Multi-Elemental Analysis and Geographical Discrimination of Greek "Gigantes Elefantes" Beans Utilizing Inductively Coupled Plasma Mass Spectrometry and Machine Learning Models.

Greek giant beans, also known as "Gigantes Elefantes" (elephant beans, Phaseolus vulgaris L.,) are a traditional and highly cherished culinary delight in Greek cuisine, contributing significantly to the economic prosperity of local producers. However, the issue of food fraud associated with these products poses substantial risks to both consumer safety and economic stability. In the present study, multi-elemental analysis combined with decision tree learning algorithms were investigated for their potential to determine the multi-elemental profile and discriminate the origin of beans collected from the two geographical areas. Ensuring the authenticity of agricultural products is increasingly crucial in the global food industry, particularly in the fight against food fraud, which poses significant risks to consumer safety and economic stability. To ascertain this, an extensive multi-elemental analysis (Ag, Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cs, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na, Nb, Ni, P, Pb, Rb, Re, Se, Sr, Ta, Ti, Tl, U, V, W, Zn, and Zr) was performed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Bean samples originating from Kastoria and Prespes (products with Protected Geographical Indication (PGI) status) were studied, focusing on the determination of elemental profiles or fingerprints, which are directly related to the geographical origin of the growing area. In this study, we employed a decision tree algorithm to classify Greek "Gigantes Elefantes" beans based on their multi-elemental composition, achieving high performance metrics, including an accuracy of 92.86%, sensitivity of 87.50%, and specificity of 96.88%. These results demonstrate the model's effectiveness in accurately distinguishing beans from different geographical regions based on their elemental profiles. The trained model accomplished the discrimination of Greek "Gigantes Elefantes" beans from Kastoria and Prespes, with remarkable accuracy, based on their multi-elemental composition.

Stable Isotope Ratio Analysis for the Geographic Origin Discrimination of Greek Beans "Gigantes-Elefantes" (Phaseolus coccineus L.).

Adulteration of high-value agricultural products is a critical issue worldwide for consumers and industries. Discrimination of the geographical origin can verify food authenticity by reducing risk and detecting adulteration. Between agricultural products, beans are a very important crop cultivated worldwide that provides food rich in iron and vitamins, especially for people in third-world countries. The aim of this study is the construction of a map of the locally characteristic isotopic fingerprint of giant beans, "Fasolia Gigantes-Elefantes PGI", a Protected Geographical Indication product cultivated in the region of Kastoria and Prespes, Western Macedonia, Greece, with the ultimate goal of the discrimination of beans from the two areas. In total, 160 samples were collected from different fields in the Prespes region and 120 samples from Kastoria during each cultivation period (2020-2021 and 2021-2022). The light element (C, N, and S) isotope ratios were measured using Isotope Ratio Mass Spectrometry (IRMS), and the results obtained were analyzed using chemometric techniques, including a one-way ANOVA and Binomial logistic regression. The mean values from the one-way ANOVA were δ15NAIR = 1.875‱, δ13CV-PDB = -25.483‱, and δ34SV-CDT = 4.779‱ for Kastoria and δ15NAIR = 1.654‱, δ13CV-PDB = -25.928‱, and δ34SV-CDT = -0.174‱ for Prespes, and showed that stable isotope ratios of C and S were statistically different for the areas studied while the Binomial logistic regression analysis that followed correctly classified more than 78% of the samples.

The Ecophysiological Response of Olive Trees under Different Fruit Loads.

Olive trees have a unique reproductive pattern marked by biennial fruiting. This study examined the repercussions of alternate fruit bearing on the water relations of olive trees and the associated ecophysiological mechanisms. The experiment spanned two consecutive years: the "ON" year, characterized by a high crop load, and the "OFF" year, marked by minimal fruit production. Key ecophysiological parameters, including sap flow, stomatal conductance, and photosynthetic rate, were monitored in both years. Pre-dawn water potential was measured using continuous stem psychrometers and the pressure chamber technique. Biochemical analyses focused on non-structural carbohydrate concentrations (starch, sucrose, and mannitol) and olive leaves' carbon-stable isotope ratio (δ13C). Results revealed a higher leaf gas exchange rate during the "ON" year, leading to an average 29.3% increase in water consumption and a 40.78% rise in the photosynthetic rate. Higher water usage during the "ON" year resulted in significantly lower (43.22% on average) leaf water potential. Sucrose and starch concentrations were also increased in the "ON" year, while there were no significant differences in mannitol concentration. Regarding the carbon-stable isotope ratio, leaves from the "OFF" year exhibited significantly higher δ13C values, suggesting a higher resistance to the CO2 pathway from the atmosphere to carboxylation sites compared to the "ON" year plants.

