Orientador: Solange Cadore / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-10T02:39:07Z (GMT). No. of bitstreams: 1 Paes_LorenaCristine_M.pdf: 387202 bytes, checksum: 46a0d9c60b50d24a3a34de8a99f50153 (MD5) Previous issue date: 2007 / Resumo: Visando o desenvolvimento de um método analítico para uma matriz heterogênea de interesse comercial e ambiental e, também, a fim de acrescentar novas informações sobre o mel nacional, este trabalho avaliou diferentes estratégias de tratamento do mel, diferentes modificadores químicos e otimizou os parâmetros instrumentais para a determinação de cobre, manganês e cádmio, por Espectrometria de Absorção Atômica com Forno de Grafite. O tratamento do mel com banho de ultrasom foi o procedimento mais adequado para o preparo da amostra, quando comparado às mineralizações em forno de microondas e em placa de aquecimento, bem como à solubilização com hidróxido de tetrametilamônio, devido à simplicidade e rapidez. Foi necessário o uso de peróxido de hidrogênio como modificador químico para aumentar a eficiência da eliminação da matriz nas determinações dos analitos de interesse, além do uso de 10 µg de Mg(NO3)2 como modificador químico para determinação de Mn e de 5µg de NH4H2PO4 como modificador químico para determinação de Cd. Os métodos otimizados apresentaram precisão, sensibilidade e repetibilidade adequadas e foram obtidas recuperações entre 70 e 90 %, o que indica uma exatidão satisfatória. As quantidades dos analitos nos méis brasileiros de diferentes procedências variaram entre 0,020 e 0,17 µg g de Cu, entre 0,39 e 11,9 µg g de Mn e foram menores que 6 ng g no caso do Cd. Observou-se que as amostras analisadas não são contaminadas com Cd e as altas concentrações de Mn confirmam que o mel brasileiro pode ser considerado uma boa fonte nutritiva deste elemento / Abstract: Different strategies for sample preparation, the optimization of instrumental parameters and the evaluation of different chemical modifiers for the determination of cadmium, copper and manganese in honey by graphite furnace atomic absorption spectrometry were developed. Honey is a heterogeneous matrix, which has great commercial and environmental importance. However, few studies concerning its mineral content have been carried out in Brazil. In this work the use of an ultra sonic bath was compared with digestion by microwave radiation or on a hot plate as well as solubilization with tetramethylammonium hydroxide. The best procedure for honey is that using ultrasound, considering its simplicity and speed of analysis. Hydrogen peroxide was used as chemical modifier together with 10 µg Mg(NO3)2 or 5 µg de NH4H2PO4 for the determination of Mn or copper, respectively. Satisfactory precision, sensitivity and accuracy as well as recoveries in the range of 70-90 % were obtained. Analyte concentrations in Brazilian honey, from different regions, varied between 0.020 to 0.17 µg g for Cu, and 0.3 to 11.9 for Mn. For Cd, values below 6 ng g were found. Brazilian honeys were not contaminated with Cd and may be considered a good source of manganese / Mestrado / Quimica Analitica / Mestre em Química

Made available in DSpace on 2014-06-12T23:15:38Z (GMT). No. of bitstreams: 2 arquivo9238_1.pdf: 2366208 bytes, checksum: ed56433ca9af86bbf10ef26163fc1d28 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2007 / O desenvolvimento de analisadores em fluxo e o monitoramento contínuo de alguns processos químicos levaram ao surgimento de sistemas cada vez mais baratos e simplificados com potencial para miniaturização. Para estes propósitos, o uso de sistemas em fluxo pode ser uma atraente alternativa. Dentre estes sistemas, os analisadores fluxo-batelada (FBA) foram aplicados com sucesso na implementação de vários procedimentos analíticos, como: titulações, prétratamento de amostras, adição de analito e análises screening . Apesar de suas características favoráveis, os analisadores FBA previamente propostos usam bombas peristálticas na propulsão dos fluidos. O uso destas bombas pode elevar os custos do analisador e tornar inviável sua miniaturização devido às grandes dimensões dos modelos mais vendidos no mercado. Para superar estes inconvenientes, é proposto neste trabalho um analisador de baixo custo, compacto e com propulsão pneumática de fluidos. Este sistema faz uso de uma bomba-pistão labmade provida de um motor de passo conectado mecanicamente a um pistão