Chemical mapping of Crocus sativus L. floral parts for assessing compositional consistency and auto-adulteration in saffron-based botanicals

Abstract Phytochemical variability complicates quality assessment of botanical ingredients, particularly when authenticated reference materials are limited. Saffron ( Crocus sativus L.), used both as a spice and as a food supplement ingredient, exhibits marked compositional differences across its floral parts, making evaluation of compositional balance essential for quality control and authentication. Here, saffron-based botanicals were profiled by LC-TWIMS-HRMS and evaluated within a floral part-anchored multivariate framework. Sixty-eight metabolites were tentatively identified across stigma, petal, and stamen reference tissues and nine commercial botanicals. Principal component analysis of log-transformed data revealed a dominant stigma-petal compositional gradient. Botanicals were projected onto the direction defined by anatomical centroids, and the robustness of directional estimates was assessed through compound-level and macro-class resampling. Orthogonal residual decomposition was used to characterize compositional variance not captured by the primary gradient. Most botanicals remained closely aligned with the stigma reference profile. A subset showed reproducible displacement toward petal-associated chemical patterns, driven by coordinated enrichment of flavonoids and anthocyanins relative to crocins, consistent with the presence of non-stigma floral material. These findings demonstrate that anatomically anchored chemical mapping combined with structured multivariate modelling can detect and characterize compositional deviations in saffron-based botanicals under conditions of limited reference availability.