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A research platform for food authentication was set up by combining stable isotope ratio analysis, metabolomics by gas and liquid mass-spectrometry and NMR investigations, chemometric analyses for food excellences. This multi-analytical approach was tested on samples of elephant garlic (Allium ampeloprasum L.), a species belonging to the same genus of common garlic (Allium ampeloprasum L.), mainly produced in southern Tuscany-(Allium ampeloprasum). The isotopic composition allowed the product to be geographically characterized. Flavonoids, like (+)-catechin, cinnamic acids, quercetin glycosides were identified. The samples showed also a significant amount of dipeptides, sulphur-containing metabolites and glutathione, the latter of which could be considered a molecular marker of the analyzed elephant garlic. For nutraceutical profiling to reach quality labels, extracts were investigated in specific biological assays, displaying interesting vasorelaxant properties in rat aorta by mediating nitric oxide release from the endothelium and exhibited positive inotropic and negative chronotropic effects in rat perfused heart., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Garlic ( Allium sativum L.) is not only appreciated for its flavour and taste, but it is also recognized for various health properties. The European Commission, through the attribution of the Protected Designation of Origin (PDO) certification mark, has officially recognized some specific varieties of garlic. To protect not only the commercial value but also the reputation of this appreciated product, effective tools are therefore required. For the first time, a new compound specific isotope analysis method based on carbon stable isotopic ratio measurement of the three major volatile garlic compounds allyl alcohol (AA), diallyl disulphide (DD) and diallyl trisulphide (DT) through head-space solid phase microextraction (HS-SPME) followed by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) was developed. A within-day standard deviation (Sr within-day ) of 0.3 ‰, 0.4 ‰ and 0.2 ‰ for δ ( 13 C) and a between-day standard deviation (Sr between-day ) of 0.8 ‰, 1.0 ‰ and 0.6 ‰ of AA, DT and DD was estimated. For the first time, the ranges of isotopic variability for the three volatile compounds of red garlic from two neighbouring Italian regions (Abruzzo and Lazio) were defined analysing 30 samples. The same dataset was also considered in analysing the percentage composition of the previously mentioned three volatile compounds through HS-SPME followed by gas chromatography-tandem mass spectrometry (GC-MS/MS). The two analytical approaches were combined in this explorative study, aiming to provide potential parameters to discriminate garlic samples based on their geographical origin., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)

Origin authentication methods are pivotal in counteracting frauds and provide evidence for certification systems. For these reasons, geographical origin authentication methods are used to ensure product origin. This study focused on the origin authentication (i.e. at the producer level) of a typical mountain cheese origin using various approaches, including shotgun metagenomics, volatilome, near infrared spectroscopy, stable isotopes, and elemental analyses. DNA-based analysis revealed that viral communities achieved a higher classification accuracy rate (97.4 ± 2.6 %) than bacterial communities (96.1 ± 4.0 %). Non-starter lactic acid bacteria and phages specific to each origin were identified. Volatile organic compounds exhibited potential clusters according to cheese origin, with a classification accuracy rate of 90.0 ± 11.1 %. Near-infrared spectroscopy showed lower discriminative power for cheese authentication, yielding only a 76.0 ± 31.6 % classification accuracy rate. Model performances were influenced by specific regions of the infrared spectrum, possibly associated with fat content, lipid profile and protein characteristics. Furthermore, we analyzed the elemental composition of mountain Caciotta cheese and identified significant differences in elements related to dairy equipment, macronutrients, and rare earth elements among different origins. The combination of elements and isotopes showed a decrease in authentication performance (97.0 ± 3.1 %) compared to the original element models, which were found to achieve the best classification accuracy rate (99.0 ± 0.01 %). Overall, our findings emphasize the potential of multi-omics techniques in cheese origin authentication and highlight the complexity of factors influencing cheese composition and hence typicity., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Balsamic vinegar of Modena (ABM) is a product obtained from concentrated grape must with the addition of wine vinegar. It can be adulterated with the addition of exogenous water. The official method EN16466-3, based on the analysis of the stable isotope ratio δ 18 O of the water, is not applicable to ABM with high density (above 1.20 at 20 °C). In this work, for the first time, the official method was modified, providing for a prior dilution of the sample and applying a correction of the data in order to eliminate the isotopic contribution of the diluent, whereupon the within- and between-day standard deviations of repeatability (Sr) were estimated. Considering the limit values of δ 18 O for vinegar and concentrated must, the threshold limit of δ 18 O, below which the ABM product can be considered adulterated, has been identified.

