Exploring the potential of high-resolution LC-MS in combination with ion mobility separation and surrogate minimal depth for enhanced almond origin authentication.

Almonds (Prunus dulcisMill.) are consumed worldwide and their geographical origin plays a crucial role in determining their market value. In the present study, a total of 250 almond reference samples from six countries (Australia, Spain, Iran, Italy, Morocco, and the USA) were non-polar extracted and analyzed by UPLC-ESI-IM-qToF-MS. Four harvest periods, more than 30 different varieties, including both sweet and bitter almonds, were considered in the method development. Principal component analysis showed that there are three groups of samples with similarities: Australia/USA, Spain/Italy and Iran/Morocco. For origin determination, a random forest achieved an accuracy of 88.8 %. Misclassifications occurred mainly between almonds from the USA and Australia, due to similar varieties and similar external influences such as climate conditions. Metabolites relevant for classification were selected using Surrogate Minimal Depth, with triacylglycerides containing oxidized, odd chained or short chained fatty acids and some phospholipids proven to be the most suitable marker substances. Our results show that focusing on the identified lipids (e. g., using a QqQ-MS instrument) is a promising approach to transfer the origin determination of almonds to routine analysis.

Determination of the Geographical Origin of Walnuts (Juglans regia L.) Using Near-Infrared Spectroscopy and Chemometrics.

The prices of walnuts vary according to their geographical origin and, therefore, offer a financial incentive for adulteration. A reliable analysis method is required to quickly detect possible misdeclarations and thus prevent food fraud. In this study, a method to distinguish between seven geographical origins of walnuts using Fourier transform near-infrared (FT-NIR) spectroscopy combined with chemometrics as a fast, versatile, and easy to handle analytical tool was developed. NIR spectra of 212 ground and afterwards freeze-dried walnut samples, harvested in three consecutive years (2017-2019), were collected. We optimized the data pre-processing by applying and evaluating 50,545 different pre-processing combinations, followed by linear discriminant analysis (LDA) which was confirmed by nested cross-validation. The results show that in the scope of our research minimal pre-processing led to the best results: By applying just multiplicative scatter correction (MSC) and median centering, a classification accuracy of 77.00% ± 1.60% was achieved. Consequently, this complex model can be used to answer economically relevant questions e.g., to distinguish between European and Chinese walnuts. Furthermore, the great influence of the applied pre-processing methods, e.g., the selected wavenumber range, on the achieved classification accuracy is shown which underlines the importance of optimization of the pre-processing strategy.

Plant Metabolomics: Evaluation of Different Extraction Parameters for Nontargeted UPLC-ESI-QTOF-Mass Spectrometry at the Example of White Asparagus officinalis.

The extraction of metabolites turns out to be one of the most important key factors for nontargeted metabolomics approaches as this step can significantly affects the informative value of the successive measurements. Compared to metabolomics experiments of various matrices of bacterial or mammalian origins, there are only few studies, which focus on different extraction methods for plant metabolomics analyses. In this study, various solvent extraction compositions were compared and assessed using an UPLC-ESI-QTOF-MS strategy. Exemplary, white asparagus ( Asparagus officinalis) were employed as a low-fat-, low-protein-, high-water-content model commodity with the objective of designing an optimal nontargeted extraction protocol for polar and nonpolar metabolites. Furthermore, the influence of acid addition, mechanical cell disruption methods (ball mill, ultrasonic bath, vortex mixer), and extract stability have been systematically scrutinized too. The different extraction protocols were compared based on sum of features, sum of peak intensities, sum of peak areas, as well as by analyzing individual signals of as many different substance groups as possible to obtain a maximum overview.