Jasmonates and abscisic acid influence fruit ripening and plant water use: practical, physiological and morphological aspects

The aim of the present thesis was to better understand the physiological role of the phytohormones jasmonates (JAs) and abscisic acid (ABA) during fruit ripening in prospect of a possible field application of JAs and ABA to improve fruit yield and quality. In particular, the effects of exogenous application of these substances at different fruit developmental stages and under different experimental conditions were evaluated. Some aspects of the water relations upon ABA treatment were also analysed. Three fruit species, peach (Prunus persica L. Batsch), golden (Actinidia chinensis) and green kiwifruit (Actinidia deliciosa), and several of their cvs, were used for the trials. Different experimental models were adopted: fruits in planta, detached fruit, detached branches with fruit, girdled branches and micropropagated plants. The work was structured into four sets of experiments as follows: (i) Pre-harvest methyl jasmonate (MJ) application was performed at S3/S4 transition under field conditions in Redhaven peach; ethylene production, ripening index, fruit quality and shelf-life were assessed showing that MJ-treated fruit were firmer and thus less ripe than controls as confirmed by the Index of Absorbance Difference (IAD), but exhibited a shorter shelf-life due to an increase in ethylene production. Moreover, the time course of the expression of ethylene-, auxin- and other ripening-related genes was determined. Ripening-related ACO1 and ACS1 transcript accumulation was inhibited though transiently by MJ, and gene expression of the ethylene receptor ETR2 and of the ethylene-related transcription factor ERF2 was also altered. The time course of the expression of several auxin-related genes was strongly affected by MJ suggesting an increase in auxin biosynthesis, altered auxin conjugation and release as well as perception and transport; the need for a correct ethylene/auxin balance during ripening was confirmed. (ii) Pre- and post-harvest ABA applications were carried out under field conditions in Flaminia and O’Henry peach and Stark Red Gold nectarine fruit; ethylene production, ripening index, fruit quality and shelf-life were assessed. Results show that pre-harvest ABA applications increase fruit size and skin color intensity. Also post-harvest ABA treatments alter ripening-related parameters; in particular, while ethylene production is impaired in ABA-treated fruit soluble solids concentration (SSC) is enhanced. Following field ABA applications stem water potential was modified since ABA-treated peach trees retain more water. (iii) Pre- and post-harvest ABA and PDJ treatments were carried out in both kiwifruit species under field conditions at different fruit developmental stages and in post-harvest. Ripening index, fruit quality, plant transpiration, photosynthesis and stomatal conductance were assessed. Pre-harvest treatments enhance SSC in the two cvs and flesh color development in golden kiwifruit. Post-harvest applications of either ABA or ABA plus PDJ lead to increased SSC. In addition, ABA reduces gas exchanges in A. deliciosa. (iv) Spray, drench and dipping ABA treatments were performed in micropropagated peach plants and in peach and nectarine detached branches; plant water use and transpiration, biomass production and fruit dehydration were determined. In both plants and branches ABA significantly reduces water use and fruit dehydration. No negative effects on biomass production were detected. The present information, mainly arising from plant growth regulator application in a field environment, where plants have to cope with multiple biotic and abiotic stresses, may implement the perspectives for the use of these substances in the control of fruit ripening.

LCA-GIS Integrated approach for a Sustainable Land Use Under Energy Crops

In genere, negli studi di vocazionalità delle colture, vengono presi in considerazione solo variabili ambientali pedo-climatiche. La coltivazione di una coltura comporta anche un impatto ambientale derivante dalle pratiche agronomiche ed il territorio può essere più o meno sensibile a questi impatti in base alla sua vulnerabilità. In questo studio si vuole sviluppare una metodologia per relazionare spazialmente l’impatto delle colture con le caratteristiche sito specifiche del territorio in modo da considerare anche questo aspetto nell’allocazione negli studi di vocazionalità. LCA è stato utilizzato per quantificare diversi impatti di alcune colture erbacee alimentari e da energia, relazionati a mappe di vulnerabilità costruite con l’utilizzo di GIS, attraverso il calcolo di coefficienti di rischio di allocazione per ogni combinazione coltura-area vulnerabile. Le colture energetiche sono state considerate come un uso alternativo del suolo per diminuire l’impatto ambientale. Il caso studio ha mostrato che l’allocazione delle colture può essere diversa in base al tipo e al numero di impatti considerati. Il risultato sono delle mappe in cui sono riportate le distribuzioni ottimali delle colture al fine di minimizzare gli impatti, rispetto a mais e grano, due colture alimentari importanti nell’area di studio. Le colture con l’impatto più alto dovrebbero essere coltivate nelle aree a vulnerabilità bassa, e viceversa. Se il rischio ambientale è la priorità, mais, colza, grano, girasole, e sorgo da fibra dovrebbero essere coltivate solo nelle aree a vulnerabilità bassa o moderata, mentre, le colture energetiche erbacee perenni, come il panico, potrebbero essere coltivate anche nelle aree a vulnerabilità alta, rappresentando cosi una opportunità per aumentare la sostenibilità di uso del suolo rurale. Lo strumento LCA-GIS inoltre, integrato con mappe di uso attuale del suolo, può aiutare a valutarne il suo grado di sostenibilità ambientale.

