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.