Preocupados com aspectos ambientais relacionados com a recuperação de solventes e, também, com os riscos envolvidos em experimentos trivialmente executados em disciplinas de Química Orgânica Experimental, utilizamos critérios numéricos para avaliá-los e determinar a viabilidade de se adotarem práticas alternativas, em ambas as frentes. Neste contexto, comparamos, do ponto de vista ambiental, a viabilidade de recuperação de alguns solventes, por destilação, no Setor de Tratamento de Resíduos e Solventes (STRES), com a incineração completa dos mesmos materiais, em incinerador industrial. Para isto, procedemos à separação, por destilação, dos componentes de algumas misturas de solventes. Após determinação das composições dos destilados, por cromatografia em fase gasosa, inserimos os dados obtidos no software ECOSOLVENT para comparamos os impactos ambientais (considerando o EI99 como indicador da Avaliação do Ciclo de Vida) destas destilações com os das incinerações das misturas brutas. Para a maior parte dos casos, foi constatado um menor impacto ambiental para os processos de destilação, justificando-se a continuidade dos trabalhos do STRES. Quanto aos experimentos de Química Orgânica Experimental, combinamos a pontuação de riscos sugerida pela National Fire Protection Association-USA, com o critério de Economia Atômica, tanto para os processos tradicionais como para as modificações sugeridas. Estas últimas levaram, numericamente, a riscos menores, sem alteração das Economias Atômicas. / Concerned with environmental issues related to the recovery of solvents and also to the risks involved in trivial Experimental Organic Chemistry practices, we used numerical criteria to evaluate the feasibility of adopting alternative practices on both fronts. In this context, we compared, from the environmental point of view, the recovery feasibility of some solvents, by distillation, at the Setor de Tratamento de Resíduos e Solventes (STRES), with their complete incineration in an industrial incinerator. Therefore, we proceed to the separation, by distillation, of the components of some mixtures of solvents. After determining the composition of the distillates, by gas chromatography, we input the obtained data into the ECOSOLVENT software in order to compare the environmental impacts (considering the EI99 indicator for the Life Cycle Assessment calculations), arising from these distillations, with those from direct incineration of the crude mixtures of solvents. For most cases, distillation impacts were found to be smaller than those for incineration, thus justifiyng the existence of STRES. As for the Experimental Organic Chemistry practices, we cobined the American National Fire Protection Association`s risks score with the Atom Economy concept for the current, and for some suggested modified procedures. These latter ones led to numerical smaller risks without changing the Atomic Economies.

