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                <title xml:lang="en">Modifying PTR-MS operating conditions for quantitative headspace analysis of hydro-alcoholic beverages. 2. Brandy characterization and discrimination by PTR-MS</title>
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                <term xml:lang="en">PTR-MS</term>
                <term xml:lang="en">Brandy</term>
                <term xml:lang="en">Volatile organic compounds</term>
                <term xml:lang="en">Headspace</term>
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              <p>The characterization of the release of aroma compounds from beverages can bring pertinent information that can help in better understanding aroma perception. However, this kind of measurement is complex for high ethanol-containing beverages and needs to be adapted or optimized. Increasing the mean collision energy in the drift tube via the E/N ratio can be an interesting solution to prevent H3O+ depletion when high ethanol-containing samples, as distilled beverages for instance, are analyzed. However, the higher collision energy induced by these conditions impacts ionization reactions due to an increased number of fragmentation mechanisms, which could make data analysis difficult. The aim of the present study was to highlight the pertinence of using strong operating conditions (E/N = 454 Td) compared to reference conditions (E/N = 120-140 Td) for the analysis of 40% (v/v) ethanol-containing beverages. The first step was to better understand product ion distributions of 11 aroma compounds, known to be important for the overall flavor of brandies and prepared in 40% (v/v) ethanol/water solutions, at both operating conditions. As a validation, eight commercial brandies from different brands and with different aging times were analyzed under the two operating conditions. It appeared that the E/N value did not impact product ion distribution, but changed their relative abundances: increasing the E/N ratio increased fragmentation mechanisms, resulting in the detection of a greater proportion of low mass fragments to the detriment of protonated ions issued from aroma compounds. The response linearity of the PTR-MS was not modified at strong operating conditions. The application of these conditions to the analysis of brandies highlighted that, in spite of modifications on ionization mechanisms, products can be correctly discriminated, mainly according to their aging time.</p>
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