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A comparison of the ability of different sorbent systems. including mixed-mode resins and reversed-phase sorbents, to extract and isolate volatile molecules from hydroalcoholic medium has been carried Out by means of the determination of liquid-solid distribution coefficients. Eighteen volatile compounds covering a wide range of physicochemical properties (acids, bases and neutrals) and chemical functionalities, and thirteen different sorbents have been tested. LiChrolut EN and Isolute ENV (both polymeric with high surface area) showed the highest retention capability for nearly all analytes at all pHs tested. Exceptions were 2,3,5-trimethylpyrazine, most efficiently extracted with Strata XC at acidic pH, and indole best retained with Oasis MCX and Strata XC at any pH. Although nearly all basic compounds were most selectively extracted with cationic mixed-mode resins at acid pHs and 3-mercaprohexyl acetate and m-cresol show maxima alpha at pH 10 with Oasis MAX, the alpha values obtained have been relatively low, which suggests that retention is not particularly driven by ionic forces. The study has also shown that selectivity depends on the pH, the exact kind of mixed-mode sorbent and on the polarity of the analyte. High selectivity towards ionogenic compounds can be obtained by combining retention in mixed mode, a rinsing with a non-polar solvent and further elution with a solvent containing a neutralizing agent. However, not all the ionogenic molecules seem to be retained in ionic mode in the conditions tested and the complete elution of some analytes can be difficult, which suggests that analyte-specific isolation procedures should be analyzed case by case. (C) 2010 Elsevier B.V. All rights reserved.