A indústria de produção de couro gera uma grande quantidade de resíduos com características poluentes e de elevada periculosidade, entre os quais se destacam os resíduos curtidos (aparas, serragem e pó de couro curtido) e os lodos provenientes das estações de tratamento de efluentes (lodos de cromo, lodos primários e lodos secundários). Estes resíduos possuem uma considerável quantidade de compostos de Cr(III) na sua composição, os quais, sob condições oxidantes, podem transformar-se em Cr(VI), que é altamente tóxico para animais, plantas e seres humanos. No entanto, estes resíduos constituem uma potencial fonte alternativa de cromo (tradicional pigmento industrial) que poderia ser aproveitada pela indústria de vidros e de esmaltes. No presente trabalho foi realizado o estudo das propriedades físicas e químicas de um lodo de cromo proveniente do distrito industrial do município de Franca/SP, com o intuito de avaliar a viabilidade da utilização das cinzas da incineração deste resíduo como uma potencial fonte alternativa de cromo na fabricação de vidros sodo-cálcicos coloridos para embalagens. Fluorescência de Raios X (FRX), Difração de Raios X (DRX), análises termodiferencial (DTA) e termogravimétrica (TG/DTG), análise elementar, análise granulométrica, determinação de poder calorífico pelo método da bomba calorimétrica e Microscopia Eletrônica de Varredura (MEV) foram usados para determinar as características físicas e químicas do lodo de cromo. A incineração do resíduo foi realizada numa mufla elétrica a 800 C, utilizando um cadinho de alumina. A determinação da concentração de íons Cr(VI) presentes no lodo e nas cinzas foi realizada através do método colorimétrico utilizando difenilcarbazida. Vidros sodo-cálcicos contendo as cinzas da incineração do lodo de cromo foram preparados por meio da fusão das matérias-primas industriais (areia, barrilha e calcário) em cadinhos de alumina a 1500 C por 1h, sob condições similares às utilizadas no processo industrial de produção de vidros comerciais de coloração verde (composição, adição de ferro e condições redutoras). Para fins de comparação, foram preparadas também amostras de vidros contendo cromita (tradicional fonte industrial de cromo utilizada pela indústria de vidros) sob condições semelhantes. As amostras de vidros foram caracterizadas em termos de composição química por FRX, MEV, DRX, coordenadas colorimétricas (sistema CIEL*a*b*) e absorção óptica. Os resultados de FRX mostraram que as cinzas apresentam um teor de cromo de aproximadamente 47% em massa de Cr2O3, valor não muito distante do teor de cromo observado na composição da cromita (cerca de 43% em massa de Cr2O3). Os vidros preparados utilizando cromita e as cinzas da incineração de lodo de cromo apresentaram bandas de absorção óptica semelhantes no intervalo analisado (200-3300 nm), sem a presença aparente da banda de absorção óptica entorno de 370 nm, característica do íon Cr6+. Estes resultados sugerem que sob condições adequadas de incineração do lodo, bem como formulação e fusão do vidro, é possível utilizar-se as cinzas obtidas como fonte alternativa de cromo para a fabricação de vidros coloridos do sistema soda-cal-sílica. / Leather production industry generates large quantities of solid wastes with pollutant characteristics and hazardous conditions, such as tanned wastes (Chrome shaving, chrome splits and buffing dust) and sludges from wastewater treatment process (Tannery sludge, primary and secondary sludge). These wastes containing Cr(III), which, under oxidizing conditions, can turn into Cr(VI), an extremely toxic and cancerigenous form of the element. However, these wastes are a potential source of chromium (traditional industrial pigment) which could be used by the glass and ceramic enamels industries. In the present work was studied the physical and chemical properties of a tannery sludge from the industrial district of the city of Franca, São Paulo State, Brazil, in order to evaluate the feasibility of using the ashes from incineration of this waste as a potential alternative source of chromium for the manufacturing of soda-lime glasses. X-Ray Fluorescence (XRF), Xray Diffraction (XRD), Differential Thermal Analysis (DTA), Thermogravimetric Analysis (TG/DTG), elemental analysis, granulometric analysis, determination of calorific value by the bomb calorimeter method and Scanning Electron Microscopy (SEM) were used to determine the physical and chemical characteristics of tannery sludge. The tannery sludge incineration was performed using an alumina crucible in a electric oven at 800 C. Colorimetric method using diphenylcarbazide were conducted to determinate the Cr(VI) concentration in the waste and the ashes from incineration. Soda-lime glass containing the ashes from incineration of tannery sludge was prepared by melting of industrial raw materials (sand, soda ash and limestone), in alumina crucibles at 1500 C for 1 hour, under similar conditions to those used in the industrial production process of commercial green container glasses (composition, addition of iron and reducing conditions). For comparison purposes, glasses containing chromite (traditional industrial source of chromium used by the glass industry) were also prepared under similar conditions. The glass samples were characterized in terms of chemical composition by XRF, MEV, DRX, color (CIEL*a*b* system) and optical absorption. The FRX results revealed that the ashes are composed by about 47 wt% Cr2O3. This amount is not so far from the chromium content observed in the composition of chromite (about 43 wt% Cr2O3). The glasses containing chromite and the ashes from the incineration of the tannery sludge exhibited approximately similar optical absorption bands in the analyzed range (200-3300 nm), without the presence of optical absorption band around 370 nm, characteristic of Cr 6+. These results suggests that under appropriate incineration conditions of the sludge, as well as formulation and melting of glass, is possible use the chromium-rich ashes from incineration of tannery sludge as an alternative source of chromium for the manufacturing of colored glasses of the soda-lime-silica system.

Water shortage issues have been growing concerns in many cities around the world in recent years, especially in Eastern cities of Australia, which is the driest continent on the earth. The aim of this PhD thesis is a development of a model to study the use of waste incineration energy supplemented by alternative energy to power seawater desalination. It is to aid the freshwater supply of a drought stricken city in Eastern Australia. My work contributes to a development of efficient model in a simpler understandable way to reduce efforts required for modelling complex multi domain problems. This research is motivated by the successive severe drought conditions that affected many Australian cities in the past few years, compounded with an additional strain from a fast growing population. While we dump our waste into the Australian landscape, in more densely populated cities in Europe and Asia, the waste is incinerated to obtain thermal energy for various purposes. The waste is used as an energy source while at the same time reducing the amount of space needed for landfill. Seawater desalination has been uccessfully practiced for quite some time particularly in the Middle Eastern countries. To deal with increasing water shortage crisis, many cities around the world have opted or are considering seawater desalination to supplement their freshwater supply. The combination of both - waste incineration and seawater desalination - has rarely been studied. This is a twofold problem that requires modelling the problem of water demand and supply together with waste incineration to find a sustainable solution. This is a complex task. The effort needed for this can be reduced by using a modelling approach that is more efficient than the traditionally used statistical approaches. In this thesis, I present a comprehensive model developed using a dynamic system approach combined with artificial neural networks. It simulates water demand and supply as well as the possible amount of the desalinated water that can be produced using the energy from clean city waste incineration. This is done while taking in various influential factors including population growth and irregular weather patterns. This research comprises a literature review on seawater desalination and waste incineration, the establishment of water demand and supply dynamics of Gold Coast City as my case study and identifying any modelling difficulties that need to be overcome. This is followed by the development of a comprehensive model and its components, model calibration and simulation experiments. It was found that with the energy of waste incineration, up to 60% of the freshwater demand could be fulfilled by seawater desalination in a sustainable way.

