L’utilizzo degli scarti da parte dell’industria alimentare costituisce una sfida importante per ridurre le perdite di cibo, aumentare la sostenibilità della produzione alimentare e, pertanto, incrementare la sicurezza alimentare specialmente nei paesi in via di sviluppo. Obiettivo della presente tesi è ottenere aceto dagli scarti dell’ananas tramite idrolisi enzimatica preceduta da pre-trattamento fisico, fermentazione alcolica con differenti ceppi di Saccharomyces cerevisiae, addizionati di Lactobacillus delbruekii o Lactobacillus plantarum del liquido saccarificato, e fermentazione acetica con Acetobacter aceti in un impianto pilota. I campioni ottenuti dalle prove di saccarificazione, fermentazione alcolica e acetica sono stati analizzati per pH, acidità totale, grado Brix, zuccheri, acidi organici, etanolo e per i composti volatili. Una caratterizzazione dettagliata dell’aceto è stata eseguita tramite UPLC/Q-TOF e GC-MS. / Using waste from the food industry is a major challenge to reduce food losses, to increase the sustainability of food production and, therefore, increase food security, especially in developing countries. The objective of this thesis is to get vinegar from pineapple waste by means of: enzymatic hydrolysis proceeded by physical pre-treatment; alcoholic fermentation of the saccharified juice with different strains of Saccharomyces cerevisiae and Lactobacillus delbruekii or Lactobacillus plantarum; acetic fermentation with Acetobacter aceti in a pilot plant. Samples obtained from saccharification, alcoholic and acetic fermentation were analyzed for pH, total acidity, total soluble solid (TSS), sugars, acids, ethanol, and volatile compounds. A detailed characterization of vinegar was carried out through UPLC/Q-TOF and GC-MS.

La tesi di dottorato è stata sviluppata all'interno del progetto nazionale Valorvitis ed è suddivisa in due parti. La prima riguarda la caratterizzazione chimica di sei estratti di vinacce d’uva ottenute diverse varietà di uva: tre a bacca rossa( Pinot Noir, Barbera e Nebbiolo) e tre a bacca bianca (Moscato, Muller Thurgau e Chardonnay). Ogni estratto è stato caratterizzato per contenuto e composizione in composti fenolici. La seconda attività consiste nello studio di un metodo alternativo di estrazione-purificazione basato sull'impiego di Gas Aphron Colloidali (CGAs) con la finalità di ridurre i costi di processo, la quantità di solvente da utilizzare durante la fase di estrazione e, allo stesso tempo, aumentare il grado di purezza dell’estratto in termini di contenuto polifenolico. / The present PhD thesis work was carried out under the framework of the Valorvitis.Extracts have been obtained from different red (Pinot Noir, Barbera and Nebbiolo) and white (Moscato, Muller Thurgau and Chardonnay) grape marcs and quantitatively analysed for the content of total phenolics, tannins, anthocyanins, cinnamic acids, flavonoids, flavonols, sugars (glucose and fructose) and for the anti-oxidant power (AOP). A new extraction-purification process based on CGAs application has been investigated. CGAs were first reported by Sebba (1987) as micro bubbles, with dimension among 10–100 μm, composed of a gaseous inner core surrounded by a thin surfactant film, which are created by intense stirring of a surfactant solution above its critical micellar concentration. Surfactants are able to catch phenolics thanks to both electrostatic and hydrophobic interactions depending on the surfactant (ionic or non-ionic) and on the phenolic compound. In this project the low-cost non-ionic food grade surfactant Tween 20 was used.