Red yeast rice (RYR) is marketed as a dietary supplement because it contains natural 3-hydroxy-3-methylglutaryl coenzyme A reductase inhibitors (statins), including monacolin K. However, there is concern that some RYR supplements may be adulterated with the pharmaceutical drug lovastatin to enhance health claims. We have developed an optimized method to isolate monacolin K/lovastatin from complex RYR dietary supplement matrices to then test for adulteration in RYR supplements using stable carbon isotope (δ 13 C) analysis. Samples were initially screened for monacolin K/lovastatin using liquid chromatography with mass spectrometric detection (LC-MS). To ensure the extraction process did not affect the measured isotopic values (i.e., isotopic fractionation effects), neat lovastatin standards were spiked into two types of blank RYR matrices (powder and gel). The monacolin K/lovastatin peaks were detected using high performance liquid chromatography with ultraviolet detection (HPLC-UV) and isolated using fraction collection. Residual matrix components were removed from targeted fractions by solid phase extraction (SPE) using graphitized carbon black cartridges. The resulting isolates were then analyzed using elemental analyzer-isotope ratio mass spectrometry (EA-IRMS) to measure δ 13 C values. The δ 13 C values of the extracted lovastatin standards were compared to their respective neat lovastatin δ 13 C values and demonstrated negligible isotopic fractionation effects. Using this optimized clean up method and carbon isotope analysis, thirty-one samples were screened. Eight RYR dietary supplement samples had >0.8 mg/g of monacolin K/lovastatin, our minimum threshold for analyzing samples using this method. Four of these eight samples had δ 13 C values greater than -28.3‰, a previously proposed cutoff value for natural monacolin K, indicating likely adulteration. Additionally, five RYR powder samples were analyzed as part of a collaborative study using in-house methods from two laboratories and the data shows acceptable agreement in the δ 13 C values of monacolin K/lovastatin (differences ranging from ±0.02‰ to ±0.76‰). This optimized method represents a robust, reproducible procedure for detecting lovastatin adulteration in dietary supplements with minimal isotopic fractionation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier B.V.)

Cannabidiol (CBD) is a non-psychoactive cannabinoid of Cannabis sativa that exhibits several beneficial pharmacological effects, including anti-inflammatory and antioxidant properties. The molecule can be obtained via extraction from the plant or through a biosynthetic route. The two products have both advantages and disadvantages, thus necessitating the development of methods capable of distinguishing between the two products. In this study, for the first time, the analysis of the stable isotope ratios of oxygen and hydrogen demonstrated high efficiency in the discrimination of CBD of a totally natural origin from that obtained through chemical synthesis. Considering a probability level of 95%, it was possible to identify threshold values for δ 2 H and δ 18 O of the totally natural CBD of -215‱ and +23.4‱, respectively. Higher values may indicate a non-entirely natural origin of CBD (i.e., a biosynthetic molecule).

Chitosan is a natural polysaccharide which has been authorized for oenological practices for the treatment of musts and wines. This authorization is limited to chitosan of fungal origin while that of crustacean origin is prohibited. To guarantee its origin, a method based on the measurement of the stable isotope ratios (SIR) of carbon δ 13 C, nitrogen δ 15 N, oxygen δ 18 O and hydrogen δ 2 H of chitosan has been recently proposed without indicating the threshold authenticity limits of these parameters which, for the first time, were estimated in this paper. In addition, on part of the samples analysed through SIR, Fourier transform infrared spectrometry (FTIR) and thermogravimetric analysis (TGA) were performed as simple and rapid discrimination methods due to limited technological resources. Samples having δ 13 C values above -14.2‱ and below -125.1‱ can be considered as authentic fungal chitosan without needing to analyse other parameters. If the δ 13 C value falls between -25.1‱ and -24.9‱, it is necessary to proceed further with the evaluation of the parameter δ 15 N, which must be above +2.7‱. Samples having δ 18 O values lower than +25.3‱ can be considered as authentic fungal chitosan. The combination of maximum degradation temperatures (obtained using TGA) and peak areas of Amide I and NH 2 /Amide II (obtained using FTIR) also allows the discrimination between the two origins of the polysaccharide. Hierarchical cluster analysis (HCA) and principal component analysis (PCA) based on TGA, FTIR and SIR data successfully distributed the tested samples into informative clusters. Therefore, we present the technologies described as part of a robust analytical strategy for the correct identification of chitosan samples from crustaceans or fungi.

