## 2 Materials and Methods
Secondary cooling was switched off after 21 s. The Orbitrap MS was applied in both EI (70 eV) and PCI (methane, 1.5 mL/min) full-scan mode between 35 and 550 \(m/z\). Mass resolution was set at 6 \(\times\) 10\({}^{4}\) (FWHM at 200 \(m/z\)), AGC target at 1 \(\times\) 10\({}^{6}\), and emission current at 50 \(\upmu\)A. The filament delay was 6.00 min, the source temperature was 250 (EI) and 200 \({}^{\circ}\)C (PCI), quadrupole temperature was 280 \({}^{\circ}\)C, and MS transfer line temperature was 250 \({}^{\circ}\)C. Lock mass was 207.0235 \(m/z\). The instrument was tuned separately for EI and PCI analysis according to routine settings, as proposed by the manufacturer. Data were acquired with Chromeleon CDS (Thermo Scientific, Waltham, MA, USA) and subsequently processed using Thermo Scientific Compound Discoverer 3.2 and Mass Frontier 8.1 software. NIST 2020 (National Institute of Standards and Technology, Gaithersburg, MD, USA) was used as the EI spectral library (unit mass). Component Identification. In order to provide a reliable identification of these bioactive components, a standardized workflow for peak identification using GC-Orbitrap MS was applied. Initially, all data were acquired in EI mode (70 eV), allowing comprehensive fragmentation of all analytes for subsequent library export. In order to determine Kovats retention indices (RI), first, the C8-C20 alkane mix was injected and retention times of the alkanes were recorded [32]. Next, the extracts were measured under identical experimental conditions and RIs were calculated for each of the target compounds found with GC-EAD. Once collected, data were processed using the software provided with the GC-Orbitrap instrument. First, Compound Discoverer 3.2 was used in EI mode for high-resolutionspectral deconvolution and NIST library export, including RI scoring for each individual peak in the chromatogram. For each library hit, a high-resolution filtering (HRF) score was calculated by Compound Discoverer. This score indicates to which extent the elemental composition of each of the fragment ions in the NIST candidate spectra can be retrieved from the high-resolution spectrum associated with the peak under investigation [33]. The subsequent match factor includes both the HRF and library search index for each candidate. \(\Delta\)RI values were provided separately and interpreted manually. Molecular ion confirmation, which is key in the identification of unknowns, was achieved by means of a repeat analysis in PCI mode. Due to its soft nature, PCI is able to preserve the molecular ion, which is essential in order to determine (or confirm) the elemental composition of the native analyte. Typical adducts of the applied CI gas were automatically confirmed in the high-resolution spectra, and a results table was compiled that included the proposed elemental composition of all molecular ions. EI and PCI identifications were compared to provide hits that occur in both lists. As a final step in the workflow, Mass Frontier 8.1 was used to match the theoretical fragmentation of the proposed chemical structures (using common fragmentation and rearrangement rules), as derived from the elemental composition of the molecular ion, with the experimental fragmentation pattern obtained during EI analysis and expressed as Fragment Ion Search (FISH) scores [34]. Statistical Analysis. All analyses were performed in R, v3.3.1 (R Core Team 2016).