Questa tesi di dottorato ha riguardato il recupero di composti ad alto valore aggiunto dai sottoprodotti agro-alimentari e il loro utilizzo in campo alimentare. In particolare, si è studiato il frazionamento lignocellulosico di raspi d’uva e residui di potatura di melo per ottenere emicellulosa, cellulosa, lignina e antiossidanti attraverso processi di auto-idrolisi e organosolv, investigando successivamente l’influenza di sei cultivar sul frazionamento lignocellulosico dei raspi. Un processo composto da quattro fasi (trattamento di lavaggio seguito da un’idrolisi acida, un’idrolisi basica e, infine, una decolorazione basica) è stato applicato su raspi di uva rossa (Barbera, Pinot Noir, Nebbiolo) e bianca (Müller, Chardonnay and Moscato). I raspi sono stati confrontati in termini di composizione chimica della materia prima (umidità, ceneri, minerali, lipidi, fibre, proteine zuccheri liberi) e di frazioni recuperate ( lavaggio, liquors acidi e basici e residui di cellulosa finali). Si è inoltre studiato l’influenza varietale sull’estrazione di antiossidanti da vinacce di Barbera, Pinot Noir and Nebbiolo, i diversi estratti sono stati confrontati per il loro profilo fenolico e per la loro capacità antiossidante. Infine, un estratto liofilizzato di vinacce di Barbera è stato utilizzato per migliorare la shelf-life di una pasta di nocciole valutando l’ossidazione cinetica. / This thesis has focused on the recovery of high value compounds from agri-food by-products and their use in food. In particular, we studied the lignocellulosic fractionation of grape stalks and apple tree pruning for the recovery of hemicelluloses, cellulose, lignin and antioxidants through processes of auto-hydrolysis and organosolv, investigating subsequently the influence of six grape cultivar,on the lignocellulosic fractionation of grape-stalks. A four-step process (a washing treatment followed by an acid hydrolysis, a basic hydrolysis and, finally, a basic bleaching) was applied to stalks obtained from six different red (Barbera, Pinot Noir, Nebbiolo) and white (Müller, Chardonnay and Moscato) grape cultivars. The different stalks were compared in terms of chemical composition of raw material (moisture, ash, minerals, lipids, fiber, proteins, free sugars) and of the recovered fractions (washing, acid and basic liquors and final cellulose residues). We also studied the influence of variety on the antioxidants extraction from Barbera, Pinot Noir and Nebbiolo grape marc. The different extracts were compared in terms of phenolic profile and antioxidant capacity. Finally, a freeze-dried extract from Barbera grape marc was used to improve the shelf-life of hazelnut paste evaluating the oxidation kinetics.

Il verificarsi della presenza di micotossine nella granella di mais è di interesse mondiale perché la loro presenza negli alimenti è spesso associata a malattie acute e croniche nel bestiame e nell'uomo. Le micotossine sono metaboliti fungini secondari tossici per i vertebrati. Molti composti naturali e sintetici con proprietà antiossidanti sembrano avere una potenziale efficacia nella protezione contro gli effetti tossici delle micotossine. Questo lavoro ha avuto come obiettivo lo studio degli effetti degli antiossidanti naturali di mais (carotenoidi e tocoli) sulla crescita di funghi (fusarium verticillioides) e sull'accumulo di micotossine in preparati alimentari a base di mais e su alcuni sottoprodotti della lavorazione del mais. / The occurrence of mycotoxins in cereal grains is of great concern worldwide, because their presence in feeds and foods is often associated with chronic or acute mycotoxicoses in livestock and also in human. Mycotoxins are fungal secondary metabolites that are toxic to vertebrates. Several natural and synthetic compounds with antioxidant properties seem to be potentially efficient in protecting against the toxic effects of micotoxins. This work was aimed to study the effects of natural maize antioxidant (carotenoids and tocols) on fungi (fusarium verticillioides) growth and on micotoxins accumulation in maize-based food products and in maize by-products.

La presente ricerca ha lo scopo di sottolineare l'importanza degli antiossidanti naturali negli ultimi anni. Recenti studi hanno dimostrato l'importanza dei sottoprodotti della vinificazione in quanto particolarmente ricchi di composti fenolici. I fenoli possono essere recuperati da scarti (diminuendo il loro effetto inquinante) e usati come antiossidanti naturali in sostituzione di quelli chimici in sistemi alimentari per aumentare la shelf life. / The present research is aimed to underline the increasing importance that natural antioxidants have been gaining in the last years. Recent investigations have stressed the importance of vinification by-products as plant materials particularly rich in phenols. Phenols could be recovered by wastes (diminishing their pollutant effect) and used as natural antioxidant instead of chemical ones in food systems to extend the shelf life.