Increasingly intensive efforts are being made to enhance energy systems via augmented introduction of renewable energy along with improved energy efficiency. Resource constraints and sustained high fossil fuel prices have created a new phenomenon in the world market. Enhanced energy security and renewable energy development are currently high on public agenda worldwide for achieving a high standard of welfare for future generations. Biomass and municipal solid waste (MSW) have widely been accepted as important locally-available renewable energy sources offering low carbon dioxide (CO2) emissions. Concerning solid waste management, it has become a critical issue in Southeast Asia since the most popular form for waste disposal still employs open dumping and landfilling. While the need for a complete sustainable energy solution is apparent, solid waste management is also an essential objective, so it makes sense to explore ways in which the two can be joined. Electricity production in combination with energy recovery from flue gases in thermal treatment plants is an integral part of MSW management for many industrialized nations. In Sweden, MSW is considered as an important fuel resource for partially meeting EU environmental targets within cogeneration. However it is normally difficult to justify traditional cogeneration in tropical locations since there is little need for the heat produced. Similarly, MSW-fired cogeneration usually operates with low capacity during non-heating season in Sweden. Therefore, it is very important to find new alternatives for energy applications from waste, such as the implementation of thermally driven cooling processes via absorption cooling in addition to electricity production. The work presented herein concentrates first on an investigation of electricity generation from MSW power plants and various energy applications from waste in tropical urban areas. The potential for various types of absorption chillers driven by MSW power plants for providing both electricity and cooling is of particular interest. Additionally a demonstration and analysis of decentralized thermally driven cooling in district heating network supplied by low temperature heat from a cogeneration of MSW have been conducted. This study aims at developing the best system configuration as well as finding improved system design and control for a combination of district heating and distributed thermally driven cooling. Results show that MSW incineration has the ability to lessen environmental impacts associated with waste disposal, and it can contribute positively towards expanding biomass-based energy production in Southeast Asia. For electricity production, the proposed hybrid dual-fuel (MSW/natural gas) cycles feature attractive electrical efficiency improvements, leading to greenhouse gas emissions reduction. Cogeneration coupled with thermally driven cooling is a solution that holds promise for uniting enhanced sustainability with economic advantages. The system offers great opportunity for primary energy saving, increasing electrical yield and can significantly reduce CO2 emissions per unit of cooling as compared to compression chiller. The demonstration and simulation have also revealed that there is a potential with some modifications and improvements to employ decentralized thermally driven cooling in district heating networks even in temperate regions like Sweden. Thus, expanding cogeneration towards trigeneration can augment the energy supply for summer months in Europe and for year-round cooling in tropical locations. / QC 20110408

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are by-products emitted from combustion sources such as municipal solid waste (MSW) incineration plants. These organic compounds are recognized as toxic, bioaccumulative and persistent in the environment. PCDD/Fs are removed from flue gases before released from MSW incineration. However, the PCDD/Fs are not destroyed but retained in the residues, thus in the environment. Understanding the pathways that lead to their formation is important in order to develop ways to suppress their formation and prevent their release into the environment. Suppressing the formation can also allow less expensive air pollution control system to be used, and/or the costs of thermally treating the residues to be reduced. The main objective of the studies underlying this thesis was to elucidate process, combustion and fuel parameters that substantially affect the emission levels and formation of PCDD/Fs in flue gases from MSW incineration. The experiments were conducted under controllable, realistic combustion conditions using a laboratory-scale reactor combusting artificial MSW. The parameter found to most strongly reduce the PCDD/F emissions, was prolonging the flue gas residence time at a relatively high temperature (460°C). Increasing the sulfur dioxide (SO2) to hydrogen chloride (HCl) ratio to 1.6 in the flue gas was also found to reduce the PCDF levels, but not the PCDD levels. Fluctuations in the combustion process (carbon monoxide peaks), high chlorine levels in the waste (1.7%) and low temperatures in the secondary combustion zone (660°C) all tended to increase the emission levels. The PCDD/PCDF ratio in the flue gas was found to depend on the chlorine level in the waste, fluctuations in the combustion process and the SO2:HCl ratio in the flue gas. The formation pathways were found to be affected by the quench time profiles in the post-combustion zone, fluctuations in the combustion process and addition of sulfur. In addition, increased levels of chlorine in the waste increased the chlorination degrees of both PCDDs and PCDFs. A tendency for increased SO2 levels in the flue gas to increase levels of polychlorinated dibenzothiophenes (sulfur analogues of PCDFs) was also detected, however the increases were much less significant than the reduction in PCDF levels.

