Fluorescent paper-based sensor integrated with headspace thin-film microextraction for the detection of acyclic N-nitrosamines following in situ photocatalytic decomposition.

Background: In this work, a novel analytical approach based on the photocatalytic decomposition of N-nitrosamines combined with headspace thin-film microextraction of the generated nitrogen oxides such as NO has been developed for the determination of the acyclic N-nitrosamine fraction in drinking water samples. A hydrophilic cellulose substrate modified with fluorescent silver nanoclusters (Ag NCs) was used both as extractant and sensing platform. A quenching effect of Ag NCs fluorescence occurs as the concentration of N-nitrosamines increases. Front-face fluorescence spectroscopy with a solid sample holder was employed for directly measuring the fluorescence quenching onto the cellulose substrate.

Results: In order to achieve an optimal analytical response, different parameters involved in the photocatalytic reaction as well as those concerning the microextraction step were fully investigated. It is demonstrated that the photodegradation rate of cyclic N-nitrosamines at acidic pH is much lower than that of acyclic ones, which can be the basis for the determination of the later fraction in waters. Under optimal conditions, a detection limit for the acyclic N-nitrosamine fraction around 0.08 μg L using N-nitrosodimethylamine (NDMA) as model compound for calibration was obtained. Several drinking waters were spiked with acyclic N-nitrosamines showing recoveries in the range of 98-102% with a relative standard deviation of 3-4% (N = 3).

Significance And Novelty: N-nitrosamines generated as by-products during disinfection processes applied to water cause multiple adverse effects on human health being classified as potential human carcinogens. This study highlights the suitability of a fluorescent paper-based sensor for the rapid analysis of the acyclic N-nitrosamine fraction (i.e. the most abundant fraction) as a total index in drinking water, being useful as screening tool before exhaustive chromatographic analysis, which saves costs, time and reduces waste generation.