Mapping Metabolomic Relationships of Hop Cultivars in an Ancestral Lineage Context

Hops (<i>Humulus lupulus</i>) are one of the most valuable raw materials in the global brewing industry as they provide resins and essential oils highly relevant to beer production. Hop cultivars commonly used in brewing are predominantly derived from European and American genetic lineages, whose agronomic and phytochemical traits are frequently studied to support the development of new varieties increasingly adapted for beer production. Herein, we investigated the chemical profiles of 76 different commercial hop cultivars using gas chromatography coupled to mass spectrometry (GC-MS) analysis and a metabolomic approach. Unsupervised statistical analyses revealed a clustering tendency between cultivars of North American or European lineages. Chemical composition exploration was conducted through molecular networking, allowing the annotation of 26 metabolites that distinguished the two groups. American lineage hops exhibited a chemical profile characterized by mono- and sesquiterpenoids, ketones, and esters, whereas hops from European lineage presented higher abundances of α- and β-selinene, <i>trans-</i>α-bergamotene, humulene epoxide II, neophytadiene, and tocopherols. Our findings strengthen the evidence for selinenes as potential markers for differentiating hops of European genetic background and highlight <i>trans-</i>α-bergamotene as an important chemical marker in hop cultivars. Thus, GC-MS-based metabolomic signatures of multiple commercial hop cultivars revealed distinguished chemical relationships of kinship among American and European lineages, advancing our understanding of cultivar chemical diversity in an ancestral lineage context and providing a metabolomic basis for hop cultivar classification and traceability.