Abstract
A method that utilizes solid-phase microextraction (SPME) coupled with gas chromatography (GC) and chemical ionization tandem mass spectrometry (MS/MS) was developed for analyzing a group of emerging pollutants, N-nitrosamines, in water. The developed analytical method requires a water sample of less than 5 ml and only 1.5 h for complete analysis. The method detection limits for N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine, and N-nitrosodi-n-propylamine were in the range of 3.2 to 3.5 ng/l; for N-nitrosomorpholine, it was 15.2 ng/l. The method was successfully employed to measure the N-nitrosamine concentration at trace levels of nanogram per liter in four water treatment plants (WTPs) and one water distribution system. In the WTPs, only NDMA was detected in the treatment processes. Within the treatment train, NDMA was observed after chlorination. The level of NDMA significantly declined after slow sand filtration due presumably to microbial degradation. The NDMA concentration collected from consumer tap water was about 40% higher on average than that in the finished water. The excellent performance of the SPME/GC/MS/MS method in various water matrices as well as the shorter analysis time and smaller sample volume compared to currently used extraction techniques makes it an alternative means for the analysis of N-nitrosamine in drinking water, wastewater, and laboratory research with small reactors.





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Alpendurada, M. D. (2000). Solid-phase microextraction: A promising technique for sample preparation in environmental analysis. Journal of Chromatography A, 889(1–2), 3–14.
American Public Health Association (APHA), American Water Works Association (AWWA), & Water Environment Federation (WEF). (1998). Standard methods for the examination of water and wastewater (20th ed.). USA: Maryland.
Andrade, R., Reyes, F. G. R., & Rath, R. (2005). A method for the determination of volatile N-nitrosamines in food by HS–SPME–GC–TEA. Food Chemistry, 91(1), 173–179.
Barrett, S., Hwang, C., Guo, Y., Andrews, S. A., & Valentine, R. (2003). Occurrence of NDMA in drinking water: A north American survey, 2001–2002. In Proceedings of the Annual American Water Works Association Conference, June 15–19, Anaheim, California, USA.
Charrois, J. W. A., Arend, M. W., Froese, K. F., & Hrudey, S. E. (2004). Detecting N-nitrosamines in drinking water at nanogram per liter levels using ammonia positive chemical ionization. Environmental Science & Technology, 38(18), 4835–4841.
Charrois, J. W. A., & Hrudey, S. E. (2007). Breakpoint chlorination and free-chlorine contact time: Implications for drinking water N-nitrosodimethylamine concentrations. Water Research, 41(3), 674–682.
Cheng, R. C., Hwang, C. J., Andrews-Tate, C., Guo, Y., Carr, S., & Suffet, I. H. (2006). Alternative methods for the analysis of NDMA and other nitrosamines in water. Journal American Water Works Association, 98(12), 82–96.
MOE (Ontario Ministry of the Environment) (2002). Ontario drinking water quality standards, Ontario regulation 169/03, Safe Drinking Water Act.
Grebel, J. E., & Suffet, I. H. (2007). Nitrogen–phosphorus detection and nitrogen chemiluminescence detection of volatile nitrosamines in water matrices: optimization and performance comparison. Journal of Chromatography A, 1175(1), 141–144.
Grebel, J. E., Young, C. C., & Suffet, I. H. (2006). Solid-phase microextraction of N-nitrosamines. Journal of Chromatography A, 1117(1), 11–18.
Gunnison, D., Zappi, M. E., Teeter, C., Pennington, J. C., & Bajpai, R. (2000). Attenuation mechanisms of N-nitrosodimethylamine at an operating intercept and treat groundwater remediation system. Journal of Hazardous Materials, 73(2), 179–197.
Hsieh, S. T., Wang, G. S., & Lin, T. F. (2010). Biodegradation of MIB and geosmin with slow sand filters. Journal of Environmental Science and Health. Part A (in press).
Hung, H. W., & Lin, T. F. (2006). Adsorption of MTBE from contaminated water by carbonaceous resins and mordenite zeolite. Journal of Hazardous Materials, 135(1–3), 210–217.
Jurado-Sáncheza, B., Ballesterosb, E., & Gallegoa, M. (2007). Comparison of the sensitivities of seven N-nitrosamines in pre-screened waters using an automated preconcentration system and gas chromatography with different detectors. Journal of Chromatography A, 1154(1–2), 66–73.
