Chemometrics-assisted isotope ratio fingerprinting based on gas chromatography/combustion/isotope ratio mass spectrometry for saffron authentication

Abstract

In the present contribution, the capability of isotopic ratio mass spectrometry (IRMS) for saffron authentication and detection of four common plant-derived adulterants (marigold flower, safflower, rubia, and saffron style) was investigated. For this purpose, 62 authentic saffron samples were analyzed by elemental analyzer-IRMS (EA-IRMS) and gas chromatography-combustion-IRMS (GC-C-IRMS). In this regard, EA-IRMS and GC-C-IRMS isotope fingerprints of carbon-13 and nitrogen-15 isotopes of saffron components were provided and then analyzed by chemometric methods. Principal component analysis (PCA) showed two different behaviors regarding two main regions. Then, a representative saffron sample was provided to study adulteration. On this matter, binary mixtures of saffron and adulterants were prepared at five different weight percentages (5%, 10%, 15%, 25%, and 35%) and analyzed by EA-IRMS and GC-C-IRMS. Data-driven soft independent modeling of class analogy (DD-SIMCA) was used to model authentic saffron samples and find a boundary between authentic and adulterated samples with a sensitivity of 100% by GC-C-IRMS. After that, discriminant models of linear discriminant analysis (LDA), quadratic discriminant analysis (QDA), and partial least squares-discriminant analysis (PLS-DA) were tested to find the best discrimination line and also detection of the lowest level of adulterants. Among different models, the QDA model outperformed other methods and showed the ability to predict adulterants at 5% w/w level with 100% accuracy and precision. Finally, the developed QDA model was successfully used to discriminate a set of mixed samples of saffron and four adulterants as well as some commercial samples.