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.

Emerging contaminants in agricultural ecosystems: impact of selected pharmaceutical on water and soil ecology and pratical implications

Pharmaceuticals are useful tools to prevent and treat human and animal diseases. Following administration, a significant fraction of pharmaceuticals is excreted unaltered into faeces and urine and may enter the aquatic ecosystem and agricultural soil through irrigation with recycled water, constituting a significant source of emerging contaminants into the environment. Understanding major factors influencing their environmental fate is consequently needed to value the risk, reduce contamination, and set up bioremediation technologies. The antiviral drug Tamiflu (oseltamivir carboxylate, OC) has received recent attention due to the potential use as a first line defence against H5N1 and H1N1 influenza viruses. Research has shown that OC is not removed during conventional wastewater treatments, thus having the potential to enter surface water bodies. A series of laboratory experiments investigated the fate and the removal of OC in surface water systems in Italy and Japan and in a municipal wastewater treatment plant. A preliminary laboratory study investigated the persistence of the active antiviral drug in water samples from an irrigation canal in northern Italy (Canale Emiliano Romagnolo). After an initial rapid decrease, OC concentration slowly decreased during the remaining incubation period. Approximately 65% of the initial OC amount remained in water at the end of the 36-day incubation period. A negligible amount of OC was lost both from sterilized water and from sterilized water/sediment samples, suggesting a significant role of microbial degradation. Stimulating microbial processes by the addition of sediments resulted in reduced OC persistence. Presence of OC (1.5 μg mL-1) did not significantly affect the metabolic potential of the water microbial population, that was estimated by glyphosate and metolachlor mineralization. In contrast, OC caused an initial transient decrease in the size of the indigenous microbial population of water samples. A second laboratory study focused on basic processes governing the environmental fate of OC in surface water from two contrasting aquatic ecosystems of northern Italy, the River Po and the Venice Lagoon. Results of this study confirmed the potential of OC to persist in surface water. However, the addition of 5% of sediments resulted in rapid OC degradation. The estimated half-life of OC in water/sediment of the River Po was 15 days. After three weeks of incubation at 20 °C, more than 8% of 14C-OC evolved as 14CO2 from water/sediment samples of the River Po and Venice Lagoon. OC was moderately retained onto coarse sediments from the two sites. In water/sediment samples of the River Po and Venice Lagoon treated with 14C-OC, more than 30% of the 14C-residues remained water-extractable after three weeks of incubation. The low affinity of OC to sediments suggests that the presence of sediments would not reduce its bioavailability to microbial degradation. Another series of laboratory experiments investigated the fate and the removal of OC in two surface water ecosystems of Japan and in the municipal wastewater treatment plant of the city of Bologna, in Northern Italy. The persistence of OC in surface water ranged from non-detectable degradation to a half-life of 53 days. After 40 days, less than 3% of radiolabeled OC evolved as 14CO2. The presence of sediments (5%) led to a significant increase of OC degradation and of mineralization rates. A more intense mineralization was observed in samples of the wastewater treatment plant when applying a long incubation period (40 days). More precisely, 76% and 37% of the initial radioactivity applied as 14C-OC was recovered as 14CO2 from samples of the biological tank and effluent water, respectively. Two bacterial strains growing on OC as sole carbon source were isolated and used for its removal from synthetic medium and environmental samples, including surface water and wastewater. Inoculation of water and wastewater samples with the two OC-degrading strains showed that mineralization of OC was significantly higher in both inoculated water and wastewater, than in uninoculated controls. Denaturing gradient gel electrophoresis and quantitative PCR analysis showed that OC would not affect the microbial population of surface water and wastewater. The capacity of the ligninolytic fungus Phanerochaete chrysosporium to degrade a wide variety of environmentally persistent xenobiotics has been largely reported in literature. In a series of laboratory experiments, the efficiency of a formulation using P. chrysosporium was evaluated for the removal of selected pharmaceuticals from wastewater samples. Addition of the fungus to samples of the wastewater treatment plant of Bologna significantly increased (P < 0.05) the removal of OC and three antibiotics, erythromycin, sulfamethoxazole, and ciprofloxacin. Similar effects were also observed in effluent water. OC was the most persistent of the four pharmaceuticals. After 30 days of incubation, approximately two times more OC was removed in bioremediated samples than in controls. The highest removal efficiency of the formulation was observed with the antibiotic ciprofloxacin. The studies included environmental aspects of soil contamination with two emerging veterinary contaminants, such as doramectin and oxibendazole, wich are common parasitic treatments in cattle farms.

