Valorization of Citrus spp. Cultivars cultivated in Sicily for the industrial use of citrus derivatives and in particular for potential alternative uses of essential oils for the enhancement of the island's citrus production

[ES] En esta tesis doctoral se discuten una serie de cuestiones científicas relacionadas con a la producción y el procesamiento de algunas especies de cítricos de especial relevancia en Sicilia y en el área mediterránea. Los objetivos se centran en estudiar la trazabilidad y sostenibilidad de la producción de algunas especies de cítricos, así como encontrar nuevas aplicaciones a los subproductos y productos de desecho de la industria, con el fin de mejorar su rentabilidad. Por lo tanto, los temas que se desarrollarán serán los siguientes: caracterización de los compuestos bioactivos presentes en aceites esenciales y en el hidrolato de diferentes especies de cítricos; seguimiento del efecto del estrés hídrico controlado sobre la producción de aceites esenciales en hojas y flores del cv. Sanguinelli de Citrus sinensis y del cv. Clemenules de Citrus reticulata; estudio de los efectos fitotóxicos de los aceites esenciales en cuatro especies arvenses importantes en el área mediterránea, dos monocotiledóneas (Echinochloa crus-galli (L.) P.Beauv. y Avena fatua L.) y dos dicotiledóneas (Amaranthus retroflexus L. y Portulaca oleracea L.) mediante experimentos in vitro e in vivo; estudio del efecto bioestimulantes de las aguas residuales de la industria procesadora de cítricos sobre la comunidad microbiana del suelo; cuantificación de elementos de tierras raras en frutos de limón cultivados en diferentes áreas geográficas, para su posible uso como trazador geoquímico. Los principales resultados obtenidos son la caracterización de diferentes aceites esenciales, de los cuales los producidos por los residuos de la poda podrían ser utilizados como método de extracción de nuevos aceites esenciales con alto rendimiento. También se han encontrado sustancias nutracéuticas y farmacológicas en los hidrolatos industriales de naranja. Por otra parte, el aceite esencial industrial de limón mostró un buen potencial como agente herbicida, siendo, por tanto, de gran interés en la fabricación de herbicidas de origen natural, biodegradables y ecológicos. La aplicación del estrés hídrico controlado después del reposo invernal y, por tanto, en el momento de la brotación incrementó el diámetro final del fruto. La respuesta en el árbol no fue inmediata. La aplicación de hidrolatos de limón, naranja y mandarina al suelo junto al agua de riego, potenció los depósitos de C contribuyendo a aumentar la biomasa y mejoró la actividad microbiana. Estos resultados ponen de manifiesto el papel que los hidrolatos pueden desempeñar en la agricultura sostenible mejorando la fertilidad del suelo. Finalmente, el modelo de elementos de tierras raras podría utilizarse como una herramienta de conexión entre la producción de limón y el suelo del que proviene, contribuyendo, de esta manera, a su caracterización geográfica. En resumen, los resultados obtenidos en esta tesis contribuyen a impulsar el sector cítrico siciliano ya que: proporcionan medios para una agricultura sostenible; aumentan el valor de los subproductos y residuos de la industria; proponen aplicaciones para que el ciclo de producción y transformación sea más rentable y revalorizan los limones sicilianos vinculándolos a su zona de producción.[CA] En esta tesi doctoral es discutixen una sèrie de qüestions científiques relacionades amb la producció i el processament d'algunes espècies de cítrics d'especial rellevància a Sicília i a l'àrea mediterrània. Els objectius, acordats prèviament amb la indústria de cítrics "EuroFood" i finançats pel projecte d'investigació "PON Industrial Ph.D. - a.a. 2016/2017", es centren en estudiar la traçabilitat i sostenibilitat de la producció d'algunes espècies de cítrics, així com de trobar noves aplicacions als subproductes i productes de rebuig de la indústria, amb el fi de millorar la seua rentabilitat. Per tant, els temes que es desenvoluparan seran els següents: caracterització dels compostos bioactius presents en els olis essencials i en el l'hidrolato de diferents espècies de cítrics; seguiment de l'efecte de l'estrés hídric controlat en la producció d'olis essencials en fulles i flors del cv. Sanguinelli de Citrus sinensis i del cv. Clemenules de Citrus reticulata; estudi dels efectes fitotòxicos dels olis essencials de cítrics en quatre espècies arvenses importants en l'àrea mediterrània, dos monocotiledònies (Echinochloa crus-galli (L.) P.Beauv. i Avena fàtua L.) i dos dicotiledònies (Amaranthus retroflexus L. i Portulaca oleracea L.) per mitjà de diferents experiments in vitro i in vivo; estudi de l'efecte bioestimulant de les aigües residuals de la indústria processadora de cítrics sobre la comunitat microbiana del sòl; quantificació d'elements de terres rares en fruits de llima cultivats en diferents àrees geogràfiques, per al seu possible ús com a traçador geoquímic. Els principals resultats obtinguts són la caracterització de diferents olis essencials, dels quals els produïts pels residus de la poda podrien ser utilitzats com a mètode d'extracció de nous olis essencials amb alt rendiment. També s'han trobat substàncies nutracéutiques i farmacològiques en els hidrolats industrials de taronja. D'altra banda, l'oli