Dry ice fog extraction of volatile organic compounds

Abstract

Extraction of volatile organic compounds (VOCs) into a condensed phase requires maximizing the surface-to-volume ratio of the extracting medium. In the case of the solid-phase extracting media, the surface-to-volume ratio can be increased by implementing porous monoliths or particles with different size. In the case of the liquid-phase extracting media, the surface-to-volume ratio can be increased by generating microbubbles or aerosol microdroplets. Here, we propose dry ice fog extraction (DIFE) approach. Briefly, aerosol microdroplets are generated by inserting dry ice into the extraction solvent. The produced fog, containing high-density microdroplets, is directed toward the sample headspace, where the gas-liquid extraction occurs. The microdroplets, containing the extracted VOCs, subsequently coalesce on a cold surface. The movement of the microdroplets is facilitated by a small pressure difference between the fog generator and the extract collector. Within several minutes, a few hundred microliters of the extract are collected, which is sufficient for chromatographic and mass spectrometric analyses. In this proof-of-concept study, the DIFE approach was characterized by using gas chromatography coupled with electron ionization mass spectrometry (MS), as well as direct infusion atmospheric pressure chemical ionization MS. The limits of detection for linalool and menthol were 2.0 × 10−6 and 4.7 × 10−5 M, respectively. The method was further applied in analyses of VOCs emanating from a variety of liquid and solid matrices (e-cigarette “vapor”, cinnamon branch, curly spearmint leaves, lily petal, garlic bulb, ginger root, mouthwash, shampoo, spoiled seafood, toothpaste, and red wine). DIFE effectively isolated the VOCs associated with these complex matrices.