Synthesis and application of new ion-tagged ligands and organocatalysts

We report the synthesis and application of some ion-tagged catalysts in organometallic catalysis and organocatalysis. With the installation of an ionic group on the backbone of a known catalyst, two main effects are generally obtained. i) a modification of the solubility of the catalyst: if judicious choice of the ion pair is made, the ion-tag can confer to the catalyst a solubility profile suitable for catalyst recycling. ii) the ionic group can play a non-innocent role in the process considered: if stabilizing interaction between the ionic group and the developing charges in the transition state are established, the reaction can speed up. We describe the use of ion-tagged diphenylprolinol as Zn ligand. The chiral ligand grafted onto an ionic liquid (IL) was recycled 10 times with no loss of reactivity and selectivity, when it was employed in the first example of enantioselective addition of ZnEt2 to aldehydes in ILs. An ammonium-tagged phosphine displayed the capability to stabilize Pd catalysts for the Suzuki reaction in ILs. The ionic phase was recycled 6 times with no detectable loss of activity and very low Pd leaching in the organic phase. This catalytic system was also employed for the functionalization of the challenging substrate 5,11-dibromotetracene. In the field of organocatalysis, we prepared two ion-tagged derivatives of the McMillan imidazolidinone. The results of the asymmetric Diels-Alder reaction between trans-cinnamaldehyde and cyclopentadiene exhibited great dependence on the position and nature of the ionic group. Finally, when O-TMS-diphenylprolinol was tagged with an imidazolium ion, exploiting a silyl ether linker, an efficient catalyst for the asymmetric addition of aldehydes to nitroolefins was achieved. The catalyst displayed enhanced reactivity and the same high level of selectivity of the untagged parent catalyst and it could be employed in a wide range of reaction conditions, included use of water as solvent.

Il calcestruzzo con aggregati di riciclo: sviluppi ed applicazioni nel panorama nazionale ed internazionale.

Il calcestruzzo è uno dei materiali più utilizzati nell’edilizia, ma il meno sostenibile. Per la sua produzione vengono sfruttate elevate quantità di risorse naturali non rinnovabili con un impatto ambientale non trascurabile, sia per le sostanze emesse in atmosfera, sia per le macerie derivate post utilizzo. L’ingresso nel XXI secolo ha segnato definitivamente l’affermazione del concetto di sviluppo sostenibile nei riguardi di tutti i processi produttivi dei beni, che devono essere necessariamente strutturati secondo una logica di risparmio energetico e di controllo della produzione di scorie e rifiuti, prevedendone un loro riutilizzo in altri settori, o un loro smaltimento senza provocare danni all’ambiente. Anche l’industria del cemento e del calcestruzzo è chiamata a svolgere il proprio ruolo per contribuire ad un miglior bilancio ecologico globale, indirizzando la ricerca verso possibilità d’impiego di materiali “innovativi”, che siano in grado di sostituire parzialmente o totalmente l’uso di materie prime non rinnovabili, tenendo conto dell’enorme richiesta futura di infrastrutture, soprattutto nei paesi in via di sviluppo. Negli ultimi anni si sta sempre più affermando il potenziale del riciclo dei materiali ottenuti dalla demolizione di edifici (C&DW – Construction and Demolition Waste), questo dovuto anche a politiche di gestione dei rifiuti che incentivano il risparmio, il riutilizzo, il riciclo e la valorizzazione dei beni. I calcestruzzi con aggregati di riciclo sono generalmente suddivisi in due macrogruppi: quelli ottenuti da aggregati di riciclo di solo calcestruzzo (RCA – Recycled Coarse Aggregate) e quelli da aggregati da demolizione totale (MRA – Mixed Recycled Aggregate) che però contengono molte impurità. Come anche uno può subito pensare gli aggregati riciclati hanno delle proprietà diverse da quelli naturali, questi contengono oltre l’aggregato naturale anche il legante coeso, polveri di laterizio, vetro, ceramica, plastica eccet., i quali offrono una miscela ricca di cloruri, solfati, silice amorfa ed altri componenti dannosi per la nuova miscela di calcestruzzo. In presenza di questi prodotti, gli aggregati non solo non soddisfano i requisiti chimici, ma influiscono negativamente anche sulle proprietà fisico-meccaniche del calcestruzzo. Per questo vedremmo in questa tesi tramite un accurata analisi degli aggregati, e del loro “contributo” per il corretto comportamento del calcestruzzo, leggendo criticamente come le normative regolano i requisiti che gli aggregati debbono soddisfare, vedendo le varie possibilità di riutilizzo dei materiali di riciclo da demolizione. La tesi mira all'incentivo dei materiali da riciclo, come scelta sostenibile per il futuro dell'edilizia. E' stato calcolato che la produzione totale di macerie da demolizione nel mondo, non supera il 20% in massa degli aggregati che vengono utilizzati per la produzione del calcestruzzo nei paesi sviluppati. Dai vari studi è stato valutato in media che col solo 20% di riciclato sostituito, le caratteristiche del calcestruzzo indurito cambiano di poco dal normale miscelato con aggregati naturali; ovviamente se gli aggregati da riciclo sono stati selezionati e sottoposti ai vari test delle norme europee standardizzate. Quindi uno può subito pensare in linea teorica, tralasciando i costi di gestione, trasporto eccet. , che basta utilizzare per ogni metro cubo di calcestruzzo 20% di riciclato, per rispondere allo smaltimento dei rifiuti da C&D; abbassando cosi i costi degli inerti naturali, sempre parlando di economie di scala. Questo è in linea teorica, ma riflette un dato rilevante. Nel presente lavoro si partirà da una veloce lettura sul comportamento del calcestruzzo, su i suoi principali costituenti, concentrandoci sugli aggregati, analizzandone le sue proprietà fisico-meccaniche, quali la granulometria, la resistenza meccanica e la rigidezza, valutando l’importanza dei legami coesivi tra aggregato alla pasta cementizia. Verranno inoltre analizzate le azioni deleterie che possono instaurarsi tra aggregato di riciclo e pasta cementizia. Dopo aver visto le varie politiche sulla gestione dei rifiuti, la legislazione passata e presente sull’uso dei materiali riciclati, si analizzeranno vari studi sulle proprietà fisico-meccaniche dei calcestruzzi con aggregati di riciclo seguiti da università e poli di ricerca internazionali. Se gli aggregati di riciclo sono selezionati con metodo, in presenza di piani di gestione regionale e/o nazionale, è possibile soddisfare le prestazioni richieste del calcestruzzo, nel rispetto delle politiche di sostenibilità economico-ambientali. Può essere il calcestruzzo riciclato una scelta non solo sostenibile, ma anche economica per il settore edile? Si può avere un calcestruzzo riciclato ad alte prestazioni? Quali sono le politiche da mettere in atto per un mercato di produzione sostenibile del riciclato? Questo e molto altro verrà approfondito nelle pagine seguenti di questa tesi.

