Dispersive multi-walled carbon nanotubes extraction of benzenesulfonamides, benzotriazoles, and benzothiazoles from environmental waters followed by microwave desorption and HPLC-HESI-MS/MS.

This work shows a novel analytical method for the simultaneous extraction of environmental emerging contaminants as benzenesulfonamides (BSAs), benzotriazoles (BTRs), and benzothiazoles (BTs) from water samples. Pristine multi-walled carbon nanotubes (MWCNTs), not yet tested for such analytes, are here employed as the sorbent phase for dispersive solid-phase extraction (d-SPE) followed by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry (HPLC-HESI-MS/MS). Quantitative sorption is gained by treating 50 mL sample with 100 mg MWCNTs (2 g L-1 ) in 10 min contact, both in tap and raw river water. After sorption, the analytes are quantitatively desorbed by microwaves (20 min, 160 °C, 250 W) by using 5 mL methanol-ethylacetate-acetic acid (10:70:20, v/v), according to the indications obtained by a chemometric study. The extract is reduced to small volume before analysis, thus reaching overall enrichment factors up to 400. Recovery of the entire procedure, evaluated on tap and surface water samples spiked with 0.1/0.5-50 μg L-1 of each analyte, was in the range 70-116%, with excellent inter-day precision (RSD < 7%). Selectivity and firm analyte identification were assured by MRM detection, and suitable sensitivity was obtained for determination of these pollutants in actual matrices (experimental MDLs 30-170 ng L-1 ). The proposed analytical method was applied to the analysis of surface water samples, containing concentrations of these contaminants ranging from 100 ng L-1 to 2 μg L-1 . Pristine MWCNTs proved to be a valid alternative to other commercial sorbents, both in terms of cost and sorption capacity. Graphical abstract Determination of benzenesulfonamides, benzotriazoles, and benzothiazoles in environmental waters by dispersive multi-walled carbon nanotube extraction prior HPLC-MS.