Rozprawy doktorskie na temat „PCDFs”

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Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES
Law No. 8213/91, known as the Quota Law was formulated as a tool to implement the National Policy on Employment Dues for Persons with Disabilities. This law today is one of the main means for the insertion of PCDs (Persons with Disabilities) into the labor market. However, the implementation of this law occurs in the face of some difficulties, such as accessibility, for example, in addition to prejudice regarding PCDs in the social environment, which ultimately interferes with its effectiveness. The purpose of this paper is to understand the meanings attributed to the Quota Law by HR Managers who act or have acted in organizations that apply the Quota Law. In order to achieve this goal, nine interviews were conducted, of which eight interviews were conducted with managers, some of whom were in full exercise until the date of the interview, and others who had recently left the organization in which they performed HR functions, and was also interviewed the coordinator of the State Nucleus for Assistance to the Disabled (NEAD). Besides the interviews, this work made use of the technique of observation and the analysis of the collected material occurred through the Nuclei of Meaning. The results show that the managers interviewed still perceive the Quota Law as a merely punitive Law, however, they understand the Quota Law also, as an important one, if not unique, tool for the insertion of PCDs into the labor market. With this, it can be said that the meanings that managers attribute to the Quota Law are loaded with prejudice and the way the Quota Law is signified by these managers reflects in the way they execute this Law, and it can be affirmed that the issue is cultural.
A lei n? 8213/91, conhecida como Lei de Cotas foi formulada como ferramenta para implementar a Pol?tica Nacional de Cotas Empregat?cias para Portadores de Defici?ncia. Esta lei hoje ? um dos principais meios para a inser??o das PCDs (Pessoas com Defici?ncia) no mercado de trabalho. Contudo, a implementa??o desta lei ocorre diante de algumas dificuldades, como a acessibilidade, por exemplo, al?m do preconceito no que tange ?s PCDs no meio social, o que acaba interferindo na efetividade da mesma. Este trabalho tem como objetivo, compreender os sentidos atribu?dos ? Lei de Cotas pelos Gestores de RH que atuam, ou atuaram, em organiza??es que se aplica a Lei de Cotas. Para atingir este objetivo foram realizadas nove entrevistas, sendo oito entrevistas realizadas com gestores, dos quais alguns estavam em pleno exerc?cio da fun??o at? a data da entrevista e outros que haviam sa?do recentemente da organiza??o em que exercia a fun??o de gestor de RH, e ainda, foi entrevistada a coordenadora do N?cleo Estadual de Atendimento ao Deficiente (NEAD). Al?m das entrevistas este trabalho fez uso da t?cnica de observa??o e a an?lise do material levantado ocorreu por meio dos N?cleos de Significa??o. Os resultados mostram que os gestores entrevistados ainda percebem a Lei de Cotas como uma Lei meramente punitiva, entretanto, entendem a Lei de Cotas tamb?m, como uma importante, sen?o ?nica, ferramenta para a inser??o das PCDs no mercado de trabalho. Com isso, pode-se afirmar que os sentidos que os gestores atribuem a Lei de Cotas s?o carregados de preconceito e a forma como a Lei de Cotas ? significada por esses gestores reflete na forma como executam essa Lei, e ainda, pode-se afirmar que a quest?o ? cultural

The United States leads the world in per capita production of Municipal Solid Waste (MSW), generating approximately 200 million tons per year. By 2000 A.D. the US EPA predicts a 20% rise in these numbers. Currently the major strategies of MSW disposal are (i) landfill and (ii) incineration. The amount of landfill space in the US is on a rapid decline. There are -10,000 landfill sites in the country, of which only 65-70% are still in use. The Office of Technology Assessment (OTA) predicts an 80% landfill closure rate in the next 20 years. The development of a viable energy resource from MSW, in the form of densified Refuse Derived Fuel (dRDF), provides solutions to the problems of MSW generation and fossil fuel depletions. Every 2 tons of MSW yields approximately 1 ton of dRDF. Each ton of dRDF has an energy equivalent of more than two barrels of oil. At current production rates the US is "throwing away" over 200,000,000 barrels of oil a year. In order to be considered a truly viable product dRDF must be extensively studied; in terms of it's cost of production, it's combustion properties, and it's potential for environmental pollution. In 1987 a research team from the University of North Texas, in conjunction with the US DOE and Argonne National Laboratory (ANL), cofired over 550 tons of dRDF and bdRDF with a high sulfur Kentucky coal in a boiler at ANL. This work examines the emission rates of polychlorinated dioxins (PCDDs) and furans (PCDFs) during the combustion of the dRDF, bdRDF, and coal. Even at levels of 50% by Btu content of dRDF in the fuel feedstock, emission rates of PCDDs and PCDFs were below detection limits. The dRDF is shown to be an environmentally acceptable product, which could help resolve one of the major social and environmental problems facing this country today.

