water treatment plants (DWTPs) from 30 cities across major watersheds of China, and the formation potential (FP) and cancer risk of the dominant nitrosamines were studied for profiling purposes. The results showed that N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA) and N-nitrosodi-n-butylamine (NDBA) were the most abundant in DWTPs, and the concentrations in source water and finished water samples were not detected (ND) -53.6ng/L (NDMA), ND -68.5ng/L (NDEA), ND -48.2ng/L (NDBA). The frequencies of detection in source waters were 64.8%, 61.1% and 51.8%, and 57.4%, 53.7%, and 37% for finished waters, respectively. Further study indicated that the FPs of the three main nitrosamines during chloramination were higher than those during chlorination and in drinking water. The results of Principal Components Analysis (PCA) showed that ammonia was the most closely associated factor in nitrosamine formation in the investigated source water; however, there was no significant correlation between nitrosamine-FPs and the values of dominant water-quality parameters. The advanced treatment units (i.e., ozonation and biological activated carbon) used in DWTPs were able to control the nitrosamine-FPs effectively after disinfection. The target pollutants posed median and maximum cancer risks of 2.99×10-5 and 35.5×10-5 to the local populations due to their occurrence in drinking water.
Toxicology studies of mixtures have additional complications and their applicability to risk assessment is a developing science. This work should be considered hypothesis generating. In general, conducting risk assessments for individual chemicals yields very conservative results. Addressing mixtures is very speculative and the combinations are endless.
Ma F, Zhang Z, Jiang J, Hu J. Chromium (VI) potentiates the DNA adducts (O6-methylguanine) formation of N-nitrosodimethylamine in rat: Implication on carcinogenic risk. Chemosphere. 2015 Jul 2;139:256-259. doi: 10.1016/j.chemosphere.2015.06.077.
Chromium (VI) [Cr(VI)] and nitrosamines such as N-nitrosodimethylamine (NDMA) exist commonly in the environment. To evaluate the potential influence of Cr(VI) co-exposure on the carcinogenic risk of NDMA, Female Wistar rats were treated with various concentrations of Cr(VI) and/or NDMA via drinking water for 15days and the DNA adducts (O6-methylguanine, O6-MeG) of NDMA in liver tissue was used as a bioindicator. The results showed that Cr(VI) synergistically enhanced the O6-MeG formation, which could lead to an increase in DNA damage and carcinogenic potential. Although Cr(VI) did not alter the CYP 2E1 enzyme activity, it decreased GSH content, which would be an potential mechanism for the potentiated O6-MeG formation by Cr(VI) co-exposure. These results would contribute to the development of quantitative risk assessment of NDMA or even for a group of nitrosamines under environmental mixture exposure.
Li T1, Yu D, Xian Q, Li A, Sun C. Variation of levels and distribution of N-nitrosamines in different seasons in drinking waters of East China. Environ Sci Pollut Res Int. 2015 Apr 11.
We surveyed the occurrence of nine N-nitrosamine species in ten bottled drinking waters from supermarket and other water samples including raw waters, finished waters, and distribution system waters from nine municipal drinking water treatment plants in eight cities of Jiangsu Province, East China. N-nitrosodimethylamine (NDMA) was detected in one of ten bottled drinking water samples at concentration of 4.8 ng/L and N-nitrosomorpholine (NMor) was detected in four of the ten bottles with an average concentration and a standard deviation of 16 ± 15 ng/L. The levels of nitrosamines in the distribution system water samples collected during summer season ranged from below detection limit (BDL) to 5.4 ng/L for NDMA, BDL to 9.5 ng/L for N-nitrosomethylethylamine (NMEA), BDL to 2.7 ng/L for N-nitrosodiethylamine (NDEA) and BDL to 8.5 ng/L for N-nitrosopyrrolidine (NPyr). Samples of distribution system waters collected in winter season had levels of nitrosamines ranged from BDL to 45 ng/L for NDMA, BDL to 5.2 ng/L for NPyr, and BDL to 309 ng/L for N-nitrosopiperidine (NPip). A positive correlation of the concentration of NDMA as well as the total nine N-nitrosamines between finished waters and distribution system waters was observed. Both dissolved organic carbon and nitrite were found to correlate linearly with N-nitrosamine levels in raw waters.