Zellulärer Transport von Myelinproteinen

Während der Myelinbildung im zentralen Nervensystem (ZNS) umwinden Oligodendrozyten mit Ausläufern ihrer Plasmamembran mehrfach das Axon. Myelin ermöglicht die saltatorische Erregungsweiterleitung entlang der Axone und ist zudem für die Aufrechterhaltung der axonalen Integrität erforderlich (Edgar and Garbern, 2004). Ein Oligodendrozyt myelinisiert bis zu 40 Axonsegmente gleichzeitig, wodurch er in seiner aktivsten Myelinisierungsphase 5 bis 50 x 103 µm2 Membranfläche pro Tag produziert (Pfeiffer et al., 1993). Die vollständig ausgebildete Myelinscheide besteht aus Subdomänen mit charakteristischen Protein- und Lipidzusammensetzungen. Die Entwicklung und der Erhalt der komplexen Myelinmembran erfordert die kontinuierliche Kommunikation zwischen Neuronen und Glia-Zellen, die Koordination der Protein- und Lipidsynthese sowie angepasste intrazelluläre Sortier- und Transportwege der Myelinkomponenten. Über die molekularen Mechanismen, die zur Ausbildung des Myelins und seiner Domänen führen, ist bisher nicht sehr viel bekannt. Im Rahmen dieser Arbeit wurden Endo- und Exozytosemechanismen von Myelinproteinen analysiert. Dabei wurden drei Proteine untersucht, die in unterschiedlichen Subdomänen der Myelinmembran des ZNS lokalisiert sind. Das Hauptmyelinprotein Proteolipid Protein (PLP), das Myelin-assoziierte Glykoprotein (MAG) und das Myelin Oligodendrozyten Glykoprotein (MOG). Die Exozytose des Hauptmyelinproteins PLP erfolgt möglicherweise durch sekretorische Lysosomen (Trajkovic et al., 2006) und ist Ca2+-abhängig. Interessanterweise konnte gezeigt werden, dass PLP, MAG und MOG unterschiedlichen endosomalen Transportwegen und Sortierprozessen unterliegen. PLP wird über einen Clathrin-unabhängigen, MAG und MOG hingegen über einen Clathrin-abhängigen Mechanismus endozytiert. Zudem gelangen die Proteine zu unterschiedlichen endosomalen Zielkompartimenten und recyceln zu verschiedenen oligodendroglialen Membrandomänen. Diese Ergebnisse legen nahe, dass die endosomale Sortierung und das Recycling der Myelinproteine, die für die Bildung der Subdomänen erforderliche Umgestaltung der oligodendroglialen Plasmamembran unterstützen.