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Apesar do relativo avanço no sentido de manter a igualdade entre os cidadãos, a sociedade brasileira ainda não atende às necessidades específicas de alguns grupos, como: idosos, enfermos, crianças, gestantes e pessoas com deficiência (PcDs). Porém, no caso das PcDs, atualmente existem leis que visam incluí-las no mercado de trabalho, o que vem contribuindo para a sua contratação. Este trabalho objetivou investigar os principais desafios encontrados no processo de capacitação de PcDs pertencentes ao quadro efetivo do Centro Federal de Educação Tecnológica Celso Suckow da Fonseca (Cefet-RJ), que é uma instituição pública destinada ao ambiente educacional com formação humana, científica e tecnológica. Foi realizada uma pesquisa bibliográfica a partir dos conceitos-chave que auxiliaram na identificação de publicações da temática estudada. A metodologia utilizada foi o estudo de caso com aplicação de questionários, os quais foram respondidos por grupos de funcionários com deficiência, de seus gestores, e também do setor de capacitação, sendo todos servidores públicos pertencentes ao quadro de profissionais do Cefet-RJ. O tratamento dos dados foi realizado através da análise de conteúdo. O trabalho de campo mostrou o envolvimento do profissional PcD com a instituição. Os objetivos almejados nesta pesquisa foram atingidos e direcionados para propostas de melhorias nos processos de inserção, contratação e adaptação das PcDs em seu ambiente de trabalho.
Despite relative efforts in order to sustain citizen equality, Brazilian society still remains inattentive to some groups’ especial needs, such as the elderly, children, pregnant, sick and people with disability (PwD). However, concerning the PwDs, a current legislation aiming to insert them in the labor market actually exists and have been contributing to their hiring. This paper focused on the main challenges found during the PwDs capacitation process in the Centro Federal de Educação Tecnológica Celso Suckow da Fonseca (Cefet-RJ) full-time staff. Cefet-RJ is a public institution destined to be an education environment for human, scientific and technological formation. From key concepts that helped identify publications for this studied theme, a bibliographical research was achieved. We used the case study methodology, in addition of questionnaires, answered by groups of employees with disability, their managers and also by the resource and training center. All questioned employees are from Cefet’s full-time staff. The data handling was done by analyzing the content. The fieldwork showed PwDs’ involvement with the Institution. The targets were achieved and the results directed as improvement proposals for insertion, hiring and adaptation processes in the working environment.

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Planaltina , Programa de Pós-Graduação em Ciências Ambientais, 2018.