metálico e controlada por microcomputador, acoplada a uma câmara de mistura adaptada. O analisador proposto foi aplicado na preparação automática de soluções de calibração para determinação de manganês em águas minerais por espectrometria de absorção atômica em forno de grafite (GF AAS). Para fins de comparação, foram preparados dois conjuntos de soluções de calibração, de forma manual e automática (cinco para cada método de preparação), para a construção das curvas de calibração. Não foram observadas diferenças estatísticas significativas entre os resultados obtidos com a aplicação de um teste estatístico (tstudent) para um nível de confiança de 95%. Os desvios-padrão dos procedimentos manual e automático foram sempre menores ou iguais a 0,1 μg·L-1, com capacidade de processar até 80 soluções de calibração por hora. Depois de verificada sua viabilidade de uso, o analisador foi aplicado também na análise de amostras de gasolina usando microemulsões no pré-tratamento desta amostra para determinação de cobre também por GF AAS. Após a realização de estudos e ensaios acerca das microemulsões desenvolvidas para este trabalho, e da otimização dos parâmetros operacionais do analisador, foram realizadas as análises das amostras de gasolina pré-tratadas automaticamente. Mesmo com os problemas apresentados na análise das microemulsões preparadas de forma automática, foi verificada a aplicabilidade do analisador desenvolvido para preparação de soluções de calibração e preparação de microemulsões em linha, com versatilidade, simplicidade, robustez, flexibilidade, sem a pulsação característica do bombeamento peristáltico e custos operacionais baixos foi demonstrada. Além disso, este sistema pode ser também utilizado em análises in situ, pois, devido a suas pequenas dimensões, pode se tornar portátil depois de simples adaptações

This PhD thesis is concerned with the influence of sustainable design in further education (FE) college buildings on whole institutional change for sustainability. The research focuses on the first decade of the 21st century in England and Wales when increasing engagement with the sustainability agenda in the FE sector included linking sustainability criteria to the funds for new building projects. The original contribution of the thesis is twofold. Firstly, it reveals the extent to which these new buildings contributed to institutional change for sustainability in the FE sector and identifies ways to maximise future sustainable building projects as a resource for institutional change. Although there was substantial investment in new buildings and a growing interest in sustainability during the period of the study, no evidence exists of research into the links between sustainable design and institutional change in the FE sector. Secondly, the thesis develops an original research approach, contributing to the multi-disciplinary field of research into sustainability and sustainable development. The thesis adopts a biographical approach from social science research and adapts it to produce narrative accounts of the development of two buildings with recognised sustainability qualities, one in England and one in Wales. These biographies are then analysed for evidence of institutional change for sustainability using the systems perspective that underpins the view of sustainability presented in the thesis. The thesis establishes two frameworks, one for recognising sustainable design within FE college buildings and one for identifying change for sustainability in FE institutions. The biographies of the buildings were developed using data collected by biographical research methods and the focus of the analyses is on the relationships that existed around each building’s development and its physical presence on campus. The thesis reveals that even colleges with a reputation for sustainability have not fully exploited the introduction of a sustainably designed building onto a campus as a catalyst for institutional change. The outcomes from the research offer key points for maximising the influence of future building projects in terms of achieving institutional change for sustainability and identify areas for further research into the influence of sustainable design on institutions in the FE and other education sectors. The development of the research approach in this thesis presents an alternative for researching sustainability in education and other fields.

Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Three analytical methods were developed for the determination of chlorine, iodine and mercury in solid and liquid samples, directly by high resolution continuum source atomic and molecular absorption spectrometry in graphite furnace. The first method objected the determination of chlorine in solid and slurry samples of different natures and chlorine contents (CRM 81002b human hair, SRM 1568b rice flour, ERM EC681 polyethylene, CRM BCR 460 coal, SRM 2692c bituminous coal, SRM 1575 sheet Of pine, CRM 686-1 iron oxide, SRM 1549 powdered milk) through the molecular formation of CaCl. The results were compared with those already available for the SrCl molecule and were superior, especially in samples with a high calcium content. The limit of detection and quantification obtained for the two molecular absorption lines of CaCl were 2.6 and 8.7 ng (620.862 nm) and 14.2 and 61.6 ng (377.501 nm), respectively. The iodine determination was performed through the formation of the SrI molecule in two samples of medicines containing iodine. The accuracy of the method was proved by comparative analysis by inductively coupled plasma mass spectrometry. The results obtained were higher compared to the existing BaI molecule that does not provide direct determination in solids. The limit of detection and quantification obtained were 0.035 and 0.117 μg, respectively. Finally, an analytical method for the determination of mercury in blood samples (SERONORM® LEVEL III and II) and urine (SERONORM®, Clincheck Control level I and II batch 432 and level II batch 923) were developed, directly, using gold nanoparticles. The method was compared to the existing method that uses potassium permanganate as oxidizing agent. The limit of detection and quantification obtained were 0.057 and 0.190 ng, respectively. / Foram desenvolvidos três métodos analíticos para a determinação de cloro, iodo e mercúrio em amostras sólidas e líquidas, de forma direta por espectrometria de absorção atômica e molecular de alta resolução com fonte contínua em forno de grafite. O primeiro método objetivou a determinação de cloro em amostras sólidas e em suspensão de diferentes naturezas e teores de cloro (CRM 81002b cabelo humano, SRM 1568b farinha de arroz, ERM EC681 polietileno, CRM BCR 460 carvão, SRM 2692c carvão betuminoso, SRM 1575 folha de pinheiro, CRM 686-1 óxido de ferro, SEM 1549 leite em pó), através da formação molecular de CaCl. Os resultados foram comparados com os já existentes para a molécula de SrCl e mostraram-se superiores, especialmente em amostras com alto teor de cálcio. O limite de detecção e quantificação obtidos para as duas linhas de absorção molecular de CaCl foram de 2,6 e 8,7 ng (620,862 nm) e 14,2 e 61,6 ng (377,501 nm), respectivamente. Já a determinação de iodo realizou-se através da formação da molécula de SrI, em duas amostras de medicamentos contendo iodo. A exatidão do método foi comprovada através de analise comparativa por espectrometria de massas com plasma acoplado indutivamente. Os resultados obtidos se mostraram superiores em comparação com molécula já existente BaI que não proporciona a determinação direta em sólidos. O limite de detecção e quantificação obtidos foram de 0,035 e 0,117 μg, respectivamente. Por fim, foi desenvolvido um método analítico para a determinação de mercúrio em amostras de sangue (SERONORM® LEVEL III e II) e urina (SERONORM®, Clincheck Control nível I e II lote 432 e nível II lote 923) certificadas, de forma direta, utilizando nanopartículas de ouro. O método foi comparado ao método já existente que utiliza permanganato de potássio como agente oxidante. O limite de detecção e quantificação obtidos foram de 0,057 e 0,190 ng, respectivamente.

Infectious diseases are a major public health burden causing millions of deaths every year. Government authorities need to be able to monitor disease incidence and evaluate their interventions for disease control. Monitoring the status of infectious diseases is one of the most challenging problems facing the public health sector, and epidemiological surveillance systems for infectious diseases, particularly notifiable diseases are essential. Despite initiatives to encourage reporting of infectious diseases, underreporting and poor surveillance are on-going challenges for many developing countries. Most surveillance systems in these settings use traditional paper-based methods, which are both inefficient and impractical. There is a need for alternative tools to strengthen infectious disease surveillance systems in resource-limited settings. The remarkable progress made in mobile computing technology has the potential to improve infectious disease surveillance systems. However, user experience in digital technologies and infrastructure needs to be given greater attention. My study investigated the use of mobile phone devices as surveillance tools in health information systems. A mobile phone-based surveillance system was developed and applied in Tanzania as an alternative approach to traditional paper-based systems. Using this system different factors that affect the usability of mobile phone-based systems were investigated, by examining the quality of surveillance data in the context of completeness, timeliness and costs. After two years of operation in twenty-eight