essencial industrial de llima va mostrar un bon potencial com a agent herbicida, sent, per tant, de gran interés en la fabricació d'herbicides d'origen natural, biodegradables i ecològics. L'aplicació de l'estrés hídric controlat després del repòs hivernal i, per tant, en el moment de la brotació va incrementar el diàmetre final del fruit. La resposta en l'arbre no va ser immediata. L'aplicació de hidrolats de llima, taronja i mandarina al sòl amb l'aigua de reg, va augmentar els depòsits de carbó (C) contribuint a augmentar la biomassa i va millorar l'activitat microbiana. Aquests resultats posen de manifest el paper dels hidrolats en l'agricultura sostenible millorant, d'aquesta manera, la fertilitat del sòl. Finalment, el model d'elements de terres rares podria utilitzar-se com una ferramenta d'enllaç entre la producció de llima i el sòl del què prové, contribuint, d'esta manera, a la seua caracterització geogràfica. En resum, els resultats obtinguts en esta tesi doctoral contribueixen a impulsar el sector cítric sicilià ja que: - proporcionen mitjans per a una agricultura sostenible; - augmenten el valor dels subproductes i residus de la indústria; - proposen aplicacions perquè el cicle de producció i transformació siga de més rendabilitat; - revaloritzen les llimes d'origen sicilià vinculant-les a la seua zona de producció.[EN] In this doctoral thesis are discussed a series of scientific issues regarding citrus fruits production and processing, species of particular relevance in Sicily and in the Mediterranean area. Objectives and research activities addressed in this thesis were agreed with the citrus industry "EuroFood" and financed by the research project "PON industrial Ph.D. - a.a. 2016/2017". The research project was targeted to study the traceability and sustainability of citrus production, and to find new applications to the by-products and waste products of citrus industry with the objective of appreciate and enhance the Sicilian citrus industry. The following topics are addressed and developed in this thesis: - Characterization of the bioactive compounds present in essential oils (EOs) and in the hydrolate of different citrus species. - Monitoring of the effect of controlled water stress on the production of EOs in leaves and flowers of Citrus sinensis (L.) Osbeck cv. 'Sanguinelli' and Citrus reticulata Blanco cv. 'Clemenules'; -Test the phytotoxic effects of citrus EOs on four important weed species in the Mediterranean area, two monocotyledon (Echinochloa crus-galli (L.) P.Beauv. and Avena fatua L.) and two dicotyledon (Amaranthus retroflexus L., and Portulaca oleraceaL.) by different experiments in vitro and in greenhouse conditions; -Evaluation of the effect as natural biostimulants of wastewaters from citrus processing industry by its application on soil microbial community; -Quantification of rare earth elements in lemon fruits from different geographical areas for its possible use as geochemical tracers applied to lemon production. Different Citrus EOs have been characterized in this study and it has been verified that the oils produced by the pruning waste could be used for the extraction of EOs with high yields. In addition, nutraceutical and pharmacological substances have been found in the orange industrial hydrolates. Industrial lemon EO showed good potential when testing its herbicidal activity. Lemon EO represents a good basis for the development of herbicides of natural origin, biodegradable and eco-friendly. Thanks to the application of water stress after the winter vegetative restart, a conclusion found was that water stress increased the diameter of the fruit and it was observed that the effects of stress were not immediate on citrus trees, but were evident after some time. The study of the application of lemon, orange and mandarin hydrolates in the soil, as irrigation water provided the effects on stable and labile soil C pools, on biomass and microbial activity and on main microbial groups. Overall, hydrolates can play a role in sustainable agriculture because when added to a soil, they improve soil quality and fertility. The Rare Earth Element model could be used as a tool to connect lemon production to the soil where they were produced, for a possible geographical characterization and a direct link between the production and the territory or soil. The results obtained were very interesting because: - they provided the means for sustainable agriculture; - they increased the value of the by-products and waste products of the citrus industry; - they proposed applications for the citrus production and transformation cycle being more sustainable; - they could valorize the Sicilian lemons by linking them to their production area. These results could have practical repercussions in the production cycle of citrus fruits and give a boost to the Sicilian citrus fruit sector.Objectives and research activities addressed in this thesis were agreed with the citrus industry "EuroFood" and financed by the research project PON industrial Ph.D. - a.a. 2016/2017Ioppolo, A. (2020). Valorization of Citrus spp. Cultivars cultivated in Sicily for the industrial use of citrus derivatives and in particular for potential alternative uses of essential oils for the enhancement of the island's citrus production [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/159385TESI