Food Safety and Mineral Oil Contaminated Paperboard Packaging: an Analytical Challenge and a Migration Study

Food packaging protects food, but it can sometimes become a source of undesired contaminants. Paper based materials, despite being perceived as “natural” and safe, can contain volatile contaminants (especially if made from recycled paper) able to migrate to food, as mineral oil, phthalates and photoinitiators. Mineral oil is a petroleum product used as printing ink solvent for newspapers, magazines and packaging. From paperboard printing and from recycled fibers (if present), mineral oil migrates into food, even if dry, through the gas phase. Its toxicity is not fully evaluated, but a temporary Acceptable Daily Intake (ADI) of 0.6 mg kg-1 has been established for saturated mineral oil hydrocarbons (MOSH), while aromatic hydrocarbons (MOAH) are more toxic. Extraction and analysis of MOSH and MOAH is difficult due to the thousands of molecules present. Extraction methods for packaging and food have been optimized, then applied for a “shopping trolley survey” on over 100 Italian and Swiss market products. Instrumental analyses were performed with online LC-GC/FID. Average concentration of MOSH in paperboards was 626 mg kg-1. Many had the potential of contaminating foods exceeding temporary ADI tens of times. A long term migration study was then designed to better understand migration kinetics. Egg pasta and müesli were chosen as representative (high surface/weight ratio). They were stored at different temperatures (4, 20, 30, 40 and 60°C) and conditions (free, shelved or boxed packs) for 1 year. MOSH and MOAH kinetic curves show that migration is a fast process, mostly influenced by temperature: in egg pasta (food in direct contact with paperboard), half of MOSH is transferred to food in a week at 40°C and in 8 months at 20°C. The internal plastic bag present in müesli slowed down the startup of migration, creating a “lag time” in the curves.

Integration of MFA and LCA methodologies: the anthropogenic aluminium cycle in Italy

MFA and LCA methodologies were applied to analyse the anthropogenic aluminium cycle in Italy with focus on historical evolution of stocks and flows of the metal, embodied GHG emissions, and potentials from recycling to provide key features to Italy for prioritizing industrial policy toward low-carbon technologies and materials. Historical trend series were collected from 1947 to 2009 and balanced with data from production, manufacturing and waste management of aluminium-containing products, using a ‘top-down’ approach to quantify the contemporary in-use stock of the metal, and helping to identify ‘applications where aluminium is not yet being recycled to its full potential and to identify present and future recycling flows’. The MFA results were used as a basis for the LCA aimed at evaluating the carbon footprint evolution, from primary and electrical energy, the smelting process and the transportation, embodied in the Italian aluminium. A discussion about how the main factors, according to the Kaya Identity equation, they did influence the Italian GHG emissions pattern over time, and which are the levers to mitigate it, it has been also reported. The contemporary anthropogenic reservoirs of aluminium was estimated at about 320 kg per capita, mainly embedded within the transportation and building and construction sectors. Cumulative in-use stock represents approximately 11 years of supply at current usage rates (about 20 Mt versus 1.7 Mt/year), and it would imply a potential of about 160 Mt of CO2eq emissions savings. A discussion of criticality related to aluminium waste recovery from the transportation and the containers and packaging sectors was also included in the study, providing an example for how MFA and LCA may support decision-making at sectorial or regional level. The research constitutes the first attempt of an integrated approach between MFA and LCA applied to the aluminium cycle in Italy.

Response of nutrient cycles of an old-growth montane forest in Ecuador to experimental low-level nutrient amendments