L'obiettivo principale di questo progetto è quello di trovare diverse soluzioni per migliorare le caratteristiche tecnologiche, sensoriali, di sostenibilità e nutrizionali dei prodotti da forno. Come campione sono stati scelti i biscotti perché ampiamente consumati e rappresentano una buona fonte energetica, nonostante l'elevato contenuto di zuccheri e grassi. Sono state studiate diverse strategie. 1. Produzione di una farina funzionale grazie al condizionamento enzimatico del grano per ottenere una farina intera con una migliore qualità tecnologica e un migliore profilo nutrizionale. 3. Sostituzione dell'olio di palma con un ingrediente grasso più sostenibile e più sano, come l'olio extravergine di oliva, l'olio di vinaccioli, rispetto all'olio di girasole, ampiamente utilizzato. 3. Arricchimento con diversi ingredienti funzionali: a. proteine del siero di latte: l'idrolisi enzimatica è stata studiata come strategia per ottenere ingredienti proteici adatti a produrre biscotti; b. fibre: diverse fibre, principalmente derivate da sottoprodotti, sono state testate per valutare il loro potenziale ruolo come ingredienti funzionali per migliorare la consistenza e la stabilità ossidativa dei biscotti; c. estratto di buccia d'uva di scarto: la tecnologia di stampa 3D è stata utilizzata per ridurre l'effetto termico del processo di cottura sull'attività antiossidante di un estratto incapsulato aggiunto ai biscotti. / The main objective of this Ph.D. project was to find different solutions to improve the technological, sensorial, sustainability and nutritional characteristics of bakery products. Biscuits were used because of their characteristics: they are widely consumed and they are a good energy source, despite the high content in sugars and fats. Different strategies were investigated. 1. Production of a functional flour thanks to enzymatic conditioning of the wheat to obtain a whole flour with both better technological quality and improved nutritional profile for dietetic fibre composition and antioxidant compounds. 2. Substitution of palm oil with a more sustainable and healthier fat ingredient, such as extra virgin oil, grape seeds oil, in comparison with the widely used, sunflower oil. 3. Enrichment with different functional ingredients: a. whey proteins: enzymatic hydrolysis was investigated as a strategy to get protein ingredients suitable to produce acceptable high proteins biscuits; b. fibers: different fibres, mainly derived from by-products, were tested to evaluate their potential role as functional ingredients to improve texture and oxidative stability of biscuits; c. waste grape skins extract: 3D-printing technology was used to minimize the degradation effect of the baking process on antioxidant activity of an encapsulated grape-skin extract added to biscuits.

La Valle d'Aosta, pur non avendo grandi superfici destinate alla viticoltura, è caratterizzata dalla presenza di un ricco patrimonio ampelografico di cui fanno parte dodici varietà autoctone a bacca rossa: Bonda, Cornalin, Crovassa, Fumin, Mayolet, Ner d'Ala, Petit rouge, Premetta, Roussin, Roussin de Morgex, Vien de Nus e Vuillermin. Malgrado i numerosi vitigni menzionati, nella produzione dei vini a D.O.C troviamo in prevalenza il Petit rouge e poche altre varietà che, nell'insieme, rappresentano circa il 34% della produzione totale. Al fine di implementare la presenza di prodotti tipici che esprimano i caratteri distintivi della zona di provenienza sono state approfondite le conoscenze dei vitigni autoctoni per evidenziarne le attitudini e le potenzialità per la produzione di vini rossi di qualità. Allo stesso scopo sono stati valutati gli effetti dell'applicazione di alcune tecniche di vinificazione alternative sull'espressione dei caratteri qualitativi del Petit rouge, le cui uve sono da tempo vinificate in purezza o in assemblaggi nella produzione di vini a D.O.C. / Aosta Valley has a little viticulture surface and it is characterised by a rich ampelographic collection including the following twelve red grape autochthonous varieties: Bonda, Cornalin, Crovassa, Fumin, Mayolet, Ner d'Ala, Petit rouge, Premetta, Roussin, Roussin de Morgex, Vien de Nus e Vuillermin. Only the 34% of the D.O.C. wine production is represented by some of the above mentioned cultivars, in particular the Petit Rouge, despite of the huge number of cultivars. The Petit rouge is used in purity or in miscellaneous in the D.O.C. wine production. In order to implement the presence of typical products, this study was carried out to evaluate the aptitude of Aosta Valley ancient grapes to produce quality red wines. Moreover to improve quality of the most diffused Aosta Valley red wine the effects of some alternative winemaking were evaluated on the Petit rouge characters.