Distribution of REEs in soil-citrus limon system(L.) Osbeck

The consumers have an increasing interest about food traceability with respect to safety, quality and typicality issues. The knowledge of a chemistry relationship between the soil and the agricultural products is an important tool for the quality assessment of food. Citrus Limon is the most important fruit tree crop in the world and the detection of potential fraud could improve by using tools linking the chemistry composition of this production to its typical growing area. This study use rare earth elements (REEs) as geochemical tracers. The REEs are a set of 14 elements, from lanthanum to lutetium that can be divided in light rare earth elements (LREEs), from La to Gd and heavy rare earth elements (HREEs), from Tb to Lu. The REEs have recognized as very useful tracers due to their generally coherent and predictable behaviour. The aim of the research is to observe whether the fruits of various cultivars of citrus cultivated on the same soil and their products (fruit and juice) reproduce the same distribution of REEs. Taking into account of our previous works carried out on grapevine – soil system [1,2], we applied the same technique to evaluate and trace the REEs distribution in soil– Citrus Limon fruits system. Sampling of soil and of fruits was carried out in the CREA experimental farm located in Acireale (CT, Sicily) where are present several Citrus Limon cultivars cultivated in Sicily. The REEs amount, the HREEs/LREEs relations and their distribution in the fruit and citrus juice with respect to the own soil were determined and calculated. The intriguing results obtained with a geochemical approach are the first on the soil–Citrus Limon fruits system

Soil bioindicators and weed emergence as affected by essential oils extracted from leaves of three different Eucalyptus species

The widespread use of synthetic herbicides has resulted in herbicide-resistant weeds, altered ecological balance and negative effects on human health. To overcome these problems, efforts are being made to reduce the reliance on synthetic herbicides and shift to natural products. Essential oils (EOs) extracted from plants have been demonstrated to have potential herbicide activity. EOs, composed by volatile organic compounds and characterized by a strong odor, are used in the cosmetic, pharmaceutical and food industries as they are thought to be safe compounds for humans, animals, and the environment. EOs extracted from Eucalyptus leaves have antimicrobial, antiviral, fungicidal, insecticidal, anti-inflammatory, anti-nociceptive and anti-oxidant effects. Moreover, in vitro studies have demonstrated that they have inhibitory effects on germination of seeds of many crops and weeds. The aim of this work was to evaluate the in vivo effects of EOs extracted from Eucalyptus leaves on both weed emergence and biochemical soil properties. Furthermore, since the diverse species of Eucalyptus have shown to have different biological activities, EOs were extracted from three Eucalyptus species (E. camaldulensis, E. globulus, E. occidentalis). Fresh leaves were collected from an afforested area near Piazza Armerina (province of Enna, Italy) and their EOs extracted by hydrodistillation. Soil samples were collected from the topsoil (<5 cm) of an Inceptisol within the experimental farm of the University of Palermo, air-dried and sieved at 1 cm. Five hundred grams of this soil were filled in each of 20 aluminum pots (10×20 cm). The soil samples were brought up to 100% of the water holding capacity (WHC) by adding 150 mL of tap water, followed by 70 mL of tap water containing 8 mL L-1 of one of the three extracted EOs. This experimental test was repeated for remaining two EOs. Fitoil was used as emulsifier at a concentration of 0.1% (v/v). The control consisted of the soil treated as the EO treatment but with Fitoil only. The soils were incubated in greenhouse conditions. After 2 days, the 100% WHC halved and then it was kept to this level (50% WHC) by watering soil daily. The experiment was carried out in quadruplicate. After one month the soil were brought up to 100% of WHC, plant biomass and height of germinated weeds and soil biochemical properties were evaluated. This work reports the results and discuss them