districts in southern Tanzania, numerous factors were identified that affect user accuracy and speed of use of the mobile phone-based surveillance. These include user experience in digital technology, particularly mobile device ownership; digital technology literacy, such as access and use of SMS and user’s age. The mobile phone-based surveillance system was more accurate compared to the traditional paper-based system with greater data reporting, more complete data and timelier reporting. Initially the mobile phone-based surveillance system required more capital investment, although the running costs of paper-based surveillance were greater. The utility of the mobile phone-based surveillance in monitoring and evaluating large-scale rabies control interventions was examined and the data produced was used to analyse the impacts of interventions on reducing disease incidence. Significant relationships were detected between the incidence of reported bite injuries in the focal district the previous month and in neighbouring districts that month, with more injuries detected in mainland Tanzania than on the island of Pemba. The relationship between bite injuries and vaccination coverage was complicated, with some evidence that vaccination reduced bite incidence. However, more data and a better model are needed to fully understand the impact of vaccination on bite incidence. The system provided timely information on the implementation of control measures and incidence of bite injuries, vital for improving control efforts. Use of automated short text messages (SMS) as part of the mobile phone-based surveillance was assessed to determine whether they could improve patient’s adherence to treatment regimens. Patients who received SMS reminders had significantly better compliance than those who did not, with attendance improved by at least 10%. Use of SMS reminders has the potential to improve patients’ compliance in other treatment regimens that require repeat clinic visits or administration of medicines. This thesis documented how the use of mobile phone devices can be used to improve surveillance in resource-limited settings. The use of effective integrated surveillance system could empower major stakeholders concerned with public health problems by providing them with appropriate real-time information on disease incidence and control interventions. In the final chapter the challenges encountered and insights gained in the application of mobile computing in strengthening infectious diseases surveillance are discussed. Despite infrastructural challenges such as unreliable power and Internet, mobile computing technologies can improve patient care and authorities can be prompted in a timely manner about infectious disease outbreaks and of supply shortages. In conclusion, innovative tools that can strengthen and integrate human and animal surveillance can improve the control and prevention of infectious diseases. Mobile phones have great potential for this, and can be used to strengthen health information systems.

Fuels: Non-renewable fossil fuels are the largest man-made contributor to global warming. Biofuel market share will increase, promoted by renewability, inherent lower net CO\(_2\) emissions, and legislation. The environmental and human health impact of diesel exhaust emission particulate matter (PM) is a major concern. Fossil diesel PM aftertreatment systems exist. Near future fuel PM research and the evaluation of current aftertreatment technology, highlight a route for future development. Using a holistic approach this body of work studies the interdependence between the fuel, the CI engine and associated aftertreatment system. The overall objective of this thesis is the evaluation of current diesel aftertreatment using renewable near future fuels. Diesel blends with 1st and 2nd generation biodiesel fuels are viable. Carefully selected blends like B20G10 can make all round regulated emission improvements. Green additive dimethyl carbonate (DMC) enhances diesel combustion by oxygenation. Regulated emissions of THC, CO (>30% reduced) and PM (50% reduced) for 2% DMC in diesel. 1st generation biodiesel (RME) is widely available. Combustion produces significantly less solid PM than diesel (<50%) and slightly more liquid PM. RME produces less particulate at nearly all particle sizes, but more of the small nano sized liquid SOF. The potentially negative health effect of nano-sized SOF material raises questions. There is a case for more research into the health effects of nano-sized SOF material. Oxygenated fuel combustion PM contains more voids (facilitates DPF oxidation), plus unregulated carcinogenic compounds are reduced. ii Aftertreatment: The efficiency of the oxidation catalyst for the near future fuels was comparable to diesel and PM matter at all particulate sizes is reduced for all near future fuels tested. Aftertreatment total PM filtration levels are >90% by mass >98% by number, for all fuels. For synthetically produced 2nd generation gas to liquid (GTL) fuels there are potentially DPF regeneration implications. Current aftertreatment solutions are as effective for bio alternatives as they are for fossil diesel. Biodiesels, green additives and aftertreatment are effective clean emissions improvements, until the promise of true zero emission vehicles is realised.

