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

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-nitrosodin-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.

Determination of eight nitrosamines in water at the ng L−1 levels by liquid chromatography coupled to atmospheric pressure chemical ionization tandem mass spectrometry

“…The highest nitrosamine levels (mainly NDMA, NDEA and NMor residues) were detected in samples after ozonation and high chlorination processes. A SPME-GC-MS/MS based methodology has been recently reported [19], allowing the fast and selective determination of four N-nitrosamines in water. Only NDMA was detected in most of the water treatment plant (WTP) samples investigated and below 9 ng L −1 in tap waters.…”

Analysis of N-nitrosamines in water by isotope dilution gas chromatography–electron ionisation tandem mass spectrometry

“…Recent examples include Hung et al [20] and Llop et al [21]. The most common alternative to this has been analysis by high pressure liquid chromatography with tandem mass spectrometry (HPLC-MS/MS) [22][23][24].…”

Measurement of pollution levels of N-nitroso compounds of health concern in water using ultra-performance liquid chromatography–tandem mass spectrometry

“…18 Kadmi et al (2014) and Kadmi et al (2015c). In their work, Hung et al (2010) also reported that the complicated natural water matrix did not affect the performance of the SPME-GC/MS/MS method developed for the trace analysis of N-nitrosamines. At contrary, the matrix effect appears as significant in the case of the analysis of NDMA in wastewater samples because of the high organic matter concentrations.…”

“…(Perez et al, 2008;Huang et al, 2010;Taguchi et al, 1994). However, the LLE generally requires large amounts of organic solvents, potentially harmful for environment, and the analytical process is time consuming and labor-intensive (Hung et al, 2010). Indeed the time required for analyte extraction and quantification with such technique may range from 3 to 16 h.…”