This study aim at the valorization of wine industry by products; particularly on the extraction and characterization of grape seeds oil using supercritical CO2 (SC-CO2) and polyphenols from grape skins and defatted grape seeds using subcritical water (SW) and then, modeling of the kinetics of extractions and process economic analysis. The overall objective of the work is to develop recovery strategies for wine-making wastes in order to reduce their environmental impact and to valorize them in order to provide wine-makers with the possibility of selling by-products at a profitable price. To address the objectives, the work is divided into seven Chapters. In Chapter 1, some general overview and the fundamental of SC-CO2 and SW technologies along with emerging areas of applications are presented. Special emphasis is given to the work in the field of valorization of agro-industrial by-products. Then, the Chapter ends by stating the general and specific objectives of the thesis. The second Chapter is devoted to the characterization of grape seeds oil. To make the result more holistic, grape seeds from six grape cultivars were extracted using SC-CO2 in two subsequent harvesting years and the resulting oils were characterized. Comparative extractions were also performed by utilizing conventional solvent extraction using n-hexane and by mechanical press. The results testify the potentiality of grape seed oil as a source of unsaturated fatty acids and tocols. Moreover, they offers a clear picture of the similarities and differences among oils from different grape cultivars and obtained through different extraction techniques. The third Chapter is dedicated to compare the effectiveness of the models used to evaluate the kinetic of SC-CO2 extraction curves. Particularly, three models, the broken and intact cells (BIC), the shrinking core (SC), and the bridge (combined BIC-SC) models are critically analyzed. The objective of the Chapter is to objectively choose the best model that can be used in the subsequent Chapters. In order to model the kinetics of SC-CO2 extraction, one of the very important parameter is the solute solubility. But solubility data (especially of grape seed oil) is very scares in the literature. The bulk majority of the scientific works estimate the value of solubility of solute in SC-CO2 from theoretical models. So, the fourth Chapter is devoted to experimental determination of solubility of grape seed oil in SC-CO2 over a range of pressure and temperature of practical importance and the data were modeled by different models to compare their effectiveness. The fifth Chapter is aimed to study the effect of the main process variables affecting the SC-CO2 extraction of oil from grape seeds, both experimentally and through modeling. The dependency of the extraction kinetics on the variables more tested in the literature (pressure, temperature, particle size and solvent flow rate) was confirmed, and original trends were obtained for the less investigated variables, such as the bed porosity (ε), the extractor diameter to length ratio (D/L), the extractor free volume and the type of cultivars. In the sixth Chapter the attention is moved to the valorization of grape skins and defatted grape seeds by using SW. The results show that, both skins and defatted seeds contain significant concentration of polyphenols and SW is a potential green solvent for extracting valuable polyphenols from wine-making by-products. The extraction kinetics was also simulated by a simple model available in the literature. In the seventh and last Chapter, a preliminary economic feasibility study was investigated for the establishment of SC-CO2 extraction plant for the extraction of grape seeds oil. The result shows that, a SC-CO2 extraction plant is technically viable and economically feasible for the extraction of grape seed oil with estimated rate of return on investment at 8.5% and payback period of 5 year at current minimum retail selling price of grape seed oil in the market. The project has an attractive socio-economic and environmental benefit and generates substantial revenue for the local government in the form of tax and will allow wine-makers to sell wet grape marc at a price of up to US$ 10/ton.