Mediterranean Plants as Potential Source of Biopesticides: An Overview of Current Research and Future Trends.

The development and implementation of safe natural alternatives to synthetic pesticides are urgent needs that will provide ecological solutions for the control of plant diseases, bacteria, viruses, nematodes, pests, and weeds to ensure the economic stability of farmers and food security, as well as protection of the environment and human health. Unambiguously, production of botanical pesticides will allow for the sustainable and efficient use of natural resources and finally decrease the use of chemical inputs and burden. This is further underlined by the strict regulations on pesticide residues in agricultural products and is in harmony with the Farm to Fork strategy, which aims to reduce pesticide use by 50% by 2030. Thus, the present work aims to compile the scientific knowledge of the last 5 years (2017-February 2023) regarding the Mediterranean plants that present biopesticidal effects. The literature review revealed 40 families of Mediterranean plants with at least one species that have been investigated as potential biopesticides. However, only six families had the highest number of species, and they were reviewed comprehensively in this study. Following a systematic approach, the extraction methods, chemical composition, biopesticidal activity, and commonly used assays for evaluating the antimicrobial, pesticidal, repellant, and herbicidal activity of plant extracts, as well as the toxicological and safety aspects of biopesticide formulation, are discussed in detail. Finally, the aspects that have not yet been investigated or are under-investigated and future perspectives are highlighted.

Application of Stable Isotope Analysis for Detecting the Geographical Origin of the Greek Currants "Vostizza": A Preliminary Study.

There is a plethora of food products with geographical indications registered in the European Union without any study about their discrimination from other similar products. This is also the case for Greek currants. This paper aims to analyze if stable isotope analysis of C, N, and S could discriminate the Greek currants "Vositzza", registered as a product of Protected Designation of Origin, from two other currants registered as products of Protected Geographical Indication coming from neighboring areas. The first results show that the stable isotope ratio of sulfur is not detectable due to the very low sulfur content in the samples, and the analysis should be based on the stable isotope ratios of carbon and nitrogen to discriminate these products. The mean value of δ15N (1.38‱) of PDO "Vostizza" currants is lower than that of currants grown outside the PDO zone (2.01‱), while the mean value of δ13C of PDO "Vostizza" currants is higher (-23.93‱) in comparison to that of currants grown outside the PDO zone (-24.83‱). Nevertheless, the results indicate that with only two isotopic ratios, discrimination could not be achieved, and further analysis is required.

Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), a Useful Tool in Authenticity of Agricultural Products' and Foods' Origin.

Fraudulent practices are the first and foremost concern of food industry, with significant consequences in economy and human's health. The increasing demand for food has led to food fraud by replacing, mixing, blending, and mislabeling products attempting to increase the profits of producers and companies. Consequently, there was the rise of a multidisciplinary field which encompasses a large number of analytical techniques aiming to trace and authenticate the origins of agricultural products, food and beverages. Among the analytical strategies have been developed for the authentication of geographical origin of foodstuff, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) increasingly dominates the field as a robust, accurate, and highly sensitive technique for determining the inorganic elements in food substances. Inorganic elements are well known for evaluating the nutritional composition of food products while it has been shown that they are considered as possible tracers for authenticating the geographical origin. This is based on the fact that the inorganic component of identical food type originating from different territories varies due to the diversity of matrix composition. The present systematic literature review focusing on gathering the research has been done up-to-date on authenticating the geographical origin of agricultural products and foods by utilizing the ICP-MS technique. The first part of the article is a tutorial about food safety/control and the fundaments of ICP-MS technique, while in the second part the total research review is discussed.

Stable Isotope Analysis for the Discrimination of the Geographical Origin of Greek Bottarga 'Avgotaracho Messolongiou': A Preliminary Research.

