Sorption of volatile organic compounds on the inner surface of polymer sampling bags leads to important underestimations of the real headspace concentration. Introducing a wide range of volatiles in a two-phase system containing Nalophan revealed that recoveries decreased down to 57 % in a period of 22 h. In this work, a phase ratio variation approach is investigated to quantify the degree of scalping, and thus enabling to compensate for sorption phenomena. This method requires limited measurements, without the need for time-consuming calibrations. By spiking identical amounts of volatiles in three two-phase systems, each having unique polymer volume/mass ratios β (β 1 = 0, β 2 = 80.9, β 3 = 161.9), individual partitioning coefficients could be experimentally determined for a wide range of compounds. Additionally, a correlation was found between these partitioning coefficients and the liquid molar volume for a number of aliphatic, aromatic, and oxygenated compounds.
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