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Abstract: A method is described for characterization of sulfur compounds in unaged and aged whisky. The method is based on full evaporation dynamic headspace (FEDHS) of 100μL of whisky samples followed by selectable one-dimensional (1D) or two-dimensional (2D) retention-time-locked (RTL) gas chromatography (GC)–mass spectrometry (MS) with simultaneous element-specific detection using a sulfur chemiluminescence detector (SCD) and a nitrogen chemiluminescence detector (NCD). Sequential heart-cuts of the 16 sulfur fractions were used to identify each individual sulfur compound in the unaged whisky. Twenty sulfur compounds were positively identified by a MS library search, linear retention indices (LRI), and formula identification using MS calibration software. Additionally eight formulas were also identified for unknown sulfur compounds. Simultaneous heart-cuts of the 16 sulfur fractions were used to produce the 2D RTL GC-SCD chromatograms for principal component analysis. PCA of the 2D RTL GC-SCD data clearly demonstrated the difference between unaged and aged whisky, as well as two different whisky samples. Fourteen sulfur compounds could be characterized as key sulfur compounds responsible for the changes in the aging step and/or the difference between two kinds of whisky samples. The determined values of the key sulfur compounds were in the range of 0.3–210ngmL−1 (RSD: 0.37–12%, n =3). [Copyright &y& Elsevier]

Abstract: Gas and liquid chromatography (GC and LC) coupled to mass spectrometry (MS) serve as the most powerful analytical tools commonly used to monitor pesticide residues in food, among other applications. However, both GC–MS and LC–MS are susceptible to matrix effects which can adversely affect quantification depending on the analyte, matrix, sample preparation, instrumentation, and operating conditions. Among the approaches that reduce matrix effects, the most common in pesticide residue applications is matrix-matched calibration because it is relatively inexpensive and simple. Also, it has been shown to work well during method validation when fortified samples are exactly matched with samples used for calibration. However, the quality of matrix-matched results in real-world analyses depends on the consistency of matrix effects among diverse samples. In this study, the variability of matrix effects was measured for 38 representative pesticides in 20 samples each (including different varieties) of rice, orange, apple, and spinach extracted using the “quick, easy, cheap, effective, rugged, and safe” (QuEChERS) method for analysis by LC–MS/MS and low-pressure GC–MS. Using LC–MS/MS, only oranges gave >20% matrix effects for a few pesticides. GC–MS exhibited larger matrix effects, but as in LC–MS/MS, the differences were reasonably consistent among the 20 samples tested. Main conclusions of this study are that for the conditions utilized: (1) matrix-matching was not needed for most pesticides in the simpler food matrices; and (2) for the more complex orange matrix, acceptably accurate quantitative results were achieved by using matrix-matching even with a different sample of the same type. However, full confidence cannot be extended to matrix-matched results, and for consequential applications such as regulatory enforcement, confirmatory analyses using alternate quantitative determinations should also be conducted. [Copyright &y& Elsevier]