One of the most common ways to produce heat and electricity in Europe today is by the incineration of waste or combustion of coal. These materials can be very sulfurous and during combustion sulfur dioxide is produced. This is an environmental and health related toxic substance which is why power plants have strict regulations on removing it from the flue gas. Sulfur dioxide is removed from the flue gas by adding a limestone reagent. The sulfur dioxide reacts with the limestone and the synthetic product obtained is “Flue Gas Desulfurization gypsum”. This byproduct, from combustion, provides an environmentally friendly solution when used in building material such as plasterboards. The FGD gypsum that is being used in different types of building materials does not derive from waste incinerated power plants. We have more than 30 of these in Sweden and some of them get FGD gypsum as a byproduct. The purpose of this thesis was to find out whether a particular waste incineration plant in Sweden can reuse their gypsum waste instead of disposing it at landfill.

Non-conventional techniques for polymerization and depolymerization were investigated. The rates of polymerization were enhanced higher in ultrasonic, supercritical fluids and microwaves. However in these system under certain conditions, simultaneous degradation also occurred. Depolymerization was studied by various methods like thermal degradation in supercritical fluids and in presence of oxidizers, Lewis acid and other organic acids. Degradation by ultrasound and thermal degradation of polymer mixtures were also investigated. The scission of the polymer backbone is random for thermal degradation while the scission occurs at the midpoint for ultrasonic degradation. The degradation rates in all the investigated techniques were higher than the degradation rates observed for pyrolysis. Degradation was possible at low temperature (< 50°C) for oxidative and ultrasound degradation while the degradation rates were two orders of magnitude higher in supercritical conditions. The molecular weight distribution was obtained by GPC analysis and the continuous distribution models were used to obtain the rate coefficients. The activation energies were calculated from the temperature dependence of the rate coefficients.

Questa tesi ha come obiettivo quello di contribuire all'analisi empirica della struttura dei costi del ciclo dei rifiuti solidi urbani in un campione di 534 comuni italiani, per un periodo di sette anni, dal 2004 al 2010. Dopo una panoramica sia delle varie fasi del servizio RSU che del funzionamento del settore in Italia, nel primo capitolo, il secondo analizza la letteratura empirica delle funzioni di costo, con particolare attenzione per i lavori più recenti, tra cui anche i pochissimi italiani sul tema. L’argomento del terzo capitolo riguarda lo studio della presenza di economie di scala e di densità nel settore dei rifiuti utilizzando una specificazione translogaritmica per la funzione di costo stimata con il metodo SUR. L'ultimo capitolo si propone di fornire risposte a domande molto attuali come: la raccolta porta a porta è più costosa? E' meglio smaltire in discarica i rifiuti residui o bruciarli? Data una certa quantità di rifiuti da smaltire, esiste una quantità ottimale da incenerire? Inoltre, dato che molte comunità usano contemporaneamente diversi siti di smaltimento, qual è il numero ottimale di siti per portare i propri rifiuti indifferenziati? / This thesis aims to contribute to the empirical analysis of the cost structure of municipal solid waste management in a sample 534 Italian municipalities, for a period of seven years, from 2004 to 2010. After giving an overview both of the various phases of the MSW service and of the functioning of the sector in Italy in the first chapter, the second chapter reviews the cost function studies, with particular emphasis on recent years including also the very few Italian papers on the topic. This topic of the third chapter the study of the presence of scale and density economies in the Italian waste sector using a translogarithmic specification estimated with the SUR method. The last chapter aims to provide answers to very actual questions as: is the door to door collection more expensive? Is it better to burry residual waste or to incinerate it? Given a certain amount of garbage, is there an optimal quantity to be incinerated? Moreover, given that many communities use contemporaneously different dumpsites, which is the perfect number of disposal sites for unsorted waste?

