Design of porous materials derived from industrial non-hazardous waste powder for air particulate matter entrapment

L’inquinamento ambientale è uno degli argomenti più trattati al fine di trovare soluzioni efficaci a contrastarlo. L’inquinante più presente nelle aree urbane, e che desta la maggiore preoccupazione a causa della sua capacità di penetrare nel sistema respiratorio con gravi danni per la salute, è il particolato atmosferico (PM). Le concentrazioni di PM spesso superano i limiti imposti dalla normativa; nel 2021 l’Organizzazione Mondiale della Sanità (WHO) ha imposto nuovi e più restrittivi limiti alle concentrazioni di PM al fine di ridurne le concentrazioni in atmosfera. Fra le diverse soluzioni proposte per intrappolare il PM c’è la realizzazione di un nuovo e sostenibile materiale, chiamato SUNSPACE (SUstaiNable materials Synthesized from by-Products and Alginates for Clean air and better Environment) e realizzato a partire da uno scarto industriale, la silica fume (SF) con processi a basse emissioni di CO2. La sua capacità di cattura del PM è stata valutata effettuando numerosi test e ottenendo buoni risultati ma il suo colore scuro rappresenta un limite a un suo possibile sviluppo commerciale. In questa tesi di dottorato, sono state proposte delle soluzioni alternative per ottenere un materiale dal colore chiaro e per eliminare il trattamento termico semplificando la fase di realizzazione del materiale. Il primo punto è stato ottenuto utilizzando la bottom ash (BA), cenere proveniente dalla combustione dei rifiuti municipali negli inceneritori, mentre la sostituzione del bicarbonato di sodio (utilizzato la formazione dei pori) con il perossido d’idrogeno ha permesso di eliminare il trattamento termico. I campioni, caratterizzati, sono stati testati per valutarne la capacità di intrappolare il PM utilizzato un generatore di aerosol e TiO2 per simulare una fonte di PM. Buoni risultati sono stati ottenuti per i campioni realizzati con SF e per SUNSPACE BA mentre quelli realizzati con BA e perossido d’idrogeno hanno mostrato un comportamento idrorepellente che è stato studiato con delle prove di bagnabilità. I risultati hanno dimostrato che questi materiali hanno un angolo di contatto al di sopra del limite di idrofobicità. I campioni sono stati anche testati per foto degradare inquinanti organici ottenendo buoni risultati per i campioni realizzati con BA, perossido di idrogeno e TiO2 (ottimo foto catalizzatore, aggiunto durante la preparazione dei campioni). Infine, il trattamento termico di SUNSPACE è stato sostituito con un trattamento a microonde che permette di ridurre i tempi necessari alla preparazione del campione e migliorare la sua sostenibilità. I campioni sono stati caratterizzati e testati utilizzando il generatore di aerosol. Si tratta però di test preliminari volti a proporre nuove possibili applicazioni del materiale, ad esempio per realizzare vasi da esterno che aiutino a intrappolare il PM. Nell'ultimo capitolo sono stati riportati alcuni lavori, realizzati durante la COVID-19, e incentrati sulle sue conseguenze su vari aspetti ambientali e sull'estrazione di materie prime.Environmental pollution is one of the biggest issue in modern society. In particular, the most present pollutant in urban areas is particulate matter (PM) that is cause of concern as it can easily penetrate the respiratory system causing severe health problems. As PM concentrations often exceed limits imposed by legislation, in 2021 World Health Organization (WHO) imposed new and stricter limits to PM10 and PM2.5 concentrations. Several solutions have been proposed to reduce PM concentrations in cities, including the realization of a new and sustainable material, SUNSPACE (SUstaiNable materials Synthesized from by-Products and Alginates for Clean air and better Environment) realized with silica fume (SF) and low CO2 emissions processes. Its adsorption capacity was tested obtaining good results but, from a commercial development perspective, its dark color represents a limit. In this Ph.D. work, new SUNSPACE modification have been proposed to obtain a lighter colored material and to simplify the synthesis process by the elimination of the thermal treatment. The color change was obtained using another industrial by-product, the bottom ash (BA), residue of municipal waste combustion while the substitution of sodium bicarbonate (used as pore former in SUNSPACE synthesis) with hydrogen peroxide allowed to avoid the thermal treatment. Samples were fully characterized and tested to evaluate the adsorption capacity using for the first time an aerosol nanoparticle generator and a TiO2 suspension as PM source. The results obtained are encouraging for samples realized with SF and for SUNSPACE BA. On the contrary, samples realized with BA and hydrogen peroxide showed a water repellent behavior, studied with wettability tests. Results showed that the contact angle of these materials is above the hydrophobicity limit. Moreover, samples were also tested to photodegrade organic pollutants obtaining the best results for samples realized with BA, hydrogen peroxide and TiO2 (added during the samples’ preparation due to its good photocatalytic activity). Finally, the thermal treatment of SUNSPACE was changed with a microwave treatment that allows to improve the material sustainability and to speed up the treatment. Samples were characterized and tested using the aerosol nanoparticles generator. However, these are preliminary tests aimed at thinking about new possible applications of the material, for example to make outdoor vases that help trap the PM. In the last chapter, some works, carried out during COVID-19, were reported focusing on its consequences on various environmental aspects and on the extraction of raw materials

