Development of Glass Cup Aqueous Sampling and Headspace Solid-Phase Microextraction/Gas Chromatography-Mass Spectrometry for Measuring Ethanol, Acetaldehyde and Acetone Emission from Human Skin Surface

Volatile organic compounds (VOCs) emitted from human skin are promising biomarkers for non-invasive health assessment and disease diagnosis. However, efficient collection and sensitive analytical methods for skin VOCs remain challenging. We developed a method for measuring ethanol, acetaldehyde, and acetone from palmar skin using glass cup aqueous sampling followed by headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS). Compounds were extracted using a carboxen/polydimethylsiloxane fiber by HS-SPME and separated using a DB-1 capillary column within 5 min. The HS-SPME/GC-MS method showed linearity (5–1000 ng/mL, r ≥ 0.990) with detection limits of 0.56, 1.01, and 0.15 ng/mL for ethanol, acetaldehyde, and acetone, respectively. Intra-day and inter-day precision were ≤9.3% and ≤9.7%, with accuracy ranged of 94–110%. Five-minute palm contact with water caused VOC release to increase linearly, and samples remained stable for 24 h at −20 °C. Following ingestion of a 500 mL alcoholic beverage (5% ethanol), ethanol and acetaldehyde emissions peaked at 95 and 24 ng/cm²/min after 1 h, while acetone gradually increased to 1.3 ng/cm²/min after 6 h. This simple, rapid method enables practical assessment of skin VOCs for health monitoring and environmental exposure evaluation.