Decoding the Aroma Blueprint of Peanuts (Arachis hypogaea) through Sensomics and GC×GC-TOF MS: Molecular Differentiation of Geographic Origin and Industrial Quality

Peanuts (Arachis hypogaea) are among the most consumed legumes worldwide due to their nutritional value, taste, and affordability. Ensuring a final product that meets safety standards and consumer preferences including appearance, texture, flavor, and health benefits is essential for market acceptance. To preserve these attributes throughout shelf life, manufacturers must understand the key characteristics of raw materials and adopt strategies to enhance them during storage and processing. Establishing a "quality standard" requires in-depth knowledge of peanut chemical composition, sensory properties, and nutritional content. In this context, volatile compounds represent a crucial dimension of quality, particularly regarding aroma. Among the many detectable volatiles, only a limited number decisively define the distinctive aroma and hedonic profile. These odor-active molecules, referred to as potent odorants, constitute the so-called aroma blueprint, a molecular-level signature responsible for the sensory perception of peanut flavor [1]. The analytical strategy adopted to investigate the volatilome, aligned with food-metabolomics principles, exploits the potential of multi-dimensional analysis combining physicochemical separation with spectrometric detection. Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOF MS), operating in Tandem Ionisation™, was applied. The untargeted and targeted (UT) fingerprinting approach was integrated with chemometric algorithms to highlight volatilomic differences across peanut samples differing in geographic origin (Argentina, United States, China) and industrial quality (high quality and medium/low quality); medium/low quality included smaller peanuts, splits, and by-products typically excluded from premium production. A total of 500 volatile compounds were detected, of which 285 were targeted/identified. To decode the aroma blueprint of roasted peanuts, a complementary sensomics-based strategy combined gas chromatography-olfactometry (GC-O) with aroma extract dilution analysis (AEDA) was applied. This approach enabled identification of the most potent odorants contributing to aroma and construction of origin-specific profiles. Dilution factors (FDs) from AEDA guided the identification of highly odor-active compounds, including several at trace levels but with strong sensory impact (i.e., low odor thresholds). Once identified via GC-O, these compounds were traced and confirmed in the GC×GC-TOF MS dataset. The enhanced separation of two-dimensional chromatography enabled confident identification of major potent odorants, while sensomics-driven insight supported targeted search for low-abundance, high-impact volatiles otherwise unresolved by one-dimensional analysis. This integrated approach allowed monitoring of 54 potent odorants across the GC×GC-TOF MS data. Overall, the results demonstrate that the peanut volatilome encodes valuable information related to both geographic origin and industrial quality. Moreover, aroma blueprints derived from sensomics approaches provide a robust foundation for understanding the sensory identity of peanuts. This knowledge can assist the confectionery industry in evaluating the aromatic potential of raw materials, optimizing technological processes, and designing high-quality flavor profiles that reflect market expectations and consumer acceptance.