Background: Official stable isotope databases, based on the analysis of (D/H) I ethanol , (D/H) II ethanol , δ 13 C ethanol and δ 18 O water of wine, are an indispensable tool for establishing the limits beyond which the mislabeling or the addition of sugar and/or water in wine production can be detected. The present study investigates, for the first time, whether the use of hybrid varieties instead of European Vitis vinifera for wine production can have an impact on the stable isotope ratios., Results: The analyses were performed by isotope ratio mass spectrometry and site-specific natural isotope fractionation by nuclear magnetic resonance, in accordance with the official methods of the International Organization of Grapes and Wine. The comparison shows the tendency of some stable isotope ratios of hybrid varieties, in particular (D/H) I , to deviate from the regional averages of the V. vinifera samples. Notably, Baron, Monarch and Regent showed significantly different values at one of the two sampling sites. Particularly high δ 13 C values characterize Helios compared to other hybrid varieties., Conclusion: For the first time, and from an isotopic point of view, the present study investigates the wine obtained from hybrid varieties, showing that further attention should be paid to their interpretation, on the basis of the database established according to the European Regulation 2018/273. © 2022 Society of Chemical Industry., (© 2022 Society of Chemical Industry.)

The need to guarantee the geographical origin of food samples has become imperative in recent years due to the increasing amount of food fraud. Stable isotope ratio analysis permits the characterization and origin control of foodstuffs, thanks to its capability to discriminate between products having different geographical origins and derived from different production systems. The Framework 6 EU-project "TRACE" generated hydrogen ( 2 H/ 1 H), carbon ( 13 C/ 12 C), nitrogen ( 15 N/ 14 N), and sulphur ( 34 S/ 32 S) isotope ratio data from 227 authentic beef samples. These samples were collected from a total of 13 sites in eight countries. The stable isotope analysis was completed by combining IRMS with a thermal conversion elemental analyzer (TC/EA) for the analysis of δ ( 2 H) and an elemental analyzer (EA) for the determination of δ ( 13 C), δ ( 15 N), and δ ( 34 S). The results show the potential of this technique to detect clustering of samples due to specific environmental conditions in the areas where the beef cattle were reared. Stable isotope measurements highlighted statistical differences between coastal and inland regions, production sites at different latitudes, regions with different geology, and different farming systems related to the diet the animals were consuming (primarily C3- or C4-based or a mixed one).

Curcuminoid complex, a mixture of curcumin, demethoxycurcumin and didemethoxycurcumin, is one of the most popular antioxidants of natural origin, and it has a multitude of other health benefits. It is threatened by the proliferation of counterfeit products on the market containing synthetic curcuminoids whose addition is difficult to identify as they present the three curcuminoid forms in the correct ratios. Consequently, the necessity to detect this fraudulent practice is escalating. Carbon-14 analysis is the most effective available method, but it is also expensive and difficult to implement. This paper describes the first attempt to characterize natural curcuminoids and their synthetic form, used as an adulterant, through the analysis of stable isotope ratios of carbon and hydrogen (expressed as δ 13 C and δ 2 H). Carbon values greater than -28.6‱ and hydrogen values greater than -71‱ may indicate the addition of synthetic curcuminoids to the natural ones.