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Estatísticas criminais constituem parte importante da atividade policial. A adoção de ferramentas mais adequadas a cada conjunto de dados pode fornecer informações úteis para a ação da polícia na sua função de apuração das infrações penais. Danos e problemas ambientais específicos são construídos através de processos sociais complexos, constituídos por uma combinação de fatores materiais e sociais. Diferentes escritores da criminologia verde, ramo que foca questões referentes a danos, transgressões e crimes ambientais, defendem uma abordagem mais conceitual, no sentido de alocar os debates em torno da interligação entre questões sociais e ambientais. Este trabalho tem como objetivos: i) Avaliar o cenário temporal e espacial dos registros de crimes ambientais entre os anos de 2009 e 2016; ii) verificar a influência das variáveis socioeconômicas sobre os registros de crimes ambientais, determinando se as teorias da criminologia tradicional se aplicam aos crimes ambientais estudados neste trabalho. Foi possível identificar uma desproporção entre o número de registros de tipos penais, explicada pela vasta presença de Unidades de Conservação no território do DF e pelos altos índices de infraestrutura sanitária e reduzido parque industrial. Há associações consistentes entre alguns tipos penais definidos na Lei de Crimes Ambientais (Lei no 9.605/1998) e algumas Regiões Administrativas (RA) do Distrito Federal e certas delegacias de polícia, explicadas pelas singularidades de cada área. Os registros de crimes ambientais ocorrem principalmente nas áreas urbanas. Homogeneidades e particularidades no uso do solo aparecem como fatores influenciadores na distribuição espacial. A frequente relação com as variáveis relacionadas à migração sugere uma possível aplicação da teoria da desorganização social aos crimes ambientais, refletindo a incapacidade da comunidade em se organizar em prol do controle comunitário.
Criminal statistics are an important part of police activity. The adoption of more appropriate tools for each set of data can provide useful information for police investigation of criminal offenses. Specific environmental damage and problems are built through complex social processes, made up of a combination of material and social factors. Different writers of green criminology, a branch that focuses on issues related to damages, transgressions and environmental crimes, advocate a more conceptual approach, in order to allocate debates around the interconnection between social and environmental issues. This study aims to: i) Evaluate the temporal and spatial scenario of environmental crime records between 2009 and 2016; ii) to verify the influence of the socioeconomic variables on the records of environmental crimes, determining if the theories of traditional criminology apply to the environmental crimes studied in this work. It was possible to identify a disproportion between the number of records of criminal types, explained by the vast presence of Conservation Units in the territory of the Federal District and by the high rates of sanitary infrastructure and reduced industrial park. There are consistent associations between some criminal types defined in the Environmental Crimes Law (Law 9605/1998) and some Administrative Regions (RA) of the Federal District and certain police stations, explained by the singularities of each area. Records of environmental crimes occur mainly in urban areas. Homogeneities and particularities in soil use appear as influencing factors in the spatial distribution. The frequent relationship with the variables related to migration suggests a possible application of the theory of social disorganization to environmental crimes, reflecting the inability of the community to organize in favor of community control.

POPs are a group of chemicals that have been extensively studied over the last few years. The main reason that these chemicals have received so much scientific attention is the myriad of negative effects they have on the environment and human health. The properties that cause the deleterious effects include a high molecular stability, rendering them highly persistent. Added to this is the lipophilic and hydrophobic nature of the compounds. POPs will thus tend to bio-accumulate and bio-magnify in the environment, causing a direct threat to humans and wildlife. To address this threat, the Stockholm Convention on Persistent Organic Pollutants, under the supervision of United Nations Environment programme (UNEP), was initiated and became legally binding on 17 May 2004. All countries, including South Africa, which ratified this agreement, will be expected to monitor and regulate the formation of POPs. Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are all members of the dioxin-like family of POPs. This family of chemicals pose serious health threats such as carcinogenic effects and negative effects on reproduction. These substances, with the exception of PCBs, are formed unintentionally as by-products of industrial and thermal processes. One of the main sources of dioxin-like chemicals is medical waste incinerators. In this project the area surrounding a medical waste incinerator was monitored using a bio-assay technique. The determination of dioxin concentrations is usually preformed by chemical analysis, however, bio-assays have proven themselves to be a cheaper and time-saving screening method. The Toxic Equivalency Quotient (TEQs) determined through bio-assays can support chemical analysis in determining biologically-relevant risk assessments since bio-assay data has ecotoxicological relevance. These assays represent an integrated biological response to chemical pollutants, where biological effects are accounted for which is not possible in chemical analyses. One of the bio-assays used in the determination of the dioxin-like chemical TEQ is the H411 E reporter gene bio-assay. This assay is based on the Ah-receptor mediated toxicity of dioxin-like chemicals. Using this technique the TEQs for areas surrounding an active incinerator were determined, to indicate the distribution of these substances. The TEQs for the soil samples collected ranged between nondetectable and 154 ngTEQ/kg. There was no clear distributional pattern and the total organic carbon content in the soil did not seem to play a crucial role in the distribution of dioxin-like chemicals. Although a decrease in soil tillage showed a corresponding increase in TEQ. The predominant wind direction was taken into account but no correlation could be seen. However, meteorological parameters such as the ambient temperature and low precipitation in the area may have contributed to lower TEQ values. Cytotoxicity excluded data points and the phenomenon has to be addressed. High TEQ values in a residential area where free-range chickens are raised pose a serious concern to the level of dietary dioxin-like chemical intake. Eggs in the area could theoretically contain between 2.75 and 28.75 pgTEQ/g egg fat. Further studies are needed to determine how much dioxin-like chemicals are being transferred to humans through the consumption of free-range eggs
Thesis (M. Environmental Science)--North-West University, Potchefstroom Campus, 2006.

In the transition to a sustainable energy supply there is an increasing need to use biomass for replacement of fossil fuel. A key challenge is to utilize biomass conversion technologies in an environmentally sound manner. Important aspects are to minimize potential formation of persistent organic pollutants (POPs) such as dioxins and dioxin-like compounds. This thesis involves studies of formation characteristics of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and naphthalenes (PCNs) in microwave-assisted pyrolysis (MAP) and torrefaction using biomass as feedstock. The research focuses are on their levels, distributions, fingerprints (homologue profiles and isomer patterns) and the underlying formation pathways. The study also included efforts to optimize methods for extracting chlorinated aromatic compounds from thermally treated biomass. The overall objective was to contribute better understanding on the formation of dioxins and dioxin-like compounds in low temperature thermal processes. The main findings include the following: Pressurized liquid extraction (PLE) is applicable for simultaneous extraction of PCDDs, PCDFs, PCNs, polychlorinated phenols and benzenes from thermally treated wood. The choice of solvent for PLE is critical, and the extraction efficiency depends on the degrees of biomass carbonization. In MAP experiments PCDDs, PCDFs and PCNs were predominantly found in pyrolysis oils, while in torrefaction experiments they were mainly retained in solid chars with minor fractions in volatiles. In both cases, highly chlorinated congeners with low volatility tended to retain on particles whereas the less chlorinated congeners tended to volatize into the gas phase. Isomer patterns of PCDDs, PCDFs and PCNs generated in MAP were more selective than those reported in combustion processes. The presence of isomers with low thermodynamic stability suggests that the pathway of POPs formation in MAP may be governed not only by thermodynamic stabilities but also by kinetic factors. Formation of PCDDs, PCDFs and PCNs depends not only on the chlorine contents in biomass but also the presence of metal catalysts and organic/metal-based preservatives. Overall, the results provide information on the formation characteristics of PCDDs, PCDFs and PCNs in MAP and torrefaction. The obtained knowledge is useful regarding management and utilization of thermally treated biomass with minimum environmental impact.

