Fractionated dynamic headspace sampling in the analysis of matrices of vegetable origin in the food field

•New pespectives for Dynamic Headspace (D-HS).•Fractionated D-HS in the anlaysis of matrices of vegetable origin in the food field.•Tuning of D-HS parameters for fractionation in function of analyte volatility.•The role of trapping materials: Tenax, PDMS and a three carbon mixture.•Complementarity of Multi Volatile Method (MVM) and Fractionated D-HS.

Recent technological advances in dynamic headspace sampling (D-HS) and the possibility to automate this sampling method have lead to a marked improvement in its the performance, a strong renewal of interest in it, and have extended its fields of application. The introduction of in-parallel and in-series automatic multi-sampling and of new trapping materials, plus the possibility to design an effective sampling process by correctly applying the breakthrough volume theory, have make profiling more representative, and have enhanced selectivity, and flexibility, also offering the possibility of fractionated enrichment in particular for high-volatility compounds. This study deals with fractionated D-HS ability to produce a sample representative of the volatile fraction of solid or liquid matrices. Experiments were carried out on a model equimolar (0.5 mM) EtOH/water solution, comprising 16 compounds with different polarities and volatilities, structures ranging from C5 to C15 and vapor pressures from 4.15 kPa (2,3-pentandione) to 0.004 kPa (t-β-caryophyllene), and on an Arabica roasted coffee powder. Three trapping materials were considered: Tenax TA™ (TX), Polydimethylsiloxane foam (PDMS), and a three-carbon cartridge Carbopack B/Carbopack C/Carbosieve S-III™ (CBS).The influence of several parameters on the design of successful fractionated D-HS sampling. Including the physical and chemical characteristics of analytes and matrix, trapping material, analyte breakthrough, purge gas volumes, and sampling temperature, were investigated. The results show that, by appropriately choosing sampling conditions, fractionated D-HS sampling, based on component volatility, can produce a fast and representative profile of the matrix volatile fraction, with total recoveries comparable to those obtained by full evaporation D-HS for liquid samples, and very high concentration factors for solid samples.