The objective of this study was to distinguish between the Tunisian Djebel lamb meat and meat from typical Tunisian production systems (PSs) through the fatty acids (FAs) profile and the stable isotope ratio analysis (SIRA). Thirty-five lambs from three different regions and PSs (D = Djebel, B = Bou-Rebiaa, and O = Ouesslatia) were considered for this purpose. The results demonstrated that the PS and the geographic origin strongly influenced the FA profile of lamb meat. It was possible to discriminate between the Djebel lamb meat and the rest of the dataset thanks to the quantification of the conjugated linoleic acids (CLA) and the branched chain FAs. Moreover, statistically different concentrations of saturated, monounsaturated and polyunsaturated FAs and a different n-6/n-3 ratio were found for grazing (D and BR) and indoor (O) lambs, making it possible to discriminate between them. As for the stable isotope ratio analysis, all parameters made it possible to distinguish among the three groups, primarily on the basis of the dietary regimen (δ( 13 C) and δ( 15 N)) and breeding area (δ( 18 O) and δ( 2 H)).

The authenticity of grape musts is normally checked through a time-consuming stable isotopic analysis of carbon ( δ 13 C) after fermentation and distillation by following the official OIV MA AS-312-06 method. In this study, the alternative use of a technique based on δ 13 C isotopic analysis of the major sugars of the grape must by liquid chromatography coupled with isotope ratio mass spectrometry (LC-IRMS) is provided. It allows not only the detection of the fraudulent addition to grape must of exogenous glucose and fructose deriving from C4 plants but also the characterisation of it based on its geographical origin. In order to discriminate between musts from different areas of Italy, a preliminary dataset was considered; the δ 13 C isotopic ratios of glucose and fructose of around 100 authentic samples were analysed. The two analysed parameters, ranging from -29.8‱ to -21.9‱, are well correlated (R 2 = 0.7802) and the northern regions showed significantly more negative δ 13 C values for both sugars than the rest of the dataset.

Fatty acids (FAs) metabolism in animals represents an important field of study since they influence the quality and the properties of the meat. The aim of this study is to assess the possibility to discriminate the diets of cows in different animal compartments and to study the fate of dietary FAs in the bovine organism, using carbon isotopic ratios. Five FAs, both essential (linoleic and linolenic) and non-essential (palmitic, stearic, and oleic) in four compartments (feed, rumen, liver, meat) of animals fed two different diets (based on either C3 or C4 plants) were considered. For all compartments, the carbon isotopic ratio (δ 13 C) of all FAs (with few exceptions) resulted significantly lower in cows fed on C3 than C4 plants, figuring as a powerful tool to discriminate between different diets. Moreover, chemical reactions taking place in each animal compartment result in fraction processes affecting the δ 13 C values. The δ 13 C FAs tendentially increase from feed to meat in group C3. On the other hand, the δ 13 C FAs generally increase from rumen to liver in group C4, while δ 13 C FAs of rumen and meat are mostly not statistically different. Different trends in the δ 13 C FAs of the two groups suggested different FAs fates depending on the diet.

Bacterial endophytes support the adaptation of host plants to harsh environments. In this study, culturable bacterial endophytes were isolated from the African rice Oryza glaberrima L., which is well-adapted to grow with poor external inputs in the tropical region of Mali. Among these, six N-fixer strains were used to inoculate O. glaberrima RAM133 and the Asian rice O. sativa L. cv. Baldo, selected for growth in temperate climates. The colonization efficiency and the N-fixing activity were evaluated and compared for the two rice varieties. Oryza sativa -inoculated plants showed a fairly good colonization efficiency and nitrogenase activity. The inoculation of Oryza sativa with the strains Klebsiella pasteurii BDA134-6 and Phytobacter diazotrophicus BDA59-3 led to the highest nitrogenase activity. In addition, the inoculation of 'Baldo' plants with the strain P. diazotrophicus BDA59-3 led to a significant increase in nitrogen, carbon and chlorophyll content. Finally, 'Baldo' plants inoculated with Kl. pasteurii BDA134-6 showed the induction of antioxidant enzymes activity and the maintenance of nitrogen-fixation under salt stress as compared to the unstressed controls. As these endophytes efficiently colonize high-yielding crop varieties grown in cold temperate climates, they become good candidates to promote their growth under unfavorable conditions.

