Impacts of trace element pollution on sewage sludge and soil-plant systems: developing remediation techniques and assessing plant uptake prevention measures

Trace Elements (TEs) pollution is a significant environmental concern due to its toxic effects on human and ecosystem health and its potential to bioaccumulate in the food chain and to threaten species survival, leading to a decline in biodiversity. Urban areas, industrial and mining activities, agricultural practices, all contribute to the release of TEs into the environment posing a significant risk to human health and ecosystems. Several techniques have been developed to control TEs into the environment. This work presents the findings of three-year PhD program that focused on research on TEs pollution. The study discusses three fundamental aspects related to this topic from the perspective of sustainable development, environmental and human health. (1) High levels of TEs contamination prevent the use of sewage sludge (SS) as a fertilizer in agriculture, despite its potential as a soil amendment. Developing effective techniques to manage TEs contamination in SS is critical to ensure its safe use in agriculture and promote resource efficiency through sludge reuse. Another purpose of the study was to evaluate different strategies to limit the TEs uptake by horticultural crops (specifically, Cucumis Melo L.). This study addressed the effect of seasonality, Trichoderma inoculation and clinoptilolite application on chromium (Cr), copper (Cu) and lead (Pb) content of early- and late-ripening cultivars of Cucumis Melo L.. Finally, the accumulation of copper and the effect of its bioavailable fraction on bacterial and fungal communities in the rhizosphere soil of two vineyards, featuring two different varieties of Vitis vinifera grown for varying lengths of time, were evaluated.

Caratterizzazione di membrane inorganiche per la separazione di idrogeno da gas di reforming

The work of this thesis has been focused on the characterisation of inorganic membranes for the hydrogen purification from steam reforming gas. Composite membranes based on porous inorganic supports coated with palladium silver alloys and ceramic membranes have been analysed. A brief resume of theoretical laws governing transport of gases through dense and porous inorganic membranes and an overview on different methods to prepare inorganic membranes has been also reported. A description of the experimental apparatus used for the characterisation of gas permeability properties has been reported. The device used permits to evaluate transport properties in a wide range of temperatures (till 500°C) and pressures (till 15 bar). Data obtained from experimental campaigns reveal a good agreement with Sievert law for hydrogen transport through dense palladium based membranes while different transport mechanisms, such as Knudsen diffusion and Hagen-Poiseuille flow, have been observed for porous membranes and for palladium silver alloy ones with pinholes in the metal layer. Mixtures permeation experiments reveal also concentration polarisation phenomena and hydrogen permeability reduction due to carbon monoxide adsorption on metal surface.

Studio di metodi di preparazione e caratterizzazione di nanostrutture per la funzionalizzazione di materiali ceramici

This thesis was carried out in the context of a co-tutoring program between Centro Ceramico Bologna (Italy) and Instituto di Tecnologia Ceramica, Castellón de la Plana (Spain). The subject of the thesis is the synthesis of silver nanoparticles and at their likely decorative application in the productive process of porcelain ceramic tiles. Silver nanoparticles were chosen as a case study, because metal nanoparticles are thermally stable, and they have non-linear optical properties when nano-structured, and therefore they develop saturated colours. The nanoparticles were synthesized by chemical reduction in aqueous solution, a method chosen because of its reduced working steps and energy costs. Besides such a synthesis method uses non-expensive and non-toxic raw material. By adopting this synthesis technique, it was also possible to control the dimension and the final shape of the nanoparticles. Several syntheses were carried out during the research work, modifying the molecular weight of the reducing agent and/or the firing temperature, in order to evaluate the influence such parameters have on the Ag-nanoparticles formation. The syntheses were monitored with the use of UV-Vis spectroscopy and the average dimension as well as the morphology of the nanoparticles was analysed by SEM. From the spectroscopic data obtained from each synthesis, a kinetic study was completed, relating the progress of the reaction to the two variables (ie temperature and molecular weight of the reducing agent). The aim was finding equations that allow the establishing of a relationship between the operating conditions during the synthesis and the characteristics of the final product. The next step was finding the best method of synthesis for the decorative application. For such a purpose the amount of nanoparticles, their average particle size, the shape and the agglomeration are considered. An aqueous suspension containing the nanoparticles is then sprayed over the fired ceramic tiles and they are subsequently thermally treated in conditions similar to the industrial one. The colorimetric parameters of the obtained ceramic tiles were studied and the method proved successful, giving the ceramic tiles stable and intense colours.

Biologia di Tuta absoluta (Lepidoptera: Gelechiidae), interazioni con l’ambiente e valutazione di tecniche di contenimento ecocompatibili

Tuta absoluta (Meyrick) è un lepidottero originario dell’America meridionale, infeudato a pomodoro e ad altre solanacee coltivate e spontanee. Con l’attività trofica le larve causano mine fogliari e gallerie nei frutti, con conseguenti ingenti danni alle colture. T. absoluta è stato segnalato per la prima volta in Italia nel 2008 e in Piemonte nel 2009. Pertanto le ricerche sono state condotte per rilevarne la distribuzione in Piemonte, studiarne l’andamento di popolazione in condizioni naturali e controllate, e valutare l’efficacia di differenti mezzi di lotta al fine di definire le strategie di difesa. Il monitoraggio, condotto nel 2010, ha evidenziato come T. absoluta sia ormai largamente diffuso sul territorio regionale già pochi mesi dopo la segnalazione. L’insetto ha mostrato di prediligere condizioni climatiche più miti; infatti è stato ritrovato con maggiore frequenza nelle aree più calde. Il fitofago ha raggiunto densità di popolazione elevate a partire dalla seconda metà dell’estate, a ulteriore dimostrazione che, in una regione a clima temperato come il Piemonte, T. absoluta dà origine a infestazioni economicamente rilevanti solo dopo il culmine della stagione estiva. Per definire le strategie di lotta, sono state condotte prove in laboratorio, semi-campo e campo volte a valutare la tossicità nei confronti del lepidottero di preparati a base di emamectina benzoato, rynaxypyr, spinosad e Bacillus thuringiensis Berliner. In campo è stata verificata anche l’efficacia del miride dicifino Macrolophus pygmaeus (Rambur), reperibile in commercio. In tutte le prove, è stata riscontrata una maggiore efficacia di rynaxypyr ed emamectina benzoato. In campo M. pygmaeus ha mostrato difficoltà d’insediamento ed è stato in grado di contenere efficacemente il fitofago soltanto con bassi livelli d’infestazione. Per contro è stata costantemente osservata la presenza naturale di un altro miride dicifino Dicyphus errans (Wolff), che in laboratorio ha mostrato di non essere particolarmente disturbato dalle sostanze saggiate.