Beyond the half-lives, Exclusions Zones, and official imaginaries of nuclear risk, exists an informal geography of Chernobyl. This thesis explores what it is like to live with nuclear disaster. It reveals how people have developed informal coping tactics and local risk understandings that defy formal constructions of nuclear space, and help resist de facto state abandonment. This project involved in-depth ethnographic research with marginalised communities who live in the contaminated landscapes around the Chernobyl Exclusion Zone in Ukraine. Qualitative approaches including participant observation, photographic methods and semi-structured interviews were conducted with participants including liquidators (cleanup workers), border guards, evacuees, returnees, ‘Chernobyl widows’, farmers and many other people impacted by the disaster’s contested nuclear geography. The thesis reveals how Chernobyl’s constructed landscape is produced through a negotiated process of ‘nuclearity’ (Hecht 2012). The research posits that alongside formal spatialisations of Chernobyl – such as its ‘Exclusion Zones’ - are a spectrum of unofficial understandings of space and risk that contest this top-down and ‘strategic’ geography of nuclear disaster (de Certeau 1984). It demonstrates that these alternative nuclear understandings help people assert agency and oppose the status of post-atomic ‘bare life’ (Agamben 1998). Utilising theorisations of power and resistance offered by de Certeau (1984), the thesis uncovers the hidden geography of informality, local knowledge and place attachment that allow people to resist the ‘stealthy violence’ (Li 2009, 67) of abandonment and perform their own alternative narratives of nuclear space. This thesis contributes to discussions of Agamben within geographical discourses, and advances understandings of informality in the context of post-socialist marginalisation and landscapes of risk.

O consumo de fórmulas infantis no Brasil, utilizadas como substituto do leite materno, tem aumentado nos últimos anos de forma significativa. Tal fato é uma preocupação para os órgãos de saúde pois, o aleitamento materno exclusivo até no mínimo 6 meses, deixou de fazer parte de nutrição da maioria dos lactentes. Os produtos utilizados como substituto do leite materno contêm quantidades suficientes de vitaminas e nutrientes que ajudam no desenvolvimento normal do organismo dos lactentes. Entretanto, além de elementos essenciais, podem conter elementos potencialmente tóxicos presentes na matéria prima ou oriundos das etapas de processamento e armazenamento das mesmas. No presente trabalho foram desenvolvidos métodos analítico para determinar a presença de elementos potencialmente tóxicos (As, Cd, Pb e Tl) e essenciais (Cu e Mn) em fórmulas infantis, utilizando espectrometria de absorção atômica de alta resolução com fonte contínua e forno de grafite e análise direta de sólidos. As amostras utilizadas neste trabalho foram obtidas nos mercados da cidade de Porto Alegre, RS, Brasil, todas na forma sólida (pó) com diferentes composições e matéria prima (arroz, aveia, soja e leite). As curvas de calibração foram realizadas com soluções padrão aquosas e os métodos otimizados foram aplicados nas amostras em estudo. Em todas as amostras os elementos As, Cd, Pb e Tl apresentaram valores de concentração abaixo do limite de detecção. Das seis amostras analisadas, três apresentaram valores de concentração de Cu abaixo dos parâmetros mínimos estabelecidos pela legislação brasileira, enquanto que para o Mn todas amostras apresentaram valores de concentração dentro dos parâmetros mínimos da legislação brasileira. Os métodos desenvolvidos foram simples, exatos e precisos, podendo ser utilizados para análise de rotina. / The consumption of infant formula in Brazil, as a replacement of breast milk, has lately increased significantly. It is a major concern for health agencies because the exclusive breastfeeding up to at least 6 months is no longer part of most infants. The products used as a substitute of the breast milk contain sufficient amounts of vitamins and nutrients, which helps in the normal development of the infants. However, besides the essential elements, it may contain potentially toxic elements present in raw material or from of the processing and storage stages of the same. In the present work the presence of the essential (Cu e Mn) and potentially toxic elements (As, Cd, Pb e Tl) in infant formulas were evaluated. For this, analytical methods were developed for the determination of As, Cd, Cu, Mn, Pb and Tl using high-resolution continnum source graphite furnace atomic absorption spectrometry and direct solid sampling analysis in infant formulas. The samples were acquired in Porto Alegre’s market, RS, Brazil, all in powder form with different compositions and raw materials (rice, oats, soy and bovine milk). The calibration curves were performed with aqueous standard solutions and the optimized methods were applied in the study samples. In all samples, the concentration values of As, Pb, Cd and Tl were below of the limit of detection. For the analyzed samples, three of them present the concentration values of Cu lower than the minimum parameters established by Brazilian legislation, while for Mn, all samples present the concentration values within the minimum parameters of Brazilian legislation. The developed methods for the determination of these elements in infant formulas were simple, exacts and precise, and can be applicated for the routine analysis.