L-theanine involves a great number of health benefits and dietary supplements containing this molecule are becoming increasingly popular. There is, therefore, a growing need to find ways to discriminate between natural L-theanine extracted from tea leaves and the cheaper, synthetic one obtained using specific bacterial enzymes. A first attempt of stable isotope ratio analysis characterization of the possible synthetic adulterant L-theanine (δ 13 C of -14.3 ± 1.5‰), obtained from vegetable substrates with C4 photosynthetic cycle, and of the more expensive natural L-theanine (δ 13 C of -24.4 ± 1.3‰), extracted from Camellia sinensis plants with C3 photosynthetic cycle, is reported here.

The purpose of this study was to address the lack of knowledge regarding the stable isotopic composition of beef from zebu cattle reared in tropical Africa. Sixty beef carcasses belonging to the most common zebu breeds (Goudali, white Fulani, and red Mbororo) were selected and classified according to their subcutaneous fat color (white, cream or yellow). The stable isotope ratios of five bioelements-H, O, C, N, and S-in muscle fractions and the fatty acids composition were analyzed. Zebu meat from Cameroon shows peculiar δ 13 C values, related to the almost exclusive intake of grazed tropical grasses with photosynthetic cycle C4. It also shows δ 2 H and δ 18 O values higher than those reported in other areas of the world and correlated with the isotopic composition of animal drinking water. The white subcutaneous fat ("white type") zebu showed higher δ 2 H and lower δ 13 C than the "yellow type", that is correlated with a higher content of polyunsaturated fatty acid (PUFA) and a lower amount of saturated fatty acid (SFA) and monounsaturated fatty acid (MUFA). Multielement analysis seems to provide promising results for tracing the regional origin of Cameroon beef and some aspects of the livestock system, such as the nutritional status of the animals.

The contribution of dietary fatty acids to the quality of the meat and their path through the bovine organism is currently the subject of a lot of research. Stable isotope ratio analysis represents a powerful tool for this aim, one that has not been studied in depth yet. In this work, for the first time, the carbon isotopic ratios of six fatty acids (myristic 14:0, palmitic 16:0, stearic 18:0, oleic 18:1n-9, linoleic 18:2n-6 and linolenic 18:3n-3 acids) in different matrixes (diet, rumen, duodenal content, liver and loin) were analysed through gas chromatography combustion isotope ratio mass spectrometry. Moreover, the quantification of the single fatty acids was carried out, providing important information supporting the carbon isotopic ratio results. The variation in the concentration of the fatty acids in the different matrices depends on the chemical modifications they undergo in the sequential steps of the metabolic path. GC-C-IRMS turned out to be a powerful tool to investigate the fate of dietary fatty acids, providing information about the processes they undergo inside the bovine organism., Competing Interests: Decla11ration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Seventy-six samples of saffron were analysed through inductively coupled plasma-mass spectrometry (ICP-MS) and stable isotope ratio analysis. The dataset was formed by 67 samples harvested in different areas of Italy, Morocco and Iran, and nine samples purchased in the Italian market. For the first time, 42 elements and five stable isotopes (δ 13 C, δ 15 N, δ 34 S, δ 2 H and δ 18 O) were considered to carry out the discrimination of the samples on the basis of their geographical origin. Combined ICP-MS and isotopic composition data turned out to be a useful tool for the geographical discrimination of saffron among predefined cultivation sites. K, Cr, Mn, Ni, Zn, Rb, Sr, Mo, Cs, Nd, Eu, Pb, δ 13 C, δ 15 N, δ 34 S and δ 2 H were identified as the significant variables in geographical discrimination. Moreover, the class models generated for saffron cultivated in two specific areas of Central Italy exhibited 100% specificity for Moroccan, Iranian and commercial samples and a high specificity (83% and 84%) for the saffron samples cultivated in other, although close, Italian sites., (© 2020 John Wiley & Sons, Ltd.)

