Fully automated determination of N‐nitrosamines in environmental waters by headspace solid‐phase microextraction followed by GC–MS–MS

Abstract

A fully automated method for determining nine Environmental Protection Agency N-nitrosamines in several types of environmental waters at ng/L levels is presented. The method is based on a headspace solid-phase microextraction followed by GC-MS-MS using chemical ionization. Three different fibers (carboxen/PDMS, divinylbenzene/carboxen/PDMS, and PEG) were tested. Solid-phase microextraction conditions were best when a divinylbenzene/carboxen/PDMS fiber was exposed for 60 min in the headspace of 10 mL water samples at pH 7 containing 360 g/L of NaCl, at 45°C. All compounds were analyzed by GC-MS-MS within 18 min. The method was validated using effluent from an urban wastewater treatment plant and the LODs ranged from 1 to 5 ng/L. The method was then applied to determine the N-nitrosamines in samples of different complexities, such as tap water and several influent and effluent wastewater samples from urban and industrial wastewater treatment plants and a potable water treatment plant. Although the analysis of influent industrial wastewater revealed high concentrations of some compounds (N-nitrosomorpholine and N-nitrosodimethylamine at μg/L levels), in industrial effluents and other samples, the concentrations were substantially lower (ng/L levels). The new method is suitable for the simple and reliable determination of N-nitrosamines in highly complex water samples in a completely automated procedure.

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].…”

N-nitrosamine removal by reverse osmosis for indirect potable water reuse – A critical review based on observations from laboratory-, pilot- and full-scale studies

“…To address the low concentration analysis, most currently available methods involve a solid-phase extraction (SPE) procedure followed by quantification using chromatographic-mass spectrometric analytical instruments. For quantitative determination of N-nitrosamines in water samples, many recent methods use gas chromatography coupled with different detection techniques such as mass spectrometry (GC-MS) [55,56], tandem mass spectrometry (GC-MS/MS) [57][58][59] or high resolution mass spectrometry (GC-HRMS) [60,61]. These methods use deuterated N-nitrosamines (i.e.…”

Automated on‐fiber derivatization with headspace SPME‐GC‐MS‐MS for the determination of primary amines in sewage sludge using pressurized hot water extraction

“…Besides creating an unpleasant smell, these compounds are irritants of the skin, mucous membranes, eyes, and respiratory tract. Moreover, they have been considered tumor‐inducing agents, as they can react with nitrogen oxides and form nitrosamines, which are potentially carcinogenic substances 2, 6–8. The determination of these compounds in environmental samples such as river water, wastewater, sediments, and sewage sludge is therefore of great interest.…”