Atmospheric nitrogen (N) and phosphorus (P) depositions are expected to increase in the tropicsrnas a consequence of increasing human activities in the next decades. Furthermore, a possiblernshortened El Niño Southern Oscillation cycle might come along with more frequent calcium (Ca)rndepositions on the eastern slope of the Ecuadorian Andes originating from Saharan dust. It isrncrucial to understand the response of the old-growth montane forest in Ecuador to increasedrnnutrient deposition to predict the further development of this megadiverse ecosystem.rnI studied experimental additions of N, P, N+P and Ca to the forest and an untreatedrncontrol, all in a fourfold replicated randomized block design. These experiments were conductedrnin the framework of a collaborative research effort, the NUtrient Manipulation EXperimentrn(NUMEX). I collected litter leachate, mineral soil solution (0.15 and 0.30 m depths), throughfallrnand fine litterfall samples and determined N, P and Ca concentrations and fluxes. This approachrnalso allowed me to assess whether N, P and/or Ca are limiting nutrients for forest growth.rnFurthermore, I evaluated the response of fine root biomass, leaf area index, leaf area and specificrnleaf area, tree diameter growth and basal area increment contributed from a cooperating group inrnthe Ca applied and control treatments.rnDuring the observation period of 16 months after the first fertilizer application, less thanrn10, 1 and 5% of the applied N, P and Ca, respectively, leached below the organic layer whichrncontained almost all roots but no significant leaching losses occurred to the deeper mineral soil.rnDeposited N, P and Ca from the atmosphere in dry and wet form were, on balance, retained in therncanopy in the control treatment. Retention of N, P and Ca in the canopy in their respectiverntreatments was reduced resulting in higher concentrations and fluxes of N, P and Ca inrnthroughfall and litterfall. Up to 2.5% of the applied N and 2% of the applied P and Ca werernrecycled to the soil with throughfall. Fluxes of N, P and Ca in throughfall+litterfall were higher inrnthe fertilized treatments than in the control; up to 20, 5 and 25% of the applied N, P and Ca,rnrespectively, were recycled to the soil with throughfall+litterfall.rnIn the Ca-applied plots, fine root biomass decreased significantly. Also the leaf area of thernfour most common tree species tended to decrease and the specific leaf area increasedrnsignificantly in Graffenrieda emarginata Triana, the most common tree species in the study area.rnThese changes are known plant responses to reduced nutrient stress. Reduced aluminium (Al)rntoxicity as an explanation of the Ca effect was unlikely, because of almost complete organocomplexationrnof Al and molar Ca:Al concentration ratios in solution above the toxicity threshold.rnThe results suggest that N, P and Ca co-limit the forest ecosystem functioning in thernnorthern Andean montane forests in line with recent assumptions in which different ecosystemrncompartments and even different phenological stages may show different nutrient limitationsrn(Kaspari et al. 2008). I conclude that (1) the expected elevated N and P deposition will bernretained in the ecosystem, at least in the short term and hence, quality of river water will not bernendangered and (2) increased Ca input will reduce nutrient stress of the forest.

Cell death mechanisms triggered by monoclonal antibodies against CD99 in Ewing sarcoma: Cross-talk between MDM2, IGF-1R and Ras/MAPK

CD99 is a 32 kDa transmembrane protein whose high expression characterizes Ewing sarcoma (ES), a very aggressive pediatric bone tumor. In addition to its diagnostic value, CD99 has therapeutic potential since it leads to rapid and massive ES cell death when engaged with specific antibodies. Here a novel mechanism of cell death triggered via CD99 is shown, leading, ultimately, to the appearance of macropinocytotic vescicles. Anti-CD99 mAb 0662 induces MDM2 ubiquitination and degradation, which causes not only a p53 reactivation but also the IGF-1R induction and its subsequent internalization; CD99 results internalized together with IGF-1R inside endosomes, but then the two molecules display a different sorting: CD99 is degraded, while IGF-1R is recycled on the surface, causing, as a final step, the up-regulation of RAS-MAPK. High-expressing CD99 mesenchymal stem cells show mild Ras induction but no p53 activation and escape cell death, but in presence of EWS/FLI1 mesenchymal stem cells expressing CD99 show a stronger Ras induction and a p53 reactivation, leading to a significant cell death rate. We propose that CD99 triggering in a EWS/FLI1-driven oncogenetic context creates a synergy between RAS upregulation and p53 activation in ES cells, leading to cell death. Moreover, our data rule out possible concerns on toxicity related to the broad CD99 expression in normal tissues and provide the rationale for the therapeutic use of anti-CD99 MAbs in the clinic.

Sistemi tecnologici innovativi di involucro per il recupero del patrimonio edilizio recente. L'edilizia scolastica nel Comune di Bologna

