Headspace solid-phase microextraction based on the metal-organic framework CIM-80(Al) coating to determine volatile methylsiloxanes and musk fragrances in water samples using gas chromatography and mass spectrometry

Abstract

A headspace solid-phase microextraction (HS-SPME) method was developed using the metal-organic framework (MOF) CIM-80(Al) as extraction phase and in combination with gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of 6 methylsiloxanes and 7 musk fragrances in different environmental waters. The chromatographic separation was optimized in different GC instruments equipped with different detectors, allowing the correct separation and identification of the compounds. The HS-SPME method was optimized using a Box-Behnken experimental design, while the validation was carried out together with the most suitable commercial fiber (divinylbenzene/polydimethylsiloxane) for comparison purposes. The MOF-based coating was particularly efficient for the determination of volatile methylsiloxanes, showing moderately lower limits of detection (of 0.2 and 0.5 μg L−1versus 0.6 μg L−1 for cyclic methylsiloxanes) and slightly better precision (relative standard deviation values lower than 17% versus 22%) than the commercial coating, while avoiding the cross-contamination issues associated to the polymeric composition of commercial fibers. The method was applied for the analysis of seawater and wastewater samples, allowing the quantification of several analytes and the assessment of matrix effects. The proposed HS-SPME method using the CIM-80(Al) fiber constitutes a more environmentally friendly, simpler, and efficient strategy in comparison with other sample preparation methods using different extraction techniques, while the use of a MOF as fiber sorbent constitutes a potential alternative to exploit the features of SPME for the challenging environmental monitoring of these compounds.