1 H NMR‐Based Metabolomic Profiling and Chemometric Discrimination of Brazilian Olive Oils From Rio Grande do Sul: First Characterization of a New Extra Virgin Olive Oil Frontier

Extra virgin olive oil (EVOO) is a high‐value product whose quality is closely linked to composition, making it vulnerable to fraud and mislabeling. Rapid, nondestructive tools are therefore needed to support authenticity assessment. Despite the expansion of olive cultivation in Brazil, there is no consolidated metabolomic characterization of EVOOs from Rio Grande do Sul, the country’s main producing state and a new production frontier. Here, 155 EVOO samples from Rio Grande do Sul (harvests 2022–2024), covering the main commercial cultivars, were analyzed by 1 H NMR spectroscopy. A balanced subset of 61 samples was used for chemometric modeling. Spectra (CDCl 3 , 298 K) were processed with NMRProcFlow, bucketed, normalized, and Pareto‐scaled. Principal component analysis (PCA), PERMANOVA, PLS‐DA, permutation testing, and ROC analysis were applied. Spectra showed the characteristic lipid profile of high‐quality EVOO. Subtle but consistent differences related to cultivar and harvest were observed. PCA indicated partial clustering by cultivar, and PERMANOVA confirmed a significant cultivar effect ( p = 0.006). PLS‐DA model discriminated authentic EVOO from soybean oil ( R 2 Y = 0.69, Q 2 = 0.40; permutation p = 0.002). ROC analysis yielded AUC = 0.996, sensitivity 80.0%, and specificity 100.0%. Discriminant variables were associated with polyunsaturated fatty acids (bis‐allylic protons ∼2.8 ppm, n‐3 terminal methyl ∼0.98 ppm). This work provides the first systematic 1 H NMR‐based metabolomic characterization of EVOOs from Rio Grande do Sul and demonstrates the potential of 1 H NMR chemometrics as a rapid screening tool for authenticity and adulteration detection in emerging olive oil frontiers.