4-Arylbenzenesulfonamides as Human Carbonic Anhydrase Inhibitors (hCAIs): Synthesis by Pd Nanocatalyst-Mediated Suzuki–Miyaura Reaction, Enzyme Inhibition, and X-ray Crystallographic Studies

Benzenesulfonamides bearing various substituted (hetero)aryl rings in the para-position were prepared by palladium nanoparticle-catalyzed Suzuki–Miyaura cross-coupling reactions and evaluated as human carbonic anhydrase (hCA, EC 4.2.1.1) inhibitors against isoforms hCA I, II, IX, and XII. Most of the prepared sulfonamides showed low inhibition against hCA I isoform, whereas the other cytosolic isoenzyme, hCA II, was strongly affected. The major part of these new derivatives acted as potent inhibitors of the tumor-associated isoform hCA XII. An opposite trend was observed for phenyl, naphthyl, and various heteroaryl substituted benzenesulfonamides which displayed subnanomolar hCA IX inhibition while poorly inhibiting the other tumor-associated isoform hCA XII. The inhibition potency and influence of the partially restricted aryl–aryl bond rotation on the activity/selectivity were rationalized by means of X-ray crystallography of the adducts of hCA II with several 4-arylbenzenesulfonamides

Studying Income Inequality of Immigrant Communities in Italy

This article deals with the issue of economic integration of immigrants in Italy. Ethnic inequality and economic stratification are analysed based both on the European Survey on Income and Living Conditions (EU-SILC) and the ad-hoc survey on households with foreign people conducted by the National Institute of Statistics in 2009. With reference to the native group and the groups identified by the largest ethnic communities living in Italy, through the Analysis of Gini decomposition technique, the article highlights that the between-group inequality accounts for a barely four percent of the overall inequality, the largest share being due to the inequalities within the groups. The policy prescription suggested is the adoption of ‘‘peculiar’’ policies on specific subgroups of immigrants aimed at reducing the disparities within the subgroups

The Reuse of Industrial By-Products for the Synthesis of Innovative Porous Materials, with the Aim to Improve Urban Air Quality

This works concerns the characterization and the evaluation of adsorption capability of innovative porous materials synthesized by using alginates and different industrial by-products: silica fume and bottom ash. Hydrogen peroxide was used as pore former to generate a porosity able to trap particulate matter (PM). These new materials are compared with the reference recently proposed porous SUNSPACE hybrid material, which was obtained in a similar process, by using silica fume. Structural, morphological, colorimetric and porosimetric analyses were performed to evaluate the differences between the obtained SUNSPACE typologies. The sustainability of the proposed materials was evaluated in terms of the Embodied Energy and Carbon Footprint to quantify the benefits of industrial by-products reuse. Adsorption tests were also performed to compare the ability of samples to trap PM. For this aim, titania suspension, with particles size about 300 nm, was used to simulate PM in the nanoparticle range. The results show that the material realized with bottom ash has the best performance

Environmental Impact of Surgical Masks Consumption in Italy Due to COVID-19 Pandemic

The COVID-19 pandemic suddenly changed the lifestyle of billions of people. Face masks became indispensable to protect from the contagion providing a significant environmental impact. The aim of this work is to propose possible solutions to decrease masks’ impact on the environment. For this reason, different masks (surgical and fabric) were considered, and the CO2 emissions associated with the mask materials production were calculated. Carbon Footprint (CF) for each material composing the masks was evaluated through the database Ces Selector 2019. The software Qgis (version 2.18.20) allows us to elaborate the CO2 emissions maps for each Italian region. Finally, for surgical masks, which are often imported from abroad, the CF related to transport was considered. It results that fabric masks are a sustainable solution to prevent contagion. The total CO2 emission associated with the use of fabric masks from the beginning of the pandemic (March 2020) to December 2021 resulted in about 7 kton compared to 350 kton for surgical masks