Concern on a global scale gave rise to the founding of the Stockholm Convention on persistent organic pollutants (POPs) with a view to restrict the use and production of these toxic chemicals. As a signatory, South Africa is legally bound to abide to the Convention’s objectives, including participating in relevant research and monitoring. However, developing countries such as South Africa have limited information concerning POPs, partially because these countries do not have sufficient analytical capabilities, and thus method development and refinement are necessary. One group of POPs consisting of polychlorinated dibenzo-pdioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs), collectively referred to as dioxins, are of particular concern due to their high toxicity and persistence. Additionally, the analysis of dioxins is recognised as one of the most analytically challenging of its kind. This study investigated the effect of different preparatory protocols on the semi-quantification of dioxins using the H4IIE-luc-reporter gene assay. The protocols evaluated were either Soxhlet or pressurised liquid extraction (PLE) combined with a manual acid digestion, gel permeation chromatography (GPC) and Florisil fractionation clean-up procedure as well as the automated Total Rapid Prep™(TRP) system which makes use of a PLE combined with a multi-layer silica, alumina and carbon column clean-up procedure. To evaluate the protocols, an eight point matrix matched calibration curve, two soil samples and a certified reference material (CRM) were used. The extracts were semi-quantified by the H4IIE-luc bio-assay. During the course of the assay, the appropriateness of different standards was investigated, and a mixed standard containing all 17 toxic PCDD/Fs was chosen for quantification. During the data review process, higher bioassay equivalent (BEQ) values were obtained from PLE compared to Soxhlet extraction, while no statistically significant difference (Kruskal-Wallis ANOVA: p > 0.05) was found between the assay quantifications for the different preparatory techniques. However, the results of the H4IIE bio-assay were larger than the expected values. The identity of the chemicals that were in all likelihood responsible for the higher response was investigated through instrumental analysis using comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry (GCxGC-TOFMS). Instrumental results indicated a high level of PAHs in the extracts, which could lead to super induction of the aryl hydrocarbon receptor (AhR) and therefore, to a positive bias in the results. Instrumental screening proved that all selected preparatory protocols were inadequate at removing interfering compounds and not sufficiently selective for PCDD/Fs, although the TRP was more successful in removing interferences. The high matrix interference hindered peak identification. Additionally, as indicated by instrumental analysis, the weak recovery of PCDD/Fs could be ascribed to high evaporation temperatures. The effect of different reference standards in the H4IIE bio-assay used during semi-quantification needs further investigation; similarly, the optimisation of extraction, evaporation and clean-up protocols and the use of different GCxGC-TOFMS column combinations aimed at more efficient separation needs to be investigated. The assistance of the National Metrology Institute (funded through the Department of Trade and Industry) towards this research is hereby acknowledged.
Thesis (MSc (Environmental Sciences))--North-West University, Potchefstroom Campus, 2013.

Modern societies produce large quantities of municipal solid waste (MSW), which is commonly disposed of by incineration. This has several advantages: it reduces the waste’s volume and sterilizes it while also enabling energy recovery. However, MSW incineration has some notable disadvantages, the most widely debated of which is probably the production and release of persistent organic pollutants (POP) such as polychlorinated dibenzofurans (PCDF), dibenzo-p-dioxins (PCDD), biphenyls (PCB) and naphthalenes (PCN). Of the 210 PCDF and PCDD congeners, 17 are toxic, with hormone-disrupting and carcinogenic properties. Twelve of the 209 PCB congeners and at least 2 of the 75 PCN also exhibit such properties. These POP form in the post-combustion zones of MSW incineration plants and are removed from the flue gas using filtering devices that trap them in the fly ash This thesis concerns the formation and degradation of POP in processes related to MSW incineration. The first paper describes a case study in which PCDD were forming in filters designed to remove them from flue gases, causing emission-related issues in a full-scale MSW incineration plant. It was shown that the PCDD formation was probably due to chlorophenol condensation on the filters’ surfaces. The second paper describes the validation of a cooling probe designed to prevent POP formation during high temperature (>450 °C) flue gas sampling. The results obtained also confirmed that PCDF and PCDD formation takes place at temperatures below 600 °C. In the third paper, three different fly ashes were subjected to thermal treatment under an inert atmosphere in a rotary kiln and in sealed ampoules at 400 °C. The concentrations, degrees of chlorination and congener profiles of the POP in the treated ashes and emitted gases were compared to those for the untreated ashes. The trends observed for PCDF mirrored those for PCN, while the trends for PCDD closely resembled those for PCB. The PCDF congener profiles of the kiln ash were similar regardless of the initial ash composition, suggesting that the mechanisms of PCDF formation were similar in all cases. The fourth paper describes the surface characterization of the three fly ashes studied in paper three by SEM, EDX, XPS and XRD. In addition, the thermal desorption and subsequent degradation of POP from the ashes was studied at temperatures of 300-900 °C. The composition of the gases released as the temperature increased differed between the ashes and depended on their composition. Doping experiments using isotopically labelled PCDF and PCDD suggests that PCDD desorbed at lower temperatures than PCDF. This thesis examines several problems relating to POP formation during MSW incineration, from sampling to the ultimate fate of incineration residues. The results obtained illustrate the wide range of processes that contribute to thermal POP formation and degradation during and after MSW incineration.