This thesis will explore the agentive roles of material culture in ancient colonial encounters. It takes as a case study the Roman colonization of southern Britain, from the first century BC onwards. Using ethnographic and theoretical perspectives largely drawn from social anthropology, it seeks to demonstrate that the consumption of certain types of continental material culture by some members of communities in southern Britain, pre-disposed the local population to Roman political annexation in the later part of the first century AD. Once the Roman colonial project proper commenced, different material cultures were introduced by colonial agents to maintain domination over a subaltern population. Throughout, the entanglement of people and things represented a reciprocal continuum, in which things moved people's minds, as much as people got to grips with particular things. In addition it will be suggested that the confrontations of material culture brought about by the colonial encounters affected the colonizer as much as the colonized. The thesis will demonstrate the impact of a variety of novel material cultures by focusing in detail on a key area of southern Britain – Chichester and its immediate environs. Material culture will be examined in four major categories: Landscapes and Buildings; Exchange, Food and Drink; Coinages; Death and Burial. Chapters dealing with these categories will be preceded by an opening chapter on the nature of Roman colonialism, followed by an introductory one on the history and archaeology of southern Britain and the study area. The Conclusion will include some thoughts on the integration of anthropological approaches to archaeological interpretation. I intend that the thesis provides a contribution to the wider debate on the role of material culture in ancient colonial projects, and an example of the increasingly productive bidirectional entanglement of archaeology and anthropology.

Neste trabalho dois métodos de preparo de amostras para decomposição de bio-diesel foram avaliados para a posterior determinação de Cu e Ni por espectrometria de absorção atômica com forno de grafite (GF AAS). O primeiro método consistiu na de-composição ácida assistida por radiação micro-ondas em sistema fechado (MW-AD), que foi realizada com adição de HNO3 7 mol L-1 e 2 mL de H2O2 30% (m/m). O segun-do método de pré-tratamento avaliado foi a decomposição por via seca em forno mufla com programa de aquecimento até a temperatura máxima de 450 °C. O sólido resultante foi dissolvido em HNO3 1% (v/v). As temperaturas de pirólise e atomização para a téc-nica de GF AAS foram, respectivamente, 1000 ºC e 2000 ºC para Cu, e 1100 °C e 2300 °C para Ni. Os limites de detecção (LD) para Cu e Ni foram de 12,4 e 3,8 ng g-1 empre-gando o método de decomposição MW-AD. Enquanto que, para o método de decompo-sição por via seca os LD foram de 2,8 e 8,3 ng g-1 para Cu e Ni, respectivamente. A avaliação da exatidão foi efetuada a partir do ensaio de recuperação após adição de ana-lito ao biodiesel. As recuperações foram de 91 e 86% para o método MW-AD para Cu e Ni, respectivamente. Foram observadas perdas por volatilização com o emprego do mé-todo de via seca para Cu, com isso, a recuperação foi no máximo de 73%. / In this work, two methods for biodiesel digestion for determination of Cu and Ni by graphite furnace atomic absorption spectrometry (GF AAS) were evaluated. The microwave-assisted acid digestion (MW-AD) with the addition of 7 mol L-1 of HNO3 and 2 mL of H2O2 30% (m/m) was applied to biodiesel digestion. In addition, a dry ash method was applied to biodiesel digestion using a maximum temperature of 450 ºC. The inorganic residues were dissolved by addition of 1% (v/v) nitric acid. The optimiza-tion of temperature program was performed in the GF AAS for Cu and Ni using a sam-ple with standard addition. The pyrolysis and atomization temperatures were, respec-tively, 1000 ° C and 2000 ° C for Cu and 1100 ° C and 2300 °C for Ni. The limits of detection for Cu and Ni were 12,4 and 3,8 ng g-1, respectively, using a MW-AD meth-od. Using a dry ash method the limits of detection were 2,8 and 8,3 for Cu and Ni, re-spectively. The recoveries for Cu and Ni after MW-AD method were 91 and 86%, re-spectively. Using the dry ash method the recovery was 73% for Cu due to sample vo-latilization losses.