To fight counterfeits and to protect the consumer, the interest in certifying the origin of agricultural goods has been steadily growing in the last years. While numerous works focus on the finished product, an aspect often overlooked is the origin of the raw materials and the direct correlation between chemicals in the soil and the plants. With inductively coupled plasma mass spectrometry (ICP-MS) analysis, trace and ultratrace elements in Sangiovese grapes (the main component of Chianti wine) were measured and their levels were used to investigate the geographical origin of the samples. This was achieved despite the extreme closeness of some of the vineyard partners of this study (10-20 km range) by computing a multivariate model using selected elements as levels. The model was then validated on samples coming from different zones of the Chianti area, with good results for discriminating even extremely close regions.

Geographical origin authentication of agrifood products is essential for ensuring their quality, preventing fraud, and maintaining consumers’ trust. In this study, we used proton nuclear magnetic resonance (¹H NMR) and excitation–emission matrix (EEM) fluorescence spectroscopy combined with chemometric methods for the geographical origin characterization of olive drupes and leaves from different Tuscany subregions, where olive oil production is relevant. Single-block approaches were implemented for individual datasets, using principal component analysis (PCA) for data visualization and Soft Independent Modeling of Class Analogy (SIMCA) for sample classification. ¹H NMR spectroscopy provided detailed metabolomic profiles, identifying key compounds such as polyphenols and organic acids that contribute to geographical differentiation. EEM fluorescence spectroscopy, in combination with Parallel Factor Analysis (PARAFAC), revealed distinctive fluorescence signatures associated with polyphenolic content. A mid-level data fusion strategy, integrating the common dimensions (ComDim) method, was explored to improve the models’ performance. The results demonstrated that both spectroscopic techniques independently provided valuable insights in terms of geographical characterization, while data fusion further improved the model performances, particularly for olive drupes. Notably, this study represents the first attempt to apply EEM fluorescence for the geographical classification of olive drupes and leaves, highlighting its potential as a complementary tool in geographic origin authentication. The integration of advanced spectroscopic and chemometric methods offers a reliable approach for the differentiation of samples from closely related areas at a subregional level.

Biofumigation was proposed as an alternative to synthetic pesticides for the disinfection of agricultural soils, in view of the biocidal effect of isothiocyanates (ITCs) released by some vegetal species, like Brassicaceae. However, biofumigation also presents limitations; thus, a novel and viable alternative could be the direct introduction of ITCs into agricultural soils as components loaded into biodegradable hydrogels. Thus, in this work, ITCs-based microemulsions were developed, which can be loaded into porous polymer-based hydrogel beads based on sodium alginate (ALG) or sodium carboxymethyl cellulose (CMC). Three ITCs (ethyl, phenyl, and allyl isothiocyanate) and three different surfactants (sodium dodecylsulfate, Brij 35, and Tween 80) were considered. The optimal system was characterized with attenuated ATR-FTIR spectroscopy and differential scanning calorimetry to study how the microemulsion/gels interaction affects the gel properties, such as the equilibrium water content or free water index. Finally, loading and release profiles were studied by means of UV–Vis spectrophotometry. It was found that CMC hydrogel beads showed a slightly more efficient profile of micelles’ release in water with respect to ALG beads. For this reason, and due to the enhanced contribution of Fe(III) to their biocidal properties, CMC-based hydrogels are the most promising in view of the application on real agricultural soils.

To fight counterfeits, and to protect the consumer, the interest in certifying the origin of agricultural goods has been growing in recent years. In this context and to increase the accuracy of zoning models, multiple analytical techniques must be combined via a multivariate approach. During the sampling campaign, leaves and fruits (olives or drupes) were collected from multiple orchards and farms. By means of HPLC-DAD, metabolite levels were evaluated and combined with the trace and ultra-trace metal/metalloid levels evaluated by ICP-MS (QqQ). The combined dataset was then used to develop a model for geographical traceability. Furthermore, the mineral content of the soil, evaluated by means of ICP-MS, was correlated with both the mineral content in the leaves and drupes and the metabolomic profiles to further investigate the connection between the orchard’s location and characteristics of the final products.

Biofumigation was originally proposed as an alternative to toxic fumigants for the treatment of agricultural soils, owing to the biocidal effect of isothiocyanates (ITCs) released by some plant species like Brassicaceae. However, biofumigation also presents limitations; thus, an advanced and viable alternative could be the use of controlled-release systems such as gelled polymer networks. In the present work, we explore the use of biocompatible hydrogels based on sodium alginate (ALG) and sodium carboxymethylcellulose (CMC), conveniently loaded with a Brassicaceae extract for this purpose. The extract was characterized by means of HPLC-MS, showing its high glucosinolate content, especially glucoraphanin, a secondary metabolite produced by several species of this family. The physicochemical properties of the synthesized gels were investigated by means of differential scanning calorimetry (DSC), rheometry, and scanning electron microscopy (SEM), both in the presence and absence of the loaded extract. Loading and release kinetics (in water) were studied by means of HPLC-DAD, and the Weibull model was employed to interpret the results. It was found that both hydrogels can effectively confine the Brassicaceae extract’s active principle, slowly releasing it in an aqueous environment. Both systems possess excellent properties for real applications, with the CMC-based hydrogels being slightly preferable over the ALG ones due to their higher encapsulation efficiency, mechanical properties, and overall features. These systems are promising tools for combating harmful microorganisms due to the biocidal properties of glucosinolates, but their potential goes beyond their use in agriculture, as they could be applied as antifouling or antimicrobial agents in cultural heritage cleaning or other fields.