Casein δ 34 S of 725 samples of cheese from all over the world were measured using IRMS. δ 34 S alone made it possible to establish characteristic ranges of values for two types of Italian cheese (Grana Padano PDO and Parmigiano Reggiano PDO) and for the different regions and provinces of both the Grana Padano PDO and the Parmigiano Reggiano PDO zones. Moreover, δ 34 S of PDO Italian samples were compared to both Italian (not PDO) and foreign competitive cheese samples. In all the cases, sulfur isotopic ratio analysis was a powerful tool to fix characteristic ranges of values for cheeses coming from different countries and to improve the information given by other isotopic parameters., (© 2019 John Wiley & Sons, Ltd.)

Stable isotope ratio analysis of the major bioelements (δ 2 H, δ 13 C, δ 15 N, δ 18 O, δ 34 S), considered for the first time as a whole, was used to attempt a geographical characterization of red garlic (Allium sativum L.) cultivated throughout different Italian territories (Abruzzo, Lazio and Sicily). Up to now, no official methods are available to determine the geographical origin of this type of product. In this context, the Isotope Ratio Mass Spectrometry method (IRMS) represents a powerful analytical technique. The characteristic ranges of variability of the five isotope ratios in 56 red Italian garlic samples are here presented as well as their relationships. The geographical origin has some influence over the different ratios, although their data distribution shows some overlap when Principal Component Analysis (PCA) is applied. In spite of the relative closeness of the sampling sites, a model with very good predictive performance of the geographical classification was achieved byLinear Discriminant Analysis (LDA) and k-nearest neighbours (k-NN) method. Moreover, preliminary class modelling based on Soft Independent Modelling of Class Analogy (SIMCA) supports the ability of stable isotope ratios analysis for the geographical traceability of garlic., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

It is possible to distinguish precious vanillin from Vanilla species (planifolia or tahitensis) from much less expensive synthetic and nature-identical vanillin on the basis of the stable isotope ratios of H and C ( 2 H/ 1 H, 13 C/ 12 C). Analysis is usually performed using GC-IRMS (Gas Chromatography - Isotope Ratio Mass Spectrometry) after solvent extraction of vanillin from the sample. Recently, head-space solid-phase microextraction (HS-SPME) has been proposed as an alternative for determining 13 C/ 12 C. The aim of this study was to develop a method to analyse 2 H/ 1 H in vanillin using SPME-GC-IRMS for the first time, by testing different operating conditions and comparing the results with those obtained after solvent extraction. The ultimate scope was to develop a quick, robust and effective method to measure 2 H/ 1 H and 13 C/ 12 C in vanillin to assess the authenticity of labelling. Almost 50 authentic samples from vanilla pods, nature-identical (ex) and synthetic vanillin and 4 commercial food products were taken into account. All the samples were subjected to HS-SPME-GC-IRMS analysis and most of them to GC-IRMS analysis after solvent extraction of vanillin. The SPME method developed for 2 H/ 1 H analysis guarantees the absence of isotopic fractionation, repeatability and reproducibility standard deviation of below 7‰ and savings in terms of time (from 30 to 5 min) and solvent. HS-SPME GC-IRMS analysis of δ 2 H and δ 13 C can be proposed as a rapid and robust method to discriminate different types of vanillin and assess the authenticity of natural vanillin, also contained in food matrices., (Copyright © 2019 Elsevier B.V. All rights reserved.)

This work characterises and distinguishes Italian and Asian goji berries, combining three analytical approaches to determine 5 light stable isotope ratios, 57 mineral elements and 14 carotenoids. The study analyses stable isotope ratios and provides full HPLC-DAD-MS characterisation of the carotenoid fraction in goji berries for the first time. The isotopic composition of Italian berries was characterised by δ 13 C values ranging between -28.2‰ and -25.7‰, δ 15 N between 2.3 and 7.3‰, δ 34 S between 2.6 and 7.9‰, and D/H between -112 and -49‰. Italian goji berries were shown to have a particular composition and interesting nutritional characteristics, specifically a higher total carotenoid content (355 mg/100 g dw mean content vs 198 mg/100 g dw) and higher content of some micronutrients: K, B, Cu, Mo, Se, and Zn. On the basis of δ 34 S, Y, U, Cu, Rb, zeaxanthin palmitate and total carotenoid content, discriminant analysis correctly classified all samples according to their geographical origin., (Copyright © 2018 Elsevier Ltd. All rights reserved.)