Lee, C., Schmidt, C., Yoon, J., & Gunten, U. V. (2007). Oxidation of N-nitrosodimethylamine (NDMA) precursors with ozone and chlorine dioxide: Kinetics and effect on NDMA formation potential. Environmental Science & Technology, 41(6), 2056–2063.
Lin, T. F., Liu, C. L., Yang, F. C., & Hoang, S. W. (2003). Effect of residual chlorine on the analysis of geosmin, 2-MIB and MTBE in drinking water using the SPME technique. Water Research, 37(1), 21–26.
Mirvish, S. S. (1975). Formation of N-nitroso compounds: Chemistry, kinetics, and in vivo occurrence. Toxicology and Applied Pharmacology, 31(3), 325–351.
Mitch, W. A., Gerecke, A. C., & Sedlak, D. L. (2003b). A N-nitrosodimethylamine (NDMA) precursor analysis for chlorination of water and wastewater. Water Research, 37(15), 3733–3741.
Mitch, W. A., & Sedlak, D. L. (2002). Formation of N-nitrosodimethylamine (NDMA) from dimethylamine during chlorination. Environmental Science & Technology, 36(4), 588–595.
Mitch, W. A., Sharp, J. O., Trussell, R. R., Valentine, R. L., Alvarez-Cohen, L., & Sedlak, D. L. (2003a). N-Nitrosodimethylamine (NDMA) as a drinking water contaminant: A review. Environmental Engineering Science, 20(5), 389–404.
Munch, J. W., & Bassett, M. V. (2006). Method development for the analysis of N-nitrosodimethylamine and other N-nitrosamines in drinking water at low nanogram/liter concentrations using solid-phase extraction and gas chromatography with chemical ionization tandem mass spectrometry. Journal of AOAC International, 89(2), 486–497.
Najm, I., & Trussell, R. R. (2001). NDMA formation in water and wastewater. Journal American Water Works Association, 93(2), 92–99.
Perez, D. M., Alatorre, G. G., Alvarez, E. B., Silva, E. E., & Alvarado, J. F. J. (2008). Solid-phase microextraction of N-nitrosodimethylamine in beer. Food Chemistry, 107(3), 1348–1352.
CDPH (California Department of Public Health) (2008). NDMA and other nitrosamines—Drinking water issues. http://www.cdph.ca.gov/certlic/drinkingwater/pages/NDMA.aspx. Accessed 25 October 2009.
Schreiber, I. M., & Mitch, W. A. (2005). Influence of the order of reagent addition on NDMA formation during chloramination. Environmental Science & Technology, 39(10), 3811–3818.
Schreiber, I. M., & Mitch, W. A. (2006). Nitrosamine formation pathway revisited: The importance of chloramine speciation and dissolved oxygen. Environmental Science & Technology, 40(19), 6007–6014.
Sharp, J. O., Wood, T. K., & Alvarez-Cohen, L. (2005). Aerobic biodegradation of N-nitrosodimethylamine (NDMA) by axenic bacterial strains. Biotechnology and Bioengineering, 89(5), 608–618.
USEPA (US Environmental Protection Agency). (1993). Integrated risk information system (IRIS), Office of research and development, national center for environmental assessment. http://www.epa.gov/iris. Accessed 25 October 2009.
Westerhoff, P., & Mash, H. (2002). Dissolved organic nitrogen in drinking water supplies: A review. Journal of Water Supply: Research and Technology-AQUA, 51(8), 415–448.
Acknowledgments
This work was supported by the Landmark Project, National Cheng Kung University, Taiwan, under grant B-020 (2008) and by the National Science Council, Taiwan, under grants NSC96-2621-Z-006-016 and NSC97-2221-E-006-039-MY2.
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Hung, HW., Lin, TF., Chiu, CH. et al. Trace Analysis of N-Nitrosamines in Water Using Solid-Phase Microextraction Coupled with Gas Chromatograph–Tandem Mass Spectrometry. Water Air Soil Pollut 213, 459–469 (2010). https://doi.org/10.1007/s11270-010-0398-9
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DOI: https://doi.org/10.1007/s11270-010-0398-9