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Qian Y, Wu M, Wang W, Chen B, Zheng H, Krasner SW, Hrudey SE, Li X.Determination of Fourteen Nitrosamines at ng/L levels in Drinking Water. Anal Chem. 2014 Dec 19.
N-nitrosamines, probable human carcinogens, are a group of disinfection byproducts (DBPs) under consideration for drinking water regulation. Currently, no method can determine trace levels of alkyl and tobacco-specific nitrosamines (TSNAs) of varying physical and chemical properties in water by a single analysis. To tackle this difficulty, we developed a single solid-phase extraction (SPE) method with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for the determination of 14 nitrosamines of health concern with widely differing properties. We made a cartridge composed of vinyl/divinyl benzene polymer that efficiently concentrated the 14 nitrosamines in 100 mL of water (in contrast to 500 mL in other methods). This single SPE-HPLC-MS/MS technique provided calculated method detection limits (MDLs) of 0.01-8.3 ng/L and recoveries of 53-93% for the 14 nitrosamines. We have successfully demonstrated that this method can determine the presence or absence of the 14 nitrosamines in drinking water systems (eight were evaluated in Canada and the U.S.), with similar occurrence to that in other surveys. N-Nitrosodimethylamine (NDMA), N-nitrosodiphenylamine (NDPhA), and the TSNA 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) were identified and quantified in authentic drinking water. Formation potential (FP) tests demonstrated that NDMA and TSNA precursors were present in (1) water samples in which tobacco was leached and (2) wastewater-impacted drinking water. Our results showed that pre-chlorination or ozonation destroyed most of the nitrosamine precursors in water. Our new single method determination of alkyl nitrosamines and TSNAs significantly reduced the time and resource demands of analysis and will enable other studies to more efficiently study precursor sources, formation mechanisms, and removal techniques. It will be useful for human exposure and health risk assessments of nitrosamines in drinking water.
Posted in NDMA
Uzun H, Kim D, Karanfil T. Seasonal and temporal patterns of NDMA formation potentials in surface waters. Water research 2014 Nov 21;69C:162-172. doi: 10.1016/j.watres.2014.11.017.
The seasonal and temporal patterns of N-nitrosodimethylamine (NDMA) formation potentials (FPs) were examined with water samples collected monthly for 21 month period in 12 surface waters. This long term study allowed monitoring the patterns of NDMA FPs under dynamic weather conditions (e.g., rainy and dry periods) covering several seasons. Anthropogenically impacted waters which were determined by high sucralose levels (>100 ng/L) had higher NDMA FPs than limited impacted sources (<100 ng/L). In most sources, NDMA FP showed more variability in spring months, while seasonal mean values remained relatively consistent. The study also showed that watershed characteristics played an important role in the seasonal and temporal patterns. In the two dam-controlled river systems (SW A and G), the NDMA FP levels at the downstream sampling locations were controlled by the NDMA levels in the dams independent of either the increases in discharge rates due to water releases from the dams prior to or during the heavy rain events or intermittent high NDMA FP levels observed at the upstream of dams. The large reservoirs and impoundments on rivers examined in this study appeared serving as an equalization basin for NDMA precursors. On the other hand, in a river without an upstream reservoir (SW E), the NDMA levels were influenced by the ratio of an upstream wastewater treatment plant (WWTP) effluent discharge to the river discharge rate. The impact of WWTP effluent decreased during the high river flow periods due to rain events. Linear regression with independent variables DOC, DON, and sucralose yielded poor correlations with NDMA FP (R2 < 0.27). Multiple linear regression analysis using DOC and log [sucralose] yielded a better correlation with NDMA FP (R2 = 0.53).
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