Combining stir-bar sorptive extraction and large volume injection-gas chromatography-mass spectrometry for the determination of benzotriazole UV stabilizers in wastewater matrices

Stir-bar sorptive extraction and liquid desorption followed by large volume injection-gas chromatography coupled to mass spectrometry under selected ion monitoring mode acquisition (SBSE-LD/LVI-GC-MS(SIM)) was applied for the determination of six benzotriazole UV stabilizers (Tinuvin P, Allyl-bzt, Tinuvin 320, Tinuvin 326, Tinuvin 327 and Tinuvin 328) in wastewater matrices. Parameters affecting the performance of extraction and desorption steps were thoroughly evaluated using uni- and multivariate optimization strategies, based on the use of experimental factorial designs. Assays performed with stir bars, coated with 24 mu L of polydimethylsiloxane, on 25 mL of ultra-pure water samples spiked at the 0.5 ng/mL level, yielded recoveries ranging from 47.9 +/- 1.4% (Tinuvin P) to 103.1 +/- 3.6% (Tinuvin 326), under optimized experimental conditions. When applied to complex matrices (e.g. wastewater), the methodology showed also excellent linear dynamic ranges (0.0210.00ng/mL) for the six benzotriazole UV stabilizers studied with correlation coefficients higher than 0.9970, limits of quantification in between 0.004 and 0.015ng/mL, suitable repeatability (RSD<12.7%) and reproducibility (RSD<4.5%). The application of the proposed methodology to urban sewage waters from Spain and Portugal wastewater plants revealed the presence of low contents of some benzotriazole UV stabilizers.