Analytical and chemometric strategies for elucidation of yerba mate composition

•The phenolic composition of yerba mate from Brazil, Argentina, Paraguay, and Uruguay was comprehensively investigated.•Optimization of non-volatile metabolite extraction was achieved using the ultrasound-assisted technique.•Thirteen chlorogenic acids and two methylxanthines were identified using UHPLC-QTOF-MS.•PARAFAC analysis demonstrated a higher pigment content in Brazilian samples, while other countries exhibited higher phenolic content.•PCA analysis revealed elevated chlorogenic acid and flavonoid content in samples from Argentina, Paraguay, and Uruguay. Yerba mate, a popular plant consumed mainly as an infusion, possesses nutritional and medicinal properties attributed to its secondary metabolites. This study aimed to develop strategies to elucidate the phenolic composition of yerba mate samples from Brazil, Argentina, Uruguay, and Paraguay. Optimization of ultrasonic-assisted extraction (UAE) was performed, and the extracted compounds were characterized using ultra-high-pressure liquid chromatography coupled with quadrupole/time-of-flight mass spectrometry (UHPLC-QTOF-MS), molecular fluorescence and high-pressure liquid chromatography with diode-array detection (HPLC-DAD). Chemometric analysis, including parallel factor analysis (PARAFAC) and principal component analysis (PCA) explored metabolite profiles and identify patterns. PARAFAC modelling of the molecular fluorescence results revealed higher pigment content in Brazilian samples, while other countries' samples exhibited higher phenolic content. PCA modeling of HPLC-DAD results indicated that cultivated yerba mate contained higher chlorogenic acids levels, and samples from Argentina, Paraguay, and Uruguay exhibited higher concentrations of chlorogenic acids and flavonoids.