## 3 Results and Discussion  
### Non-Volatile Compounds in the Ethanol Extracts and UHPLC-MS  
XCMS analysis resulted in a table containing the 110 samples, 161 mass features (\(m/z\times\) retention time), and their peak area. After curation, 65 of these mass features were significant enough to separate the samples into distinct groups related to the individual trees. A general analysis including QCs and samples was made initially to verify the analytical instrument variations. The PCA scores graph (PC1 \(\times\) PC2) showed five distinct groups, with the QCs placed near the center confirming that there were no large variations caused by the extraction and analytical procedures (Figure S2 in Supplementary Material). The QC samples were excluded from further analyses. \begin{table}
\begin{tabular}{c c} \hline \hline \multicolumn{2}{c}{Feature Detection} \\ \hline Method & matchedFilter \\ \hline FWHM & 10 \\ \hline step & 0.3 \\ \hline \hline \multicolumn{2}{c}{Retention Time Correction} \\ \hline Method & obiwarp \\ \hline profStep & 1 \\ \hline \multicolumn{2}{c}{Alignment} \\ \hline bw & 22 \\ \hline minfrac & 0.4 \\ \hline mzwid & 0.1 \\ \hline \hline \end{tabular}
\end{table} 
Table 1: XCMS parameters optimized by IPO package in RStudio for analysis of _Schinus treebinthifolia_ LC-MS chromatograms. The PCA scores plot (PC1 \(\times\) PC2) (Figure 1A) divided the samples into four distinct groups which corresponded to the individual trees throughout the year. In this figure, each circle corresponds to individual injections of each sample and was able to explain a robust 95.4% of the chemical variability. T1 samples were placed far from the other groups in Figure 1A, hence the composition of this individual was the most different from the others, possibly because this is a tree with male flowers. The PCA biplot (Figure 1B) shows the mass features associated with each group: mass features \(m/z\) 453 and 455 were strongly associated with T1. There are some common mass features in T2, T3, and T4 extracts, but with different intensities in each, thus they are grouped separately. T2 presented a higher intensity of \(m/z\) 373 and 345 in the chromatograms whereas \(m/z\) 371 was more intense in T3. Finally, T4 was characterized by a high intensity of \(m/z\) 319. The group of mass features in the center of PCA shows that many mass features are common to all these individuals. No seasonal tendency was observed in these data (Figure S9). The heatmap of the same data, now presented as averages for each tree (Figure 2), showed these variations in mass feature intensities more clearly, mainly between T1 and the other plants, just as the PCA. This marked difference can also be observed in the UHPLC-ESI-MS chromatograms (Figure S2 in Supplementary Material), wherein the T1 chromatogram was visibly different from T2, T3, and T4 chromatograms, which present the same peaks, but with different intensities. The UHPLC-QTOF analysis resulted in more information about features of interest (Table 2), hence making it possible to propose some compounds' putative identities. The identification levels were based on [PERSON] et al., [18] considering level 1 identification by comparison to a chemical standard, but levels 2 and 3 are based on comparison to data from the literature. The extracts contained sugar (\(m/z\) 341 and 179), which is common in leaves and shikimic acid (\(m/z\) 173), and is an important precursor in the phenolic pathway. The MS/MS spectra of \(m/z\) 319, 345, 347, 371, 373, and 375 showed [M-44]- as their main fragment, corresponding to a neutral loss of a carboxyl group (CO\({}_{2}\)). These are probably anacardic acids that have different lengths of alkyl chains and numbers of unsaturations. Their phenol group results in a fragment ion of \(m/z\) 106 and \(m/z\) 119 as a result of the fragmentation in the allyl position of unsaturated acids [19]. Anacardic acids are typical of the Anacardiaceae family, to which \(S\). _terbeihntifolia_ belongs [20; 21].