Förbränning av hushållssopor är en vanlig metod för att hantera ett växande avfallsproblem. Metoden har flera fördelar, såsom minskning av volym och vikt, sterilisering och energiåtervinning. Sopförbränning har dock vissa nackdelar och det mest debatterade är sannolikt utsläpp av persistenta organiska föroreningar (POPs) som polyklorerad dibensofuran (PCDF), dibenso-p-dioxin (PCDD), bifenyl (PCB) och naftalen (PCN). Det finns totalt 210 PCDF- och PCDD- kongener, med mellan ett till åtta klor på kolskelettet, varav 17 är giftiga med hormonstörande och cancerframkallande egenskaper. Även tolv av totalt 209 PCB-kongener samt minst två av totalt 75 PCN-kongener uppvisar liknande egenskaper. Dessa klorerade organiska föroreningar bildas då rökgaserna kyls ner i sopförbränningsanläggningarna och avlägsnas från rökgaserna med hjälp av filter och hamnar i flygaskan. Denna avhandling handlar om bildning och nedbrytning av POPs i sopförbränningsrelaterade processer.   Den första artikeln är en fallstudie där PCDD bildas i filtren i en fullskalig sopförbränningsanläggning. Bildningen ledde till förhöjda halter organiska föroreningar i rökgaserna, vilket ledde till ökade utsläpp. Den funna bildningsvägen för PCDD i filtren befanns sannolikt bero på kondensation av klorfenoler på filterytorna. Den andra artikeln är en valideringsstudie av en kylprob avsedd att användas vid rökgasprovtagning vid hög temperatur (> 450 °C) för att undvika bildning av POPs under provtagningen. Studien bekräftade att majoriteten av PCDF- och PCDD- bildning i rökgaser från sopförbränning sker vid temperaturer under 600 °C. I den tredje artikeln berättas om behandling av tre olika flygaskor från olika sopförbränningsanläggningar. Askorna behandlades vid 400 °C i inert atmosfär i både en roterugn och i förseglade ampuller. De resulterande koncentrationerna, kloreringsgraderna och kongenprofilerna av de organiska föroreningarna jämfördes. Likheter hittades mellan PCDF och PCN, medan PCDD och PCB betedde sig på ett annat sätt. Studien fann också att PCDF kongenprofiler i aska som behandlats i roterugnen liknade varandra, oberoende av askornas sammansättning, vilket tyder på en liknande bildningsväg. För den fjärde artikeln, genomfördes ytkarakterisering (SEM, EDX, XPS och XRD) på de tre flygaskorna från artikel tre som sedan hettades upp från 30 °C till 900 °C i vacuum. Det som frigjordes på grund av uppvärmningen samt nedbrytningsprodukter från askorna studerades med hjälp av masspektrometri och infraröd spektroskopi. Studien fann att de gaser som frigjordes när temperaturen ökade skilde mellan askorna, beroende på deras sammansättning. Studien fann också att när aska dopad med isotopