HSSPME

HSSPME, or headspace solid-phase microextraction, is a solvent-free sample preparation technique used to extract volatile and semi-volatile compounds from the headspace above a sample. In HSSPME, a fiber coated with a sorbent material is exposed to the headspace, allowing analytes to partition onto the coating. After sampling, the fiber is removed and thermally desorbed in the inlet of a gas chromatograph, often coupled to a mass spectrometer, where the analytes are separated and detected.

The technique relies on the partitioning of compounds between the sample matrix, the headspace vapor, and the sorbent coating on the fiber. Common coatings include polydimethylsiloxane (PDMS), polyacrylate, and mixed-phase materials such as PDMS/DVB or CAR/PDMS, each offering different affinities for target analytes. Fiber choice depends on volatility range and chemical nature of the analytes. HSSPME can be performed in static headspace mode or dynamic configurations and is often used in combination with thermal desorption GC–MS for identification and quantification.

Typical method parameters include fiber coating and exposure time, extraction temperature, and whether salt is added to promote volatilization. Calibration and quantification are achieved using external standards or internal standards, with attention to fiber-to-fiber variability and potential carryover. HSSPME is widely applied in food and beverage aroma profiling, environmental monitoring of pollutants, forensic science, and pharmaceutical and fragrance analysis. Its advantages include solvent-free operation, minimal sample handling, and high sensitivity for volatile compounds, while limitations involve selectivity determined by the coating, potential fiber aging, and the need for careful method optimization.