Rapid headspace solid-phase microextraction sheets with direct analysis in real time mass spectrometry (SPMESH-DART-MS) of derivatized volatile phenols in grape juices and wines

Volatile phenols possess "smoky, spicy" aromas and are routinely measured in grapes, wines and other foodstuffs for quality control. Routine analyses of volatile phenols rely on gas chromatography - mass spectrometry (GC-MS), but slow throughput of GC-MS can cause challenges during times of surge demand, i.e. following 'smoke taint' events involving forest fires near vineyards. Parallel extraction of headspace volatiles onto sorbent sheets (HS-SPMESH) followed by direct analysis in real time mass spectrometry (DART-MS) is a rapid alternative to conventional GC-MS approaches. However, HS-SPMESH extraction is poorly suited for lower volatility odorants, including volatile phenols. This work reports development and validation of an HS-SPMESH-DART-MS approach for five volatile phenols (4-ethylphenol, 4-ethylguiacol, guaiacol, 4-methylguaiacol, and cresols). Prior to HS-SPMESH extraction, volatile phenols were acetylated to facilitate their extraction. A unique feature of this work was the use of d(6)-Ac2O as a derivatizing agent to overcome issues with isobaric interferences inherent to chromatography-free MS techniques. The use of alkaline conditions during derivatization resulted in cumulative measurement of both free and bound forms of volatile phenols. The validated HS-SPMESH-DART-MS method achieved a throughput of 24 samples in similar to 60 min (including derivatization and extraction time) with low limits of detection (<1 mu g L-1) and good repeatability (3-6% RSD) in grape and wine matrices. Validation experiments with smoke-tainted grape samples indicated good correlation between total (free + bound) volatile phenols measured by HS-SPMESH-DART-MS and a gold standard GC-MS method.