Quality control in quantification of volatile organic compounds analysed by thermal desorption–gas chromatography–mass spectrometry

This paper presents a detailed study on the calibration of a thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS)-based methodology for quantification of volatile organic compounds (VOCs) in gaseous and liquid samples. For the first time, it is documented to what extent three widely encountered problems affect precise and accurate quantification, and solutions to improve calibration are proposed. The first issue deals with the limited precision in MS quantification, as exemplified by high relative standard deviations (up to 40%, n = 5) on response factors of a set of 69 selected VOCs in a volatility range from 16 Pa to 85 kPa at 298 K. The addition of [2H8]toluene as an internal standard, in gaseous or liquid phase, improves this imprecision by a factor of 5. Second, the matrix in which the standard is dissolved is shown to be highly important towards calibration. Quantification of gaseous VOCs loaded on a sorbent tube using response factors obtained with liquid standards results in systematic deviations of 40–80%. Relative response factors determined by the analysis of sorbent tubes loaded with both analytes and [2H8]toluene from liquid phase are shown to offer a reliable alternative for quantification of airborne VOCs, without need for expensive and often hardly available gaseous standards. Third, a strategy is proposed involving the determination of a relative response factor being representative for a group of analytes with similar functionalities and electron impact fragmentation patterns. This group method approach indicates to be useful (RSD ≈ 10%) for quantifying analytes belonging to that class but having no standards available.