New water use efficiency strategies to cope with climate change

Crop water requirements are important elements for food production, especially in arid and semiarid regions. These regions are experience increasing population growth and less water for agriculture, which amplifies the need for more efficient irrigation. Improved water use efficiency is needed to produce more food while conserving water as a limited natural resource. Evaporation (E) from bare soil and Transpiration (T) from plants is considered a critical part of the global water cycle and, in recent decades, climate change could lead to increased E and T. Because energy is required to break hydrogen bonds and vaporize water, water and energy balances are closely connected. The soil water balance is also linked with water vapour losses to evapotranspiration (ET) that are dependent mainly on energy balance at the Earth’s surface. This work addresses the role of evapotranspiration for water use efficiency by developing a mathematical model that improves the accuracy of crop evapotranspiration calculation; accounting for the effects of weather conditions, e.g., wind speed and humidity, on crop coefficients, which relates crop evapotranspiration to reference evapotranspiration. The ability to partition ET into Evaporation and Transpiration components will help irrigation managers to find ways to improve water use efficiency by decreasing the ratio of evaporation to transpiration. The developed crop coefficient model will improve both irrigation scheduling and water resources planning in response to future climate change, which can improve world food production and water use efficiency in agriculture.

Effects of N fertilization on forest trees and ecosystems: water use, WUE, growth

During my three academic years, I focused on the effects of N fertilization on growth and function of plants and forest stands. The study had the dual objective of estimating the effects of atmospheric N deposition and evaluating the potential management value of N fertilization itself. In particular, the analysis took into account the changes induced in water use and intrinsic transpiration efficiency (ITE), an aspect often overlooked in world literature but of great importance especially in Mediterranean environment, where the positive effects of N fertilization may be denied by the parallel increased transpiration and exacerbated water stress.

Buone pratiche e Tecnologie Appropriate per la gestione delle risorse idriche ed il risparmio energetico in ambito urbano e rurale

Questa tesi di dottorato tratta il tema delle Tecnologie Appropriate e delle Buone Pratiche per la gestione delle risorse idriche ed il risparmio energetico nell’ambito dell’abitato urbano e rurale. Viene fatta una breve panoramica sulle principali teorie e metodologie che fino ad oggi hanno fatto da linee guida per la progettazione sostenibile e il corretto utilizzo delle risorse. Questa visione d'insieme servirà per esprimere delle valutazioni e trovare dei comuni dominatori per proporre una nuova metodologia d'approccio alla gestione delle risorse con particolare attenzione rivolta alla condizione presente e alla zona d’intervento. Site specific sustainability Approach (S3A). I casi studio: • Un progetto di approvvigionamento idrico e di desalinizzazione delle acque per un’oasi del Sahara marocchino. • Un progetto di ricerca della Columbia University e della NASA legato alla sostenibilità urbana di New York che analizza i benefici apportati dall'installazione di coperture verdi nell'area di Manhattan da un punto di vista della gestione delle risorse idriche, energetiche e delle componenti ambientali. • Un progetto di verde verticale e giardino pensile a Milano. • Un progetto di approvvigionamento idrico sostenibile e gestione del verde per la città di Porto Plata in Repubblica Domenicana. Approfondimenti e sperimentazioni. • E’ stato approfondito il tema della distillazione solare per la dissalazione e potabilizzazione delle acque in zone rurali desertiche ed isolate. • E’ stato progettato e realizzato un prototipo innovativo di distillatore tubolare con collettore solare parabolico. Il prototipo è stato testato nei laboratori della Columbia University di New York. • Sono state approfondite le Khettaras o Qanat, tunnel sotterranei per l’approvvigionamento idrico nelle zone aride. • Infine sono stati approfonditi i benefici apportati dalle coperture a verde (tetti verdi) e dal verde verticale nelle zone urbane dal punto di vista della gestione delle risorse idriche ed il risparmio energetico.