Hydrothermal carbonization (in acronym, HTC) is a thermochemical conversion process through which it is possible to directly transform wet organic substrates into a carbonaceous material, referred as hydrochar. Hydrochar has chemical and physical characteristics that make it similar to fossil peats and lignite. Depending on the process conditions, mostly temperature and residence time, this material can be enriched in its carbon content, modifying its structure and providing it interesting characteristics that make it possible to be used for several applications, such as for energy production, as a soil conditioner and improver, for carbon dioxide sorption and sequestration, and some others reported in literature. HTC is a different process, if compared to other common thermochemical processes, such as pyrolysis, torrefaction, gasification, etc., because it works in wet conditions (humidity content higher than 60%). As a matter of fact, biomass is transformed into hydrochar because of the properties of hot pressurized water, that acts both as a reactant and as a catalyst. The HTC process has been studied from many years, although at present not all the chemical reactions that occur during the process are completely known. Moreover, the application of this quite new process to different substrates can bring to different results. Even though HTC can be applied to any kind of organic material (of both animal and vegetable derivation), the possible uses of hydrochar can strongly be influenced by the characteristics of the feedstock. This, for example, can be due to legislative constraints. In Chapter 1, an overview of the existing literature is presented. To get insights on this process, a small bench scale batch reactor has been designed and built at the Department of Civil, Environmental and Mechanical engineering of the University of Trento, Italy. This reactor has been tested, prior to be used with real substrates. In Chapter 2 the reactor and the preliminary tests done are described. In this work, the HTC process applied to three different substrates have been studied: grape marc, the EWC 19.05.03 residue and the EWC 19.12.12 residue. In Chapter 3 the three raw substrates are described. Grape marc is produced by the winery industries or by distilleries. This feedstock is composed by woody seeds and holocellulosic skins and it presents an average humidity content of about 60%. At present, it is used for the production of animal food or it is landfilled. In this case, the application of HTC can be an interesting alternative to these end uses because, through this process, grape marc can be recovered, for example, for energy production. The hydrochar produced from this feedstock could be even used as a soil conditioner. In Chapter 4 several analyses on the hydrochar, on the process water and on the gaseous phase obtained during the carbonization tests are presented. The EWC 19.05.03 residue is a by-product of the composting treatment applied to the organic fraction of municipal solid waste (MSW). In collaboration with Contarina S.p.A., a company that collects and treats MSW in the province of Treviso, in the North-East of Italy, this by-product was carbonized and tested both as a soil conditioner and for energy production. Results of the analyses on the solid, liquid and gaseous phases produced by the HTC process are reported in Chapter 5. The EWC 19.12.12 residue is a by-product of the refuse derived fuel (RDF) production, from the residual fraction of the MSW. This substrate was provided by Contarina S.p.A. and preliminary tests on the exploitability of the hydrochar for energy production are reported in Chapter 6, together with analyses on both the liquid and gaseous phases. A rigorous energy balance has been proposed in Chapter 8, based on the experimental data obtained for grape seeds. In this chapter, all the hypotheses and the assumptions taken to evaluate the enthalpy of the HTC reaction at different process conditions (namely, three different temperatures and three residence times) are described. In Chapter 8 a kinetic model is proposed, based on a two-step reaction mechanism. The activation energy and pre-exponential factor of the various degradation reactions were determined by means of least square optimization versus the experimental data of grape marc. A thermo fluid model is even proposed in this chapter. The model integrates mass, momentum and heat equations within the reactor domain by means of the finite volumes method (f.v.m.) approach. Convective and radiative exchange between the reactor and the fluid within the reactor have been implemented in the f.v.m. model. Under two strong assumptions (mono-component and mono-phase fluid, which fulfils the reactor), it was possible to estimate the behaviour of an equivalent fluid (eq_fluid), in terms of thermal properties of the fluid (thermal capacity, thermal conductivity and thermal diffusivity). Moreover, a simplified dynamic analytic model is also presented – based on lumped capacitance method – in order to simulate the thermal behaviour of the system, using the actual temperature profile imposed by the reactor external heater. A resistance-capacitance network was used to describe the system. Finally, the Henry’s law has been applied to assess the amount of gas really produced during the HTC process. In Chapter 9, the main conclusions of this work are reported.