Consumers are increasingly interested in the geographical origin of the foodstuff they consume as an important characteristic of food authenticity and quality. To assure the authenticity of the geographical origin, various methods have been proposed. Stable isotope analysis is a method that has been extensively used for products such as wine, oil, meat, while only a few studies have been conducted for the discrimination of seafood origin and especially for mullet roes or bottarga products. Analysis of the stable isotopes of C, N and S of Bottarga samples from four different origins were carried out. The values of δ15N (5.45‱) and δ34S (4.66‱) for the Greek Bottarga Product named 'Avgotaracho Messolongiou', from Messolongi lagoon were lower than other areas while δ13C values were higher (-14.84‱). The first results show that the stable isotopes ratios of carbon, nitrogen and sulphur could be used to discriminate the Greek Protected Designations of Origin Bottarga product 'Avgotaracho Messolongiou' from other similar products.

Geographical Origin Authentication of Agri-Food Products: Α Review.

This study is a systematic literature review of geographical origin authentication by elemental analytical techniques. Authentication and certification of geographic origin of agri-food products is a useful tool toward the protection of the quality for products. The aim of this work was to map the current state of research in the area of agricultural products and food, identifying emerging fields to the geographical origin of products. The article is divided in three parts. The first part of the article deals with the analytical techniques applied in the food authentication. Special mention is made to elemental analysis and multiple isotope ratio. The second section focuses on statistically published data concerning published research for geographical origin authentication for the period 2015-2019. Specific results are presented inter alia: number of articles according to the type of product, articles according to the type of the analytical techniques, and others. The third part contains characteristic results from articles that were published in the period 2015-2019, on certification of geographical origin on specific agricultural products.

Effects of 4-month Fe deficiency exposure on Fe reduction mechanism, photosynthetic gas exchange, chlorophyll fluorescence and antioxidant defense in two peach rootstocks differing in Fe deficiency tolerance.

Fe deficiency was imposed by omission of Fe (-Fe), or by inclusion of bicarbonate (supplied as 20 mM NaHCO3) in the nutrient solution in two contrasting peach rootstocks (GF-677; tolerant to Fe deficiency and Cadaman; sensitive to Fe deficiency) for 4 months. In the Fe-deprived leaves and roots, and especially in those treated with bicarbonate, a decrease in Fe concentrations was recorded. Omission of Fe resulted in an increase of the activity of root Fe(III)-chelate reductase (FCR) in both rootstocks, whereas FCR activity decreased in the bicarbonate-treated roots of Cadaman. The results obtained from the FCR assay were confirmed by an agarose-based staining technique used to localize FCR activity. Also, an agar-pH-test revealed that the roots of GF-677 exposed to (-Fe) treatment induced a strong H+ extrusion. In addition, Fe deficiency resulted in reduction of the total chlorophyll (CHL) content. Apart from the (-Fe)-treated leaves of GF-677, Fe deficiency caused a decline in the photosynthetic rate (P(n)) and stomatal conductance (g(s)), without changes of the intercellular CO2 concentration (C(i)), as well as a reduction in the maximum quantum yield of PSII (F(v)/F(m)) and the ratio between variable to initial fluorescence F(v)/F0. The above changes were particularly evident for the bicarbonate-treated leaves of Cadaman. On the other hand, Fe deficiency resulted in an increase of leaf superoxide dismutase (SOD) activity and a depression of catalase (CAT) activity in the leaves and roots, irrespective of the rootstock. Although the non-enzymatic antioxidant activity (FRAP values) was increased in the roots of both rootstocks exposed to -Fe treatment, however, FRAP values were stimulated in the (-Fe)-treated leaves of GF-677 and decreased in the bicarbonate-treated leaves of Cadaman. The H2O2 content was increased in Fe-deprived tissues except for the (-Fe)-treated leaves and roots of GF-677. As a result of Fe deficiency, peroxidase (POD) activity and isoform expression were diminished in the tissues of Cadaman. However, in the tissues of GF-677 subjected to -Fe treatment POD activity was increased whereas an additional POD isoform was detected in the roots suggesting that expression of POD isoforms might be an important attribute linked to the tolerance to Fe deficiency.