Light energy management in peach: utilization, photoprotection , photodamage and recovery. Maximizing light absorption in orchard is not always the best solution

The relation between the intercepted light and orchard productivity was considered linear, although this dependence seems to be more subordinate to planting system rather than light intensity. At whole plant level not always the increase of irradiance determines productivity improvement. One of the reasons can be the plant intrinsic un-efficiency in using energy. Generally in full light only the 5 – 10% of the total incoming energy is allocated to net photosynthesis. Therefore preserving or improving this efficiency becomes pivotal for scientist and fruit growers. Even tough a conspicuous energy amount is reflected or transmitted, plants can not avoid to absorb photons in excess. The chlorophyll over-excitation promotes the reactive species production increasing the photoinhibition risks. The dangerous consequences of photoinhibition forced plants to evolve a complex and multilevel machine able to dissipate the energy excess quenching heat (Non Photochemical Quenching), moving electrons (water-water cycle , cyclic transport around PSI, glutathione-ascorbate cycle and photorespiration) and scavenging the generated reactive species. The price plants must pay for this equipment is the use of CO2 and reducing power with a consequent decrease of the photosynthetic efficiency, both because some photons are not used for carboxylation and an effective CO2 and reducing power loss occurs. Net photosynthesis increases with light until the saturation point, additional PPFD doesn’t improve carboxylation but it rises the efficiency of the alternative pathways in energy dissipation but also ROS production and photoinhibition risks. The wide photo-protective apparatus, although is not able to cope with the excessive incoming energy, therefore photodamage occurs. Each event increasing the photon pressure and/or decreasing the efficiency of the described photo-protective mechanisms (i.e. thermal stress, water and nutritional deficiency) can emphasize the photoinhibition. Likely in nature a small amount of not damaged photosystems is found because of the effective, efficient and energy consuming recovery system. Since the damaged PSII is quickly repaired with energy expense, it would be interesting to investigate how much PSII recovery costs to plant productivity. This PhD. dissertation purposes to improve the knowledge about the several strategies accomplished for managing the incoming energy and the light excess implication on photo-damage in peach. The thesis is organized in three scientific units. In the first section a new rapid, non-intrusive, whole tissue and universal technique for functional PSII determination was implemented and validated on different kinds of plants as C3 and C4 species, woody and herbaceous plants, wild type and Chlorophyll b-less mutant and monocot and dicot plants. In the second unit, using a “singular” experimental orchard named “Asymmetric orchard”, the relation between light environment and photosynthetic performance, water use and photoinhibition was investigated in peach at whole plant level, furthermore the effect of photon pressure variation on energy management was considered on single leaf. In the third section the quenching analysis method suggested by Kornyeyev and Hendrickson (2007) was validate on peach. Afterwards it was applied in the field where the influence of moderate light and water reduction on peach photosynthetic performances, water requirements, energy management and photoinhibition was studied. Using solar energy as fuel for life plant is intrinsically suicidal since the high constant photodamage risk. This dissertation would try to highlight the complex relation existing between plant, in particular peach, and light analysing the principal strategies plants developed to manage the incoming light for deriving the maximal benefits as possible minimizing the risks. In the first instance the new method proposed for functional PSII determination based on P700 redox kinetics seems to be a valid, non intrusive, universal and field-applicable technique, even because it is able to measure in deep the whole leaf tissue rather than the first leaf layers as fluorescence. Fluorescence Fv/Fm parameter gives a good estimate of functional PSII but only when data obtained by ad-axial and ab-axial leaf surface are averaged. In addition to this method the energy quenching analysis proposed by Kornyeyev and Hendrickson (2007), combined with the photosynthesis model proposed by von Caemmerer (2000) is a forceful tool to analyse and study, even in the field, the relation between plant and environmental factors such as water, temperature but first of all light. “Asymmetric” training system is a good way to study light energy, photosynthetic performance and water use relations in the field. At whole plant level net carboxylation increases with PPFD reaching a saturating point. Light excess rather than improve photosynthesis may emphasize water and thermal stress leading to stomatal limitation. Furthermore too much light does not promote net carboxylation improvement but PSII damage, in fact in the most light exposed plants about 50-60% of the total PSII is inactivated. At single leaf level, net carboxylation increases till saturation point (1000 – 1200 μmolm-2s-1) and light excess is dissipated by non photochemical quenching and non net carboxylative transports. The latter follows a quite similar pattern of Pn/PPFD curve reaching the saturation point at almost the same photon flux density. At middle-low irradiance NPQ seems to be lumen pH limited because the incoming photon pressure is not enough to generate the optimum lumen pH for violaxanthin de-epoxidase (VDE) full activation. Peach leaves try to cope with the light excess increasing the non net carboxylative transports. While PPFD rises the xanthophyll cycle is more and more activated and the rate of non net carboxylative transports is reduced. Some of these alternative transports, such as the water-water cycle, the cyclic transport around the PSI and the glutathione-ascorbate cycle are able to generate additional H+ in lumen in order to support the VDE activation when light can be limiting. Moreover the alternative transports seems to be involved as an important dissipative way when high temperature and sub-optimal conductance emphasize the photoinhibition risks. In peach, a moderate water and light reduction does not determine net carboxylation decrease but, diminishing the incoming light and the environmental evapo-transpiration request, stomatal conductance decreases, improving water use efficiency. Therefore lowering light intensity till not limiting levels, water could be saved not compromising net photosynthesis. The quenching analysis is able to partition absorbed energy in the several utilization, photoprotection and photo-oxidation pathways. When recovery is permitted only few PSII remained un-repaired, although more net PSII damage is recorded in plants placed in full light. Even in this experiment, in over saturating light the main dissipation pathway is the non photochemical quenching; at middle-low irradiance it seems to be pH limited and other transports, such as photorespiration and alternative transports, are used to support photoprotection and to contribute for creating the optimal trans-thylakoidal ΔpH for violaxanthin de-epoxidase. These alternative pathways become the main quenching mechanisms at very low light environment. Another aspect pointed out by this study is the role of NPQ as dissipative pathway when conductance becomes severely limiting. The evidence that in nature a small amount of damaged PSII is seen indicates the presence of an effective and efficient recovery mechanism that masks the real photodamage occurring during the day. At single leaf level, when repair is not allowed leaves in full light are two fold more photoinhibited than the shaded ones. Therefore light in excess of the photosynthetic optima does not promote net carboxylation but increases water loss and PSII damage. The more is photoinhibition the more must be the photosystems to be repaired and consequently the energy and dry matter to allocate in this essential activity. Since above the saturation point net photosynthesis is constant while photoinhibition increases it would be interesting to investigate how photodamage costs in terms of tree productivity. An other aspect of pivotal importance to be further widened is the combined influence of light and other environmental parameters, like water status, temperature and nutrition on peach light, water and phtosyntate management.

