Evaluation and Optimization of APGC Parameters for the Analysis of Selected Hop Essential Oil Volatiles.

Hop essential oil is a mixture of several hundred volatile metabolites that quantitatively and qualitatively distinguish hop varieties. Given the commercial relevance of hops in the brewing industry and the complexity of hop oil, analytical tools enabling a comprehensive characterization of oil constituents are required. At this, atmospheric pressure chemical ionization interfaced to gas chromatography and high-resolution mass spectrometry (APGC-MS) is a promising option that combines soft ionization, high sensitivity, and high resolution. While high sensitivity is required to detect minor or trace-level volatile metabolites, soft ionization and high resolution enable the reliable identification of unknowns based on exact masses of the molecular ion or the protonated molecule. Twenty-two volatile metabolites typically found in hop oil were studied in respect to their APGC ionization behavior. For 15 compounds, APGC-MS did not yield high molecular ion or protonated molecule intensities and considerable in-source fragmentation was observed. APGC-MS parameter optimization (cone gas flow and cone voltage) was able to yield the maximum absolute intensity for the base peak. However, in-source fragmentation could not be prevented, leading to spectra with either the protonated molecule or a characteristic fragment ion as the base peak. APGC-MS operated under optimized parameters was applied to a hop essential oil sample to verify the effect of optimization. By estimating the limit of quantification for the 22 compounds, it is concluded that APGC-MS is well suited to analyze major, minor, and trace-level volatiles from hops.