Candidate Metabolomic Biomarkers of the Geographical-Indication Pear Gaoping Dahuangli (Pyrus bretschneideri Rehd.): An Exploratory Widely Targeted Metabolomics Study

Gaoping Dahuangli is a landrace pear grown for more than four centuries in Gaoping County, Shanxi Province, and a National Geographical Indication (GI) product since 2013. What distinguishes it chemically from other pears—and how that distinction can be proved in the marketplace—has not been established. We profiled the fruit metabolome of Dahuangli and four commercial reference cultivars (Korla xiangli, Jingbaili, Clapp’s Favorite, and Akizuki) by widely targeted UHPLC-MS/MS metabolomics (five varieties × three biological replicates, single harvest season) and measured eight quality attributes. Of 2335 annotated metabolic features, 136 were consistently more abundant in Dahuangli than in every reference variety. Flavonoids (48) and terpenoids (25) made up over half of this set; the single most enriched compound was sophorabioside, an isoflavone, at a minimum fold change of 120.7×. Dahuangli combined the firmest flesh (7.27 kg/cm2) with the lowest sugar/acid ratio (38.6) and the yellowest peel (b* = 51.41). On this basis we propose a candidate two-tier authentication framework: 32 candidate biomarkers enriched more than 10-fold for laboratory confirmation, 104 further metabolites for corroborative pattern matching, and two field-measurable proxies—firmness and the sugar/acid ratio—for low-cost first-stage screening. These exploratory results give a four-century-old landrace its first objective chemical definition and offer regulators, producers, and consumers a candidate toolkit—two field-measurable proxies backed by a 32-compound laboratory panel—for exposing substitution and protecting the Dahuangli geographical indication, pending multi-year and multi-orchard validation.