L'inerbimento nell'ecosistema vigneto: confronto di metodologie di misura del consumo idrico del prato e risposta allo sfalcio

Water resources management will become increasingly important in agriculture as global warming takes place. Cover crop is largely used in viticultural areas based on the many positive agronomic and environmental benefits it provides. However, it is not clear what effect the cover crop can have on water use in the vineyard. This study is designed to develop a further understanding of the role cover crops play in total water use in the vineyard and develop our understanding of the potential use of cover crops as a water management tool. Two techniques were used to measure cover crop water use, the mini-lysimeters and a portable open chamber and data from both was compared to reference evapotranspiration (ETo) (FAO guidelines). While the mini-lysimeters seemed to be limited in their ability to accurately represent the water use of the surrounding soil, the open chamber method is a reliable and suitable instrument to be used for the accurate measurement of evapotranspiration. Further, the relationship between vineyard grass water use and the contributing environmental factors thought to influence water use were analyzed. A strong relationship between total available radiation and cover crop evapotranspiration was found suggesting the possibility of an indirect method of evapotranspiration measurement in a vineyard grass cover crop. Mowing the cover crop was determined to significantly effect transpiration as shown by both the mini-lysimeter and open chamber, however, the reduction was largely dependent on the growth rate of the grass.

Studio di caratteri correlati a stress idrico in una collezione di cultivar di frumento duro (Triticum durum Desf.)