The teeth are amongst the most resilient elements of the human skeleton and are thus often utilised in routine forensic investigation involving the identification of unknown remains. The teeth, however, also have other practical forensic applications. Teeth exposed to thermal stress have the potential to not only aid in identification but also in understanding the circumstances surrounding the fire. Previous investigations have drawn conclusions that if a fire flares up suddenly and intensively, the teeth burst and enamel is lost. If the blaze commences gently and burns slowly, then the first observable morphologic change is the colour. The teeth subsequently are difficult to handle, thus changes in teeth can indicate the history of exposure to thermal conditions. Children are twice as likely to become victims of house fire because of an inability to safely evacuate from areas of danger. The literature demonstrates, however, that research on the effects of incineration on teeth is mostly restricted to the permanent teeth. The apparent lack of knowledge on the effects of incineration on deciduous teeth thus necessitates further research in this area. This research project primarily aims at understanding the effect of extreme temperatures on deciduous teeth. It also aims to relate colour changes that occur post heating with fragility to aid in proper handling of samples in a forensic scenario and to determine the possibility of identifying incineration temperature based on tooth condition. The samples analysed composed of 90 deciduous teeth (45 molars and 45 anteriors) extracted as a part of clinical treatment were used for the study. The project involved exposing extracted deciduous teeth to temperatures ranging from 100°C to 1100°C for 30 minutes using a laboratory Gallenkamp oven. Unheated deciduous teeth were used as controls for the project. Post-incineration the teeth were then analysed under a stereomicroscope and SEM for morphological changes. A colorimetric analysis was also undertaken to evaluate the colour changes induced in the primary teeth due to the thermal stress. It was found that it was possible to identify the incineration temperature based on the tooth condition when the colour changes, stereomicroscopic findings and SEM images were utilised collectively. It was also concluded that the thermally induced changes observed in primary teeth occur at lower temperatures in comparison to the permanent teeth. It was also established that post-incineration deciduous teeth are fragile and show a tendency to fragment after minimal exposure to thermal stress as compared to the permanent teeth. Moreover enamel and dentin remained identifiable in primary teeth even after exposure to 1100°C for 30 minutes while cementum lost its structural morphology at 900°C.

Το πρόβληµα της διαχείρισης των ιατρικών αποβλήτων και ιδιαίτερα αυτών που χαρακτηρίζονται ως επικίνδυνα έχει οξυνθεί τα τελευταία χρόνια στην Ελλάδα. Το 10-25% των παραγόμενων ιατρικών αποβλήτων στις υγειονομικές μονάδες, θεωρούνται επικίνδυνα, με δυνατότητα πρόκλησης μίας σειράς κινδύνων για την υγεία, σε περίπτωση επαφής ή έκθεσης σε αυτά, διότι αποτελούν στις περισσότερες των περιπτώσεων φορείς παθογόνων µικροοργανισµών µε αποτέλεσµα η µη ασφαλής διάθεσή τους να εγκυμονεί σηµαντικότατους κινδύνους, όχι µόνο για το περιβάλλον, αλλά και για τη δηµόσια υγεία. Αντικείμενο της παρούσας εργασίας αποτελεί η μελέτη και η αξιολόγηση μεθόδων επεξεργασίας των επικίνδυνων ιατρικών απορριμμάτων. Ο όρος αξιολόγηση αναφέρεται στην διαδικασία επιλογής της κατάλληλης τεχνολογίας επεξεργασίας, λαμβάνοντας υπόψιν πληθώρα παραγόντων. Οι πιο διαδεδομένες μέθοδοι που θα εξεταστούν, είναι η αποτέφρωση, η αποστείρωση, η απολύμανση με μικροκύματα και η χημική απολύμανση. Σκοπός της εργασίας είναι να καταστήσει σαφές το ότι καμία μέθοδος δεν αποτελεί πανάκεια. Αντιθέτως, πρέπει να γίνεται προσεκτική επιλογή της μεθόδου, πάντα με σεβασμό στην υγεία και το περιβάλλον. / The problem of medical waste management, and especially of that which is characterized as hazardous, has increased in Greece during the last years. Hazardous medical waste is 10-25% of the total quantity of medical waste that is produced in health units. In most cases, this type of medical waste is carrier of pathogenic microorganisms. Thus, its ineffective way of disposal puts in danger the environment and the public health. This thesis is an assessment of different technologies that can manage hazardous medical waste. The term assessment refers to the choice of the appropriate technology, taking into account many different factors. The most widely used methods are incineration, sterilization, disinfection with microwave irradiation and chemical disinfection. Aim of this thesis is to make clear that there is not any technology that is really effective with all types of hazardous medical waste. Thus, we have to carefully choose the appropriate technology, always with respect to health and the environment.