Trace Analysis of N-Nitrosamines in Water Using Solid-Phase Microextraction Coupled with Gas Chromatograph–Tandem Mass Spectrometry

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.