L’agricoltura si trova ad affrontare una diminuzione della disponibilità d’acqua ed una crescente domanda della produzione di cereali per scopi alimentari. Sono perciò necessarie strategie di coltivazione innovative per migliorare la produttività e nuovi genotipi migliorati nell'efficienza dell’uso delle risorse in condizioni di siccità. Questi rappresentano gli obietti principali del progetto “DROPS” (Drought tolerant yielding Plants) all’interno del quale ha avuto luogo il mio progetto di Dottorato. La mia attività di ricerca è stata svolta come segue: 1. Caratterizzazione molecolare di un panel di188 accessioni di frumento duro con marcatori SSR e DaRT; 2. Esperimenti in serra su 100 accessioni del panel per valutare la Water-Use Efficiency (WUE) in sei repliche secondo un Alpha Lattice design; 3. Prove sul campo, effettuate secondo un Alpha Lattice design, in due stagioni di crescita: a. 2010/11, valutazione di 100 accessioni presso l’Azienda sperimentale dell'Università di Cadriano (BO); b. 2011/12, valutazione del panel completo in 3 ambienti, con due diversi regimi irrigui In entrambi gli anni, abbiamo valutato caratteri agronomici correlati con il ciclo di sviluppo, la resa di granella e sue componenti, nonché diversi fattori ambientali e del suolo. Per quanto riguarda WUE, abbiamo trovato differenze altamente significative tra accessioni; inoltre, cinque accessioni hanno mostrato elevati valori di WUE e cinque accessioni valori molto bassi di WUE in tutte e sei le repliche. Gli esperimenti di campo nelle stagioni 2011 e 2012 hanno evidenziato differenze altamente significative tra le accessioni del panel per la maggior parte dei caratteri analizzati, confermando inoltre che il panel di fiorisce entro una settimana. L'esperimento del secondo anno ci ha permesso osservare un significativa interazione Genotipo X Ambiente. Questi risultati saranno integrati con ulteriori analisi QTL, per identificare regioni cromosomiche coinvolte nel controllo genetico dei caratteri di interesse e verificare la stabilità dei QTL in diversi ambienti.

Salinity Effect on Horticultural Crops: Morphological, Physiological, and Biomolecular Elements of Salinity Stress Response

Among abiotic stresses, high salinity stress is the most severe environmental stress. High salinity exerts its negative impact mainly by disrupting the ionic and osmotic equilibrium of the cell. In saline soils, high levels of sodium ions lead to plant growth inhibition and even death. Salt tolerance in plants is a multifarious phenomenon involving a variety of changes at molecular, organelle, cellular, tissue as well as whole plant level. In addition, salt tolerant plants show a range of adaptations not only in morphological or structural features but also in metabolic and physiological processes that enable them to survive under extreme saline environments. The main objectives of my dissertation were understanding the main physiological and biomolecular features of plant responses to salinity in different genotypes of horticultural crops that are belonging to different families Solanaceae (tomato) and Cucurbitaceae (melon) and Brassicaceae (cabbage and radish). Several aspects of crop responses to salinity have been addressed with the final aim of combining elements of functional stress response in plants by using several ways for the assessment of plant stress perception that ranging from destructive measurements (eg. leaf area, relative growth rate, leaf area index, and total plant fresh and dry weight), to physiological determinations (eg. stomatal conductance, leaf gas exchanges, water use efficiency, and leaf water relation), to the determination of metabolite accumulation in plant tissue (eg. Proline and protein) as well as evaluation the role of enzymatic antioxidant capacity assay in scavenging reactive oxygen species that have been generated under salinized condition, and finally assessing the gene induction and up-down regulation upon salinization (eg. SOS pathway).

Evapotranspiration: Present and Future Challenges

The thesis first explored and evaluated some of the most used models that were developed to account for the effect of CO2 on evapotranspiration. This review depicts the complexity of the modeling procedure and underlines the advantages and shortcomings of each model. Then, the projected climate change in the near future (2021-2050) in different locations in Emilia-Romagna (Italy) was studied, with an emphasis on the opposite effect of an increase in both air temperature and CO2 levels on ETo. The case study used reanalysis data as a surrogate to historical weather stations measurements and an ensemble of regional climate models (RCMs) for the future projections. Results show that higher CO2 levels moderated the increase in ETo that accompanies an increase in air temperature, taking in consideration the change in other weather variables i.e. solar radiation, wind speed and dew point temperature. The outcomes of this study show that considering the CO2 fertilization effect when calculating reference evapotranspiration might give a more realistic estimation of water use efficiency and irrigation requirements in Emilia-Romagna and a better analysis of the future availability and distribution of water resources in the region. Finally, data from a model forecasting reference evapotranspiration (FRET) and the different variables involved in its calculation for the state of California (USA) were compared with similar data from the regional weather station network (CIMIS) to evaluate their accuracy and reliability. The evaluation was done in locations with different microclimates and included also sample irrigation schedules developed using FRET ETo. The obtained results demonstrate that FRET ETo forecasts are a viable alternative to traditional ETo measurements with some differences depending on the climatic condition of the location considered in this study. This implies that FRET could be replicated in other areas with similar climate settings.

