The discriminant pixel approach: a new tool for the rational interpretation of GCxGC-MS chromatograms.

GCxGC is now recognized as the most suited analytical technique for the characterization of complex mixtures of volatile compounds; it is implemented worldwide in academic and industrial laboratories. However, in the frame of comprehensive analysis of non-target analytes, going beyond the visual examination of the color plots remains challenging for most users. We propose a strategy that aims at classifying chromatograms according to the chemical composition of the samples while determining the origin of the discrimination between different classes of samples: the discriminant pixel approach. After data pre-processing and time-alignment, the discriminatory power of each chromatogram pixel for a given class was defined as its correlation with the membership to this class. Using a peak finding algorithm, the most discriminant pixels were then linked to chromatographic peaks. Finally, crosschecking with mass spectrometry data enabled to establish relationships with compounds that could consequently be considered as candidate class markers. This strategy was applied to a large experimental data set of 145 GCxGC-MS chromatograms of tobacco extracts corresponding to three distinct classes of tobacco.

Some consequences of using cigarette machine smoking regimes with different intensities on smoke yields and their variability.

When smoking cigarettes under an intense regime with a combination of 100% ventilation blocking and high flow rates, as currently mandated by Health Canada, significant increases in filter temperatures and disproportionately high levels of mainstream smoke water and moisture accumulating in the spent filter were found when compared to other smoking regimes, especially for highly filter ventilated cigarettes. These effects have been reported to decrease cigarette firmness during the course of smoking, to alter filtration properties and efficiencies and to confound the measurement of particulate matter. The high filter temperatures generated also lead to significant amounts of vapour phase compounds desorbing from carbon filters and an over-estimation of the yields of these components. Less adsorption on or more desorption from carbon filters was found for compounds with the highest volatility. Therefore, yield data from the intense regime may not reflect the effectiveness of cigarette design features to reduce certain smoke components that occurs when products are smoked under conditions closer to those used by the majority of smokers in real world situations. In addition, a combination of these interacting factors may explain the worse level of between-laboratory reproducibility data for particulate matter measurement obtained during intense machine smoking. Among-laboratory data variability for vapour phase components, other than carbon monoxide, and for particulate phase components, other than nicotine, still needs to be evaluated in collaborative studies. Before proposing smoking regimes as tools to evaluate smoke emissions, it is essential to understand these various interacting factors and subsequent uncontrolled effects that such regimes can generate and the limitations of their use. These observations imply that higher tolerances may need to be set and taken into account when smoking under the intense regime before deciding that, for a given product, there are real differences between the yields determined in different laboratories.

Comprehensive two-dimensional GC of supercritical fluid and pressurized liquid extracts of tobaccos.

The developments of an analytical strategy based on rapid extraction techniques coupled to comprehensive bi-dimensional gas chromatography (GCxGC) for the characterization of the volatile fraction of tobaccos are presented. The high-peak capacity of GCxGC allows considering global extraction techniques that do not focus on restricted chemical families of products. Thus, potential of pressurized fluid extraction and supercritical fluid extraction (SFE) to provide informative extracts is evaluated and compared. As expected, both techniques enable rapid extraction of compounds of interest. However, because of the easy removal of the extracting fluid, SFE provides more concentrated extracts, allowing a GCxGC direct injection without any concentration step. Moreover, the use of pure carbon dioxide with tuneable extraction power favors the extraction of the compounds of interest while reducing the extraction of interfering heavy compounds. GCxGC conditions, especially concerning the set of columns used, are selected thanks to the comparison of separations obtained on model compounds. The developed methodology is applied not only to compare the three main types of tobaccos but also to discriminate between different tobaccos of the same type.

Combination of dynamic time warping and multivariate analysis for the comparison of comprehensive two-dimensional gas chromatograms: application to plant extracts.

Comprehensive two-dimensional gas chromatography (GC x GC) is now recognized as the preferred technique for the detailed analysis and characterization of complex mixtures of volatile compounds. However, for comparison purposes, taking into account all the information contained in the chromatogram is far from trivial. In this paper, it is shown that the combination of peak alignment by dynamic time warping and multivariate analysis facilitated the comparison of complex chromatograms of tobacco extracts. The comparison is shown to be efficient enough to provide a clear discrimination among three types of tobacco. A tentative interpretation of loadings is presented in order to give access to the compounds which differ from one sample to another. Once located, mass spectrometry was used to identify markers of tobacco type.