Effect of the Incorporation of Functionalized Cyclodextrins in the Liposomal Bilayer

Liposomes loaded with drug–cyclodextrin complexes are widely used as drug delivery systems, especially for species with low aqueous solubility and stability. Investigation of the intimate interactions of macrocycles with liposomes are essential for formulation of efficient and stable drug-in-cyclodextrin-in-liposome carriers. In this work, we reported the preparation of unilamellar vesicles of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) embedded with native β-cyclodextrin and two synthetic derivatives: heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TMCD) and heptakis(2,3-di-O-acetyl)-β-cyclodextrin (DACD). We then studied the effect of these macrocycles on the liposomal size, membrane viscosity, and liposomal stability at different temperatures and concentrations. We observed that TMCD and DACD affected vesicle size and the change of size was related to CD concentration. Irrespective of its nature, the macrocycle established interactions with the phospholipidic head groups, preventing cyclodextrins to diffuse into the lipid bilayer, as confirmed by molecular dynamics simulations. Such supramolecular structuring improves liposome stability making these colloid systems promising carriers for biologically active compounds

Using Mobile Monitoring and Atmospheric Dispersion Modeling for Capturing High Spatial Air Pollutant Variability in Cities

Air pollution is still one of the biggest environmental threats to human health on a global scale. In urban environments, exposure to air pollution is largely influenced by the activity patterns of the population as well as by the high spatial and temporal variability in air pollutant concentrations. Over the last years, several studies have attempted to better characterize the spatial variations in air pollutant concentrations within a city by deploying dense, fixed as well as mobile, low-cost sensor networks and more recently opportunistic sampling and by improving the spatial resolution of air quality models up to a few meters. The purpose of this work has been to investigate the use of properly designed mobile monitoring campaigns along the streets of an urban neighborhood to assess the capability of an operational air dispersion model as SIRANE at the district scale to capture the local variability of pollutant concentrations. To this end, an IoT ecosystem—MONICA (an Italian acronym for Cooperative Air Quality Monitoring), developed by ENEA, has been used for mobile measurements of CO and NO2 concentration in the urban area of the City of Portici (Naples, Southern Italy). By comparing the mean concentrations of CO and NO2 pollutants measured by MONICA devices and those simulated by SIRANE along the urban streets, the former appeared to exceed the simulated ones by a factor of 3 and 2 for CO and NO2, respectively. Furthermore, for each pollutant, this factor is higher within the street canyons than in open roads. However, the mobile and simulated mean concentration profiles largely adapt, although the simulated profiles appear smoother than the mobile ones. These results can be explained by the uncertainty in the estimation of vehicle emissions in SIRANE as well as the different temporal resolution of measurements of MONICA able to capture local high concentrations

Sustainability Analysis of Processes to Recycle Discharged Lithium-Ion Batteries, Based on the ESCAPE Approach

There are several recycling methods to treat discharged lithium-ion batteries, mostly based on pyrometallurgical and hydrometallurgical approaches. Some of them are promising, showing high recovery efficiency (over 90%) of strategic metals such as lithium, cobalt, and nickel. However, technological efficiency must also consider the processes sustainability in terms of environmental impact. In this study, some recycling processes of spent lithium-ion batteries were considered, and their sustainability was evaluated based on the ESCAPE “Evaluation of Sustainability of material substitution using CArbon footPrint by a simplifiEd approach” approach, which is a screening tool preliminary to the Life Cycle Assessment (LCA). The work specifically focuses on cobalt recovery comparing the sustainability of using inorganic or organic acid for the leaching of waste derived from lithium-ion batteries. Based on the possibility to compare different processes, for the first time, some considerations about technologies optimization have been done, allowing proposing strategies able to save chemicals. In addition, the energy mix of each country, to generate electricity has been considered, showing its influence on the sustainability evaluation. This allows distinguishing the countries using more low-carbon sources (nuclear and renewables) for a share of the electricity mix, where the recycling processes result more sustainable. Finally, this outcome is reflected by another indicator, the eco-cost from the virtual pollution model 99′ proposed by Vogtländer, which integrates the monetary estimation of carbon footprint