Dynamics of terricolous alpine lichen communities of the Alps and Mediterranean Mountains in a climate change perspective

This thesis focuses on the impact of climate change in alpine ecosystems stressing the response of high elevation terricolous lichen communities. In fact, despite the strong sensitivity of cryptogams to changes in climatic factors, information is still scanty.We collected records in 154 plots placed in the summit area of the Majella Massif. In Following a multitaxon approach, Chapter 1 includes cryptogams and vascular plants. We analysed patterns in species richness, beta diversity and functional composition. In Chapter 2, we analysed the relationships between climatic variables and phylogenetic diversity and structure indices. Chapter 3 provides a long-term response relative to the consequences of climate change on a representative terricolous lichen genus across the Alps. Chapter 4 explores the relationships between the species richness and the functional composition of lichen growing on two types of substrates (carbonatic and siliceous soils) along different elevation gradients in the Eastern Alps. Climate change could affect cryptogams and lichens much more than vascular plants in Mediterranean mountains. Contrasting species-climate and traits-climate relationships were found between lichens and bryophytes, suggesting that each group may be sensitive to different components of climate change. Ongoing climate change may also lead to a loss of genetic diversity at high elevation ranges in the Mediterranean mountains, pauperising the life history richness of lichens. Alpine results forecasted that moderate range loss dynamics will occur at low elevation and in peripheral areas of the alpine chain. Results also support the view that range dynamics could be associated with functional traits mainly related to water-use strategies, dispersal, and establishment ability. We also highlighted the importance of substrates as a main driver of both species’ richness and functional traits composition. A “trade-off” also occurs between stress tolerance and the competitive response of communities of terricolous lichens that grow above siliceous and carbonatic soils.

Appropriate technologies and natural systems for wastewater treatment in low- and middle-income countries

Wastewater management is an environmental and social burden that primarily affects populations in Low- and Middle-Income Countries and the global environment. Wastewater collection, treatment, and reuse have become urgent, especially considering that 80% of the world's wastewater is untreated or improperly treated and discharged directly into water bodies. In recent years, the role of wastewater treatment plants in a sustainable water cycle has become even more critical, as they are the final destination of the collected wastewater. Indeed, the management of wastewater treatment plants should play an essential role in achieving SDG target 6.3 of the United Nations 2030 Agenda for SD. In this context, water reuse, especially wastewater reuse, plays a key role. This research focuses on investigating the valorization of wastewater resources applying Appropriate Technologies and Natural Systems for wastewater treatment in two different Low- and Middle-Income Countries, the Palestinian Territories and Sub-Saharan Africa. The research objectives are: (1) Determine the characteristics and quality of wastewater in the two case studies analysed. (2) Identify Appropriate Technology to be used in the Palestinian Territories to treat wastewater for reuse in agriculture. (3) Assess the environmental, economic, and social impacts of this project. (4) Assess the feasibility of using natural wetlands for household wastewater treatment in Sub-Saharan region. The first study, conducted in Rafah, Gaza Strip, showed that implementing existing primary treatment plant with a natural secondary treatment plant properly optimized the wastewater quality for reuse in agriculture and was suitable for the study area. The second case study was conducted in Cape Coast, Ghana. It shows that the natural wetland studied is currently overly polluted and threatened by various anthropogenic factors that cannot remove pollutants from the incoming domestic wastewater. Therefore, some recommendations were made in order to improve the efficiency of this natural wetland.

"Water users must be efficient producers". Women's access to and use of land in Chókwè irrigation scheme, Mozambique

