Comparison of the selectivity of different sorbent phases for bar adsorptive microextraction—Application to trace level analysis of fungicides in real matrices

Bar adsorptive micro-extraction combined with liquid desorption followed by large volume injection–gas chromatography–mass spectrometry operating in the selected-ion monitoring acquisition mode (BAμE–LD/LVI–GC–MS(SIM)) was developed for the determination of trace levels of ten fungicides (azoxystrobin, difenoconazole, metalaxyl-M, myclobutanil, penconazole, tebuconazole, flusilazole, cyprodinil, procymidone and benalaxyl) in aqueous matrices. By comparing different sorbent coatings (two activated carbons, two styrene–divinylbenzene and one modified pyrrolidone polymers) through BAμE, the latter phase showed much higher selectivity and capacity offering multiple mechanisms of interaction, even against polydimethylsiloxane by stir bar sorptive extraction. Assays performed on 25 mL of water samples spiked at the 0.8 μg/L level, yielded recoveries ranging from 100.0 to 107.8%, under optimized experimental conditions; BAμE(modified pyrrolidone) – equilibrium time: 4 h (1000 rpm), pH 5.5; LD – solvent:methanol/acetonitrile (1/1), 15 min with sonification. The analytical performance showed convenient detection limits (4.0–30.0 ng/L) and excellent linear dynamic ranges (0.04–1.60 μg/L) with remarkable correlation coefficients (r2 > 0.9980). Excellent repeatability was also achieved through intraday (RSD < 13.7%) and interday (RSD < 9.9%) assays. By using the standard addition methodology, the application of the present analytical approach on tap and ground water, as well as, wine samples revealed good sensitivity and absence of matrix effects. The proposed method operating under floating sampling technology proved to be a suitable sorption-based static microextraction alternative to monitor fungicides in real matrices, showing to be easy to implement, reliable, sensitive, requiring low sample volume and the possibility to choose the most selective sorbent coating according to the targets of interest.

► An alternative for trace level analysis of fungicides.
► Comparison of the selectivity of different sorbent phases for BAμE.
► Application of the novel floating sampling technologies.
► Development and validation of a novel methodology to monitor fungicides.
► Application of BAμE to monitor fungicides in water and wine samples.