La ricerca è volta a presentare un nuovo approccio integrato, a supporto di operatori e progettisti, per la gestione dell’intero processo progettuale di interventi di riqualificazione energetica e architettonica del patrimonio edilizio recente, mediante l’impiego di soluzioni tecnologiche innovative di involucro edilizio. Lo studio richiede necessariamente l’acquisizione di un repertorio selezionato di sistemi costruttivi di involucro, come base di partenza per l’elaborazione di soluzioni progettuali di recupero delle scuole appartenenti al secondo dopoguerra, in conglomerato cementizio armato, prevalentemente prefabbricate. Il progetto individua procedimenti costruttivi ecocompatibili per la progettazione di componenti prefabbricati di involucro “attivo”, adattabile ed efficiente, da assemblare a secco, nel rispetto dei requisiti prestazionali richiesti dalle attuali normative. La ricerca è finalizzata alla gestione dell’intero processo, supportato da sistemi di rilevazione geometrica, collegati a software di programmazione parametrica per la modellazione di superfici adattabili alla morfologia dei fabbricati oggetto di intervento. Tali strumenti informatizzati CAD-CAM sono connessi a macchine a controllo numerico CNC per la produzione industrializzata degli elementi costruttivi “su misura”. A titolo esemplificativo dell’approccio innovativo proposto, si formulano due possibili soluzioni di involucro in linea con i paradigmi della ricerca, nel rispetto dei principi di sostenibilità, intesa come modularità, rapidità di posa, reversibilità, recupero e riciclo di materiali. In particolare, le soluzioni innovative sono accomunate dall’applicazione di una tecnica basata sull’assemblaggio di elementi prefabbricati, dall’adozione di una trama esagonale per la tassellazione della nuova superficie di facciata, e dall’utilizzo del medesimo materiale termico isolante, plastico e inorganico, riciclato ed ecosostenibile, a basso impatto ambientale (AAM - Alkali Activated Materials). Le soluzioni progettuali proposte, sviluppate presso le due sedi coinvolte nella cotutela (Università di Bologna, Université Paris-Est) sono affrontate secondo un protocollo scientifico che prevede: progettazione del sistema costruttivo, analisi meccanica e termica, sperimentazione costruttiva, verifica delle tecniche di messa in opera e dei requisiti prestazionali.

Verhalten von Recycling-Materialien in der Umwelt : Labor- und Feldversuche

Im Baugewerbe fallen jährlich mehrere Millionen Tonnen an Baureststoffen an, die nach erfolgter Aufbereitung als Recycling-Baustoffe erneut verwendet werden können. Allerdings besteht Unklarheit hinsichtlich der Stofffreisetzung aus Recycling-Materialien sowie der Parameter, die zur Beurteilung im Wesentlichen heranzuziehen sind. Des Weiteren gilt es der Frage nachzugehen, welche Laborversuche eine realistische Prognose zum Stoffaustrag unter Freilandbedingungen ermöglichen. Ein Ergebnisvergleich aus Feld- und Laborversuchen mit Recycling-Materialien zeigt, dass weder Ammoniumnitrat-Extraktion, pH-stat Versuch noch S4- und Modifizierter S4-Test genauere Prognosen zum Stoffaustrag unter Freilandbedingungen ermöglichen. Mit einem Langzeit-Standtest sowie Schüttelversuchen mit unterschiedlichen Wasser/Feststoff-Verhältnissen lässt sich der Einfluss durch verschiedene Korngrößen sowie Materialabrieb besser kontrollieren. Diese Versuchskombination erlaubt Rückschlüsse auf die Löslichkeit und Verfügbarkeit von Stoffen in den Recycling-Materialien. Die Ergebnisse aus Säulenversuchen weisen auf eine gute Vergleichbarkeit mit den Feldversuchen hin, was sich an denselben vorherrschenden Prozessen bei der Freisetzung für eine Reihe von Stoffen zeigt. Bei mehreren Stoffen treten ähnliche Konzen-trationshöchstwerte bei Säulen- und Feldversuch auf, ebenso zeigt der Vergleich aufsummierter Massenanteile für den Säulenversuch, dass bei einer Reihe von Stoffen eine grobe Abschätzbarkeit für eine Langzeitprognose unter Freilandbedingungen existiert. Als wesentliche Parameter für die Stofffreisetzung aus den Recycling-Materialien sind neben CO2-Einfluss und pH-Wert ebenfalls Temperatureinfluss, Material-Heterogenität sowie einzusetzende Korngröße anzusehen.

Recycling of end of life concrete fines (0 - 4 mm) into silica and cement

The purpose of this work is to find a methodology in order to make possible the recycling of fines (0 - 4 mm) in the Construction and Demolition Waste (CDW) process. At the moment this fraction is a not desired by-product: it has high contaminant content, it has to be separated from the coarse fraction, because of its high water absorption which can affect the properties of the concrete. In fact, in some countries the use of fines recycled aggregates is highly restricted or even banned. This work is placed inside the European project C2CA (from Concrete to Cement and Clean Aggregates) and it has been held in the Faculty of Civil Engineering and Geosciences of the Technical University of Delft, in particular, in the laboratory of Resources And Recycling. This research proposes some procedures in order to close the loop of the entire recycling process. After the classification done by ADR (Advanced Dry Recovery) the two fractions "airknife" and "rotor" (that together constitute the fraction 0 - 4 mm) are inserted in a new machine that works at high temperatures. The temperatures analysed in this research are 600 °C and 750 °C, cause at that temperature it is supposed that the cement bounds become very weak. The final goal is "to clean" the coarse fraction (0,250 - 4 mm) from the cement still attached to the sand and try to concentrate the cement paste in the fraction 0 - 0,250 mm. This new set-up is able to dry the material in very few seconds, divide it into two fractions (the coarse one and the fine one) thanks to the air and increase the amount of fines (0 - 0,250 mm) promoting the attrition between the particles through a vibration device. The coarse fraction is then processed in a ball mill in order to improve the result and reach the final goal. Thanks to the high temperature it is possible to markedly reduce the milling time. The sand 0 - 2 mm, after being heated and milled is used to replace 100% of norm sand in mortar production. The results are very promising: the mortar made with recycled sand reaches an early strength, in fact the increment with respect to the mortar made with norm sand is 20% after three days and 7% after seven days. With this research it has been demonstrated that once the temperature is increased it is possible to obtain a clean coarse fraction (0,250 - 4 mm), free from cement paste that is concentrated in the fine fraction 0 - 0,250 mm. The milling time and the drying time can be largely reduced. The recycled sand shows better performance in terms of mechanical properties with respect to the natural one.