The irrigation scheme Eduardo Mondlane, situated in Chókwè District - in the Southern part of the Gaza province and within the Limpopo River Basin - is the largest in the country, covering approximately 30,000 hectares of land. Built by the Portuguese colonial administration in the 1950s to exploit the agricultural potential of the area through cash-cropping, after Independence it became one of Frelimo’s flagship projects aiming at the “socialization of the countryside” and at agricultural economic development through the creation of a state farm and of several cooperatives. The failure of Frelimo’s economic reforms, several infrastructural constraints and local farmers resistance to collective forms of production led to scheme to a state of severe degradation aggravated by the floods of the year 2000. A project of technical rehabilitation initiated after the floods is currently accompanied by a strong “efficiency” discourse from the managing institution that strongly opposes the use of irrigated land for subsistence agriculture, historically a major livelihood strategy for smallfarmers, particularly for women. In fact, the area has been characterized, since the end of the XIX century, by a stable pattern of male migration towards South African mines, that has resulted in an a steady increase of women-headed households (both de jure and de facto). The relationship between land reform, agricultural development, poverty alleviation and gender equality in Southern Africa is long debated in academic literature. Within this debate, the role of agricultural activities in irrigation schemes is particularly interesting considering that, in a drought-prone area, having access to water for irrigation means increased possibilities of improving food and livelihood security, and income levels. In the case of Chókwè, local governments institutions are endorsing the development of commercial agriculture through initiatives such as partnerships with international cooperation agencies or joint-ventures with private investors. While these business models can sometimes lead to positive outcomes in terms of poverty alleviation, it is important to recognize that decentralization and neoliberal reforms occur in the context of financial and political crisis of the State that lacks the resources to efficiently manage infrastructures such as irrigation systems. This kind of institutional and economic reforms risk accelerating processes of social and economic marginalisation, including landlessness, in particular for poor rural women that mainly use irrigated land for subsistence production. The study combines an analysis of the historical and geographical context with the study of relevant literature and original fieldwork. Fieldwork was conducted between February and June 2007 (where I mainly collected secondary data, maps and statistics and conducted preliminary visit to Chókwè) and from October 2007 to March 2008. Fieldwork methodology was qualitative and used semi-structured interviews with central and local Government officials, technical experts of the irrigation scheme, civil society organisations, international NGOs, rural extensionists, and water users from the irrigation scheme, in particular those women smallfarmers members of local farmers’ associations. Thanks to the collaboration with the Union of Farmers’ Associations of Chókwè, she has been able to participate to members’ meeting, to education and training activities addressed to women farmers members of the Union and to organize a group discussion. In Chókwè irrigation scheme, women account for the 32% of water users of the familiar sector (comprising plot-holders with less than 5 hectares of land) and for just 5% of the private sector. If one considers farmers’ associations of the familiar sector (a legacy of Frelimo’s cooperatives), women are 84% of total members. However, the security given to them by the land title that they have acquired through occupation is severely endangered by the use that they make of land, that is considered as “non efficient” by the irrigation scheme authority. Due to a reduced access to marketing possibilities and to inputs, training, information and credit women, in actual fact, risk to see their right to access land and water revoked because they are not able to sustain the increasing cost of the water fee. The myth of the “efficient producer” does not take into consideration the characteristics of inequality and gender discrimination of the neo-liberal market. Expecting small-farmers, and in particular women, to be able to compete in the globalized agricultural market seems unrealistic, and can perpetuate unequal gendered access to resources such as land and water.

Use of solvents and environmental friendly materials for applications in Green Chemistry

The present Thesis studies three alternative solvent groups as sustainable replacement of traditional organic solvents. Some aspects of fluorinated solvents, supercritical fluids and ionic liquids, have been analysed with a critical approach and their effective “greenness” has been evaluated from the points of view of the synthesis, the properties and the applications. In particular, the attention has been put on the environmental and human health issues, evaluating the eco-toxicity, the toxicity and the persistence, to underline that applicability and sustainability are subjects with equal importance. The “green” features of fluorous solvents and supercritical fluids are almost well-established; in particular supercritical carbon dioxide (scCO2) is probably the “greenest” solvent among the alternative solvent systems developed in the last years, enabling to combine numerous advantages both from the point of view of industrial/technological applications and eco-compatibility. In the Thesis the analysis of these two classes of alternative solvents has been mainly focused on their applicability, rather than the evaluation of their environmental impact. Specifically they have been evaluated as alternative media for non-aqueous biocatalysis. For this purpose, the hydrophobic ion pairing (HIP), which allows solubilising enzymes in apolar solvents by an ion pairing between the protein and a surfactant, has been investigated as effective enzymatic derivatisation technique to improve the catalytic activity under homogeneous conditions in non conventional media. The results showed that the complex enzyme-surfactant was much more active both in fluorous solvents and in supercritical carbon dioxide than the native form of the enzyme. Ionic liquids, especially imidazolium salts, have been proposed some years ago as “fully green” alternative solvents; however this epithet does not take into account several “brown” aspects such as their synthesis from petro-chemical starting materials, their considerable eco-toxicity, toxicity and resistance to biodegradation, and the difficulty of clearly outline applications in which ionic liquids are really more advantageous than traditional solvents. For all of these reasons in this Thesis a critical analysis of ionic liquids has been focused on three main topics: i) alternative synthesis by introducing structural moieties which could reduce the toxicity of the most known liquid salts, and by using starting materials from renewable resources; ii) on the evaluation of their environmental impact through eco-toxicological tests (Daphnia magna and Vibrio fischeri acute toxicity tests, and algal growth inhibition), toxicity tests (MTT test, AChE inhibition and LDH release tests) and fate and rate of aerobic biodegradation in soil and water; iii) and on the demonstration of their effectiveness as reaction media in organo-catalysis and as extractive solvents in the recovery of vegetable oil from terrestrial and aquatic biomass. The results about eco-toxicity tests with Daphnia magna, Vibrio fischeri and algae, and toxicity assay using cultured cell lines, clearly indicate that the difference in toxicity between alkyl and oxygenated cations relies in differences of polarity, according to the general trend of decreasing toxicity by decreasing the lipophilicity. Independently by the biological approach in fact, all the results are in agreement, showing a lower toxicity for compounds with oxygenated lateral chains than for those having purely alkyl lateral chains. These findings indicate that an appropriate choice of cation and anion structures is important not only to design the IL with improved and suitable chemico-physical properties but also to obtain safer and eco-friendly ILs. Moreover there is a clear indication that the composition of the abiotic environment has to be taken into account when the toxicity of ILs in various biological test systems is analysed, because, for example, the data reported in the Thesis indicate a significant influence of salinity variations on algal toxicity. Aerobic biodegradation of four imidazolium ionic liquids, two alkylated and two oxygenated, in soil was evaluated for the first time. Alkyl ionic liquids were shown to be biodegradable over the 6 months test period, and in contrast no significant mineralisation was observed with oxygenated derivatives. A different result was observed in the aerobic biodegradation of alkylated and oxygenated pyridinium ionic liquids in water because all the ionic liquids were almost completely degraded after 10 days, independently by the number of oxygen in the lateral chain of the cation. The synthesis of new ionic liquids by using renewable feedstock as starting materials, has been developed through the synthesis of furan-based ion pairs from furfural. The new ammonium salts were synthesised in very good yields, good purity of the products and wide versatility, combining low melting points with high decomposition temperatures and reduced viscosities. Regarding the possible applications as surfactants and biocides, furan-based salts could be a valuable alternative to benzyltributylammonium salts and benzalkonium chloride that are produced from non-renewable resources. A new procedure for the allylation of ketones and aldehydes with tetraallyltin in ionic liquids was developed. The reaction afforded high yields both in sulfonate-containing ILs and in ILs without sulfonate upon addition of a small amount of sulfonic acid. The checked reaction resulted in peculiar chemoselectivity favouring aliphatic substrates towards aromatic ketones and good stereoselectivity in the allylation of levoglucosenone. Finally ILs-based systems could be easily and successfully recycled, making the described procedure environmentally benign. The potential role of switchable polarity solvents as a green technology for the extraction of vegetable oil from terrestrial and aquatic biomass has been investigated. The extraction efficiency of terrestrial biomass rich in triacylglycerols, as soy bean flakes and sunflower seeds, was comparable to those of traditional organic solvents, being the yield of vegetable oils recovery very similar. Switchable polarity solvents as been also exploited for the first time in the extraction of hydrocarbons from the microalga Botryococcus braunii, demonstrating the efficiency of the process for the extraction of both dried microalgal biomass and directly of the aqueous growth medium. The switchable polarity solvents exhibited better extraction efficiency than conventional solvents, both with dried and liquid samples. This is an important issue considering that the harvest and the dewatering of algal biomass have a large impact on overall costs and energy balance.

Demersal communities in the Mediterranean Sea: a case study of Triglidae (Osteichthyes, Scorpaeniformes) on the conservation and sustainable use of marine resources

An appropriate management of fisheries resources can only be achieved with the continuous supply of information on the structure and biology of populations, in order to predict the temporal fluctuations. This study supports the importance of investigating the bio-ecology of increasingly exploited and poorly known species, such as gurnards (Osteichthyes, Triglidae) from Adriatic Sea (Mediterranean), to quantify their ecological role into marine community. It also focuses on investigate inter and intra-specific structuring factor of Adriatic population. These objectives were achieved by: 1) investigating aspects of the population dynamics; 2) studying the feeding biology through the examination of stomach contents; 3) using sagittal otoliths as potential marker of species life cycle; 4) getting preliminary data on mDNA phylogeny. Gurnards showed a specie-specific “critical size” coinciding with the start of sexual maturity, the tendency to migrate to greater depths, a change of diet from crustaceans to fish and an increase of variety of food items eaten. Distribution of prey items, predator size range and depth distribution were the main dimensions that influence the breadth of trophic niche and the relative difference amongst Adriatic gurnards. Several feeding preferences were individuated and a possible impact among bigger-size gurnards and other commercial fishes (anchovy, gadoids) and Crustacea (such as mantis prawn and shrimps) were to be necessary considered. Otolith studies showed that gurnard species have a very fast growth despite other results in other areas; intra-specific differences and the increase in the variability of otolith shape, sulcus acusticus shape, S:O ratios, sulcus acusticus external crystals arrangement were shown between juveniles and adults and were linked to growth (individual genetic factors) and to environmental conditions (e.g. depth and trophic niche distribution). In order to facilitate correct biological interpretation of data, molecular data were obtained for comparing morphological distance to genetic ones.