Polyethersulfone solid-phase microextraction followed by liquid chromatography quadrupole time-of-flight mass spectrometry for benzotriazoles determination in water samples

Abstract

A microextraction method for the determination of 1H-benzotriazole (BTri), and four polar derivatives (4 and 5-methyl-1H-benzotriazole, 4-TTri and 5-TTri; 5,6-dimethyl-1H-benzotriazole, XTri; and 5-chloro-1H-benzotriazole, 5-ClBTri), in surface and wastewater samples is presented. Analytes were pre-concentrated using a disposable, low cost polyethersulfone (PES) sorbent and further analysed by liquid chromatography quadrupole time-of-flight mass spectrometry (LC–QTOF-MS). Parameters affecting the efficiency of sample preparation (extraction conditions and desorption solvent) and those controlling the performance of LC–MS determination were investigated. Analytes were extracted from 15mL water samples, containing a 30% (w/v) of sodium chloride (4.5g) and adjusted at pH 4.5, using a tubular PES sorbent (5cm length×0.7mm o.d., sorbent volume 42μL). After methanol desorption and solvent exchange, benzotriazoles were determined by LC–MS, with chromatograms extracted using a mass window of 20ppm, centred in their [M+H]+ ions. The identity of chromatographic peaks was confirmed with accurate ion product scan (MS/MS) spectra. The method provided limits of quantification (LOQs) between 0.005 and 0.100μgL−1, and relative recoveries from 81% to 124% (except for XTri in sewage samples, ca. 60%) with associated standard deviations between 2% and 9%. When compared with polydimethylsiloxane covered stir-bars (coating volume 24μL), the PES polymer achieved significant higher responses (5–20-fold) for these polar pollutants. BTri and tolyltriazoles (4-TTri and 5-TTri) were found in urban sewage and river water samples, affected by wastewater discharges, with the maximum concentration (5.9μgL−1) corresponding to BTri in raw wastewater.