Mesoproterozoic Deposition, Regional Metamorphism and Deformation in North-Central New Mexico: Evidence from Metamorphic Monazite and Detrital Zircon Geochronology in the Picuris Mountains

Detrital zircon and metamorphic monazite ages from the Picuris Mountains, north central New Mexico, were used to confirm the depositional age of the Marquenas Formation, to document the depositional age of the Vadito Group, and to constrain the timing of metamorphism and deformation in the region. Detrital zircon 207Pb/206Pb ages were obtained with the LA-MC-ICPMS from quartzites collected from the type locality of the Marquenas Formation exposed at Cerro de las Marquenas, and from the lower Vadito Group in the southern and eastern Picuris Mountains. The Marquenas Formation sample yields 113 concordant ages including a Mesoproterozoic age population with four grains ca. 1470 Ga, a broad Paleoproterozoic age peak at 1695 Ma, and minor Archean age populations. Data confirm recent findings of Mesoproterozoic detrital zircons reported by Jones et al. (2011), and show that the Marquenas Formation is the youngest lithostratigraphic unit in the Picuris Mountains. Paleoproterozoic and Archean detrital grains in the Marquenas Formation are likely derived from local recycled Vadito Group rocks and ca. 1.75 Ga plutonic complexes, and ca. 1.46 detrital zircons were most likely derived from exposed Mesoproterozoic plutons south of the Picuris. Ninety-five concordant grains from each of two Vadito Group quartzites yield relatively identical unimodal Paleoproterozoic age distributions, with peaks at 1713-1707 Ma. Eastern exposures of quartzite mapped as Marquenas Formation yield detrital zircon age patterns and metamorphic mineral assemblages that are nearly identical to the Vadito Group. On this basis, I tentatively assigned the easternmost quartzite to the Vadito Group. Zircon grains in all samples show low U/Th ratios, welldeveloped concentric zoning, and no evidence of metamorphic overgrowth events, consistent with an igneous origin. North-directed paleocurrent indicators, such as tangential crossbeds (Soegaard & Eriksson, 1986) and other primary sedimentary structures, are preserved in the Marquenas Formation quartzite. Together with pebble-toboulder metaconglomerates in the Marquenas, these observations suggest that this formation was deposited in a braided alluvial plain environment in response to syntectonic uplift to the south of the Picuris Mountains. Metamorphic monazite from two Vadito Group quartzite samples were analyzed with an electron microprobe (EMP). Elemental compositional variation with respect to Th and Y define core and rim domains in monazite grains, and show lower concentrations of Th (1.46-1.52 wt%) and Y (0.67 wt%) in the cores, and higher concentrations of Th (1.98 wt%) and Y (1.06 wt%) in the rims. Results show that Mesoproterozoic core and rim ages from five grains overlap within uncertainty, ranging from 1395-1469 Ma with an average age of 1444 Ma. This 1.44 Ga average age is the dominant timing of metamorphic monazite growth in the region, and represents the timing of metamorphism experienced by the region. An older 1630 Ma core observed in sample CD10-12 may be interpreted as a result of low temperature metamorphism in lower Vadito Group rocks due to heat from ca. 1.65 Ga granitic intrusions. Core ages ca. 1.5 Ga are likely due to a mixing age of two different age domains during analyses. Confirmed sedimentation at 1.48-1.45 Ga and documented mid-crustal regional metamorphism in northern New Mexico ca. 1.44-1.40 are likely associated with a Mesoproterozoic orogenic event.

Determining the Socially Optimal Recycling Rate

What municipal recycling rate is socially optimal? One credible answer would consider the recycling rate that minimizes the overall social costs of managing municipal waste. Such social costs are comprised of all budgetary costs and revenues associated with operating municipal waste and recycling programs, all costs to recycling households associated with preparing and storing recyclable materials for collection, all external disposal costs associated with waste disposed at landfills or incinerators, and all external benefits associated with the provision of recycled materials that foster environmentally efficient production processes. This paper discusses how to estimate these four components of social cost to then estimate the optimal recycling rate. (C) 2013 Elsevier B.V. All rights reserved.

Twelve factors influencing sustainable recycling of municipal solid waste in developing countries

Sustainable management of solid waste is a global concern, as exemplified by the United Nations Millennium Development Goals (MDG) that 191 member states support. The seventh MDG indirectly advocates for municipal solid waste management (MSWM) by aiming to ensure environmental sustainability into countries’ policies and programs and reverse negative environmental impact. Proper MSWM will likely result in relieving poverty, reducing child mortality, improving maternal health, and preventing disease, which are MDG goals one, four, five, and six, respectively (UNMDG, 2005). Solid waste production is increasing worldwide as the global society strives to obtain a decent quality of life. Several means exist in which the amount of solid waste going to a landfill can be reduced, such as incineration with energy production, composting of organic wastes, and material recovery through recycling, which are all considered sustainable methods by which to manage MSW. In the developing world, composting is already a widely-accepted method to reduce waste fated for the landfill, and incineration for energy recovery can be a costly capital investment for most communities. Therefore, this research focuses on recycling as a solution to the municipal solid waste production problem while considering the three dimensions of sustainability environment, society, and economy. First, twenty-three developing country case studies were quantitatively and qualitatively examined for aspects of municipal solid waste management. The municipal solid waste (MSW) generation and recovery rates, as well as the composition were compiled and assessed. The average MSW generation rate was 0.77 kg/person/day, with recovery rates varying from 5 – 40%. The waste streams of nineteen of these case studies consisted of 0 – 70% recyclable material and 17 – 80% organic material. All twenty-three case studies were analyzed qualitatively by identifying any barriers or incentives to recycling, which justified the creation of twelve factors influencing sustainable municipal solid waste management (MSWM) in developing countries. The presence of regulations, enforcement of laws, and use of incentive schemes constitutes the first factor, Government Policy. Cost of MSWM operations, the budget allocated to MSWM by local to national governments, as well as the stability and reliability of funds comprise the Government Finances factor influencing recycling in the third world. Many case studies indicated that understanding features of a waste stream such as the generation and recovery rates and composition is the first measure in determining proper management solutions, which forms the third factor Waste Characterization. The presence and efficiency of waste collection and segregation by scavengers, municipalities, or private contractors was commonly addressed by the case studies, which justified Waste Collection and Segregation as the fourth factor. Having knowledge of MSWM and an understanding of the linkages between human behavior, waste handling, and health/sanitation/environment comprise the Household Education factor. Individuals’ income influencing waste handling behavior (e.g., reuse, recycling, and illegal dumping), presence of waste collection/disposal fees, and willingness to pay by residents were seen as one of the biggest incentives to recycling, which justified them being combined into the Household Economics factor. The MSWM Administration factor was formed following several references to the presence and effectiveness of private and/or public management of waste through collection, recovery, and disposal influencing recycling activity. Although the MSWM Personnel Education factor was only recognized by six of the twenty-two case studies, the lack of trained laborers and skilled professionals in MSWM positions was a barrier to sustainable MSWM in every case but one. The presence and effectiveness of a comprehensive, integrative, long-term MSWM strategy was highly encouraged by every case study that addressed the tenth factor, MSWM Plan. Although seemingly a subset of private MSWM administration, the existence and profitability of market systems relying on recycled-material throughput, involvement of small businesses, middlemen, and large industries/exporters is deserving of the factor Local Recycled-Material Market. Availability and effective use of technology and/or human workforce and the safety considerations of each were recurrent barriers and incentives to recycling to warrant the Technological and Human Resources factor. The Land Availability factor takes into consideration land attributes such as terrain, ownership, and development which can often times dictate MSWM. Understanding the relationships among the twelve factors influencing recycling in developing countries, made apparent the collaborative nature required of sustainable MSWM. Factors requiring the greatest collaborative inputs include waste collection and segregation, MSWM plan, and local recycled-material market. Aligning each factor to the societal, environmental, and economic dimensions of sustainability revealed the motives behind the institutions contributing to each factor. A correlation between stakeholder involvement and sustainability existed, as supported by the fact that the only three factors driven by all three dimensions of sustainability were the same three that required the greatest collaboration with other factors. With increasing urbanization, advocating for improved health for all through the MDG, and changing consumption patterns resulting in increasing and more complex waste streams, the utilization of the collaboration web offered by this research is ever needed in the developing world. Through its use, the institutions associated with each of the twelve factors can achieve a better understanding of the collaboration necessary and beneficial for more sustainable MSWM.