Phytotoxic potential of Citrus essential oils on weed species

Environmental constraints of crop production systems have stimulated interest in alternative weed management strategies. In fact, the continued use of synthetic herbicides may threaten sustainable agricultural production and result in serious ecological and environmental problems, such as the increased incidence of resistance in weeds to important herbicides and increased environmental pollution and health hazards. Public awareness and demand for environmentally safer herbicides with less persistence and less contaminating potential make searches for new weed control strategies. Citrus Essential oils are generally used in the cosmetic, medicinal, and food industries, and are thought to be safe compounds for humans, animals, and the environment. EOs can be extracted by hydro distillation and cold pressing. The two methods are based on different procedures. Hydro distillation is carried out with a Clevenger-apparatus that conducts the distillation process by boiling, condensing and decantation to separate the EOs. The cold pressing consist of crushing and pressing the peels thus leading to the formation of a watery emulsion. Then, the emulsion is centrifuged to separate out the EOs. Since no external substance are needed, this process ensures that the resulting EOs retains all their properties. The allelopathic and phytotoxic effects of EOs obtained from other species and their potential use for weed management has been well documented. The objectives of this study were to evaluate in vitro the phytotoxic effects of Citrus EOs (Citrus sinensis, Citrus limon and Citrus reticulata) extracted by hydro distillation and cold pressing on main weed species (Amaranthus retroflexus, Portulaca oleracea., Echinochloa crus-galli, Avena sativa). For all EOs six concentrations were tested (0.5, 1, 2, 4, 8, 12) μl/ml and 5 repetitions with 20 seeds each (for dicotyledons) or 10 repetitions with 10 seeds each (for monocotyledons) were performed. They were applied for one hundred seeds for concentration. Twenty seeds were placed into 9 cm diameter Petri dishes for Amarantus and Portulaca. In each Petri dish, 5 ml of distilled water were added. This volume kept the filter papers uniformly soaked-wet without flooding. For Avena and Echinocloa ten seeds were placed into petri dishes and 6 ml of distilled water was added. The essential oil was placed in a sheet of filter papers in contact with the seeds. The controls were prepared with the same quantities of distilled water. Petri dishes were incubated in the room germination (EQUITEC) at 20/30 °C (±1 °C), alternating temperature (6/18 h dark and light (cool white Radium NL 36W/840; 3100 lm)). Dishes were sealed to reduce evaporation, and no more additional water was supplied during the tests. To evaluate the possible phytotoxic effects of the essential oils and their main compounds on seed germination and seedling growth data were registered by taking photos after 3,5, 7, 10 and 14 days after incubation and will be processed using Digimizer. Then data will be analysed and discussed

Dynamics of Water-Soluble Metals in Soil Moistened with Citrus Wastewaters Depends on Soil Reaction and Organic Acids

The demand for water for civil and industrial use is diminishing the availability of such a valuable environmental resource for agricultural purposes. Thus, for the next generation, it is imperative to find alternative water sources for crop irrigation. The citrus agroindustry utilizes a large amount of water for processing fruit (e.g., essential oil extraction, fruit washing). Wastewaters produced by citrus industry (CWWs) are rich in organic matter and mineral nutrients, thus making them potentially usable for crop irrigation. Conversely, due to their high content of organic acids and low pH, they may increase the availability of soluble metals, in the form of both plant nutrients and contaminants. The aim of this study was to evaluate the effect of CWWs on the dynamics of soil water-soluble metals and pH. To this end, CWWs from the processing of lemons, oranges, and tangerines at three different doses were used. CWWs were analyzed to investigate type and amount of organic acids. Soil water-soluble metals (Na, Mg, Al, K, Ca, Fe, Co, Ni, Cu, Zn, and Cd) and pH were determined at days 1, 3, 7, 21, and 28 after the addition of CWWs. Citric, ascorbic, oxalic, tartaric, acetic, and malic acids were found in CWWs, with citric acid being two orders of magnitude more concentrated than the other acids. After the addition of CWWs, soil pH promptly decreased from 7.2 to at least 5.3 depending on the type and concentration of CWWs. Concurrently, the concentration of almost all investigated metals sharply increased within 7 days after the addition of CWWs. Then, it decreased, reaching values similar to that of the control. The increase in metals availability as a consequence of pH decrease was ascribed to different causes: the exchange reaction between H+ and cations adsorbed onto colloid surfaces, the addition of organic matter by CWWs that stimulated microbial activity, and the quantity and type of organic acids added via CWWs. In conclusion, the obtained results suggest that the use of citrus wastewater for irrigation purposes could be a valid solution, with them being rich in plant nutrients and easily mobilized elements such as Ca, Mg, K, and Na. Further research is needed to refine the understanding of the impact of CWWs in the long term and to develop targeted strategies for managing industrial wastewater in agriculture

Valorization of Citrus spp. Cultivars cultivated in Sicily for the industrial use of citrus derivatives and in particular for potential alternative uses of essential oils for the enhancement of the island's citrus production

In this doctoral thesis are discussed a series of scientific issues regarding citrus fruits production and processing, species of particular relevance in Sicily and in the Mediterranean area. Objectives and research activities addressed in this thesis were agreed with the citrus industry "EuroFood" and financed by the research project "PON industrial Ph.D. - a.a. 2016/2017". The research project was targeted to study the traceability and sustainability of citrus production, and to find new applications to the by-products and waste products of citrus industry with the objective of appreciate and enhance the Sicilian citrus industry. The following topics are addressed and developed in this thesis: - Characterization of the bioactive compounds present in essential oils (EOs) and in the hydrolate of different citrus species. - Monitoring of the effect of controlled water stress on the production of EOs in leaves and flowers of Citrus sinensis (L.) Osbeck cv. ‘Sanguinelli’ and Citrus × clementina cv. ‘Clemenules’; -Test the phytotoxic effects of citrus EOs on four important weed species in the Mediterranean area, two monocotyledon (Echinochloa crus-galli (L.) P.Beauv. and Avena fatua L.) and two dicotyledon (Amaranthus retroflexus L., and Portulaca oleracea L.) by different experiments in vitro and in greenhouse conditions; -Evaluation of the effect as natural biostimulants of wastewaters from citrus processing industry by its application on soil microbial community; -Quantification of rare earth elements in lemon fruits from different geographical areas for its possible use as geochemical tracers applied to lemon production. Different Citrus EOs have been characterized in this study and it has been verified that the oils produced by the pruning waste could be used for the extraction of EOs with high yields. In addition, nutraceutical and pharmacological substances have been found in the orange industrial hydrolates. II Industrial lemon EO showed good potential when testing its herbicidal activity. Lemon EO represents a good basis for the development of herbicides of natural origin, biodegradable and eco-friendly. Thanks to the application of water stress after the winter vegetative restart, a conclusion found was that water stress increased the diameter of the fruit and it was observed that the effects of stress were not immediate on citrus trees, but were evident after some time. The study of the application of lemon, orange and mandarin hydrolates in the soil, as irrigation water provided the effects on stable and labile soil C pools, on biomass and microbial activity and on main microbial groups. Overall, hydrolates can play a role in sustainable agriculture because when added to a soil, they improve soil quality and fertility. The Rare Earth Element model could be used as a tool to connect lemon production to the soil where they were produced, for a possible geographical characterization and a direct link between the production and the territory or soil. The results obtained were very interesting because: - they provided the means for sustainable agriculture; - they increased the value of the by-products and waste products of the citrus industry; - they proposed applications for the citrus production and transformation cycle being more sustainable; - they could valorize the Sicilian lemons by linking them to their production area. These results could have practical repercussions in the production cycle of citrus fruits and give a boost to the Sicilian citrus fruit sector

Standard polynomials and matrices with superinvolutions

Let Mn(F) be the algebra of n x n matrices over a field F of characteristic zero. The superinvolutions ∗ on Mn(F) were classified by Racine in [12]. They are of two types, the transpose and the orthosymplectic superinvolution. This paper is devoted to the study of ∗-polynomial identities satisfied by Mn(F). The goal is twofold. On one hand, we determine the minimal degree of a standard polynomial vanishing on suitable subsets of symmetric or skew-symmetric matrices for both types of superinvolutions. On the other, in case of M2(F), we find generators of the ideal of ∗-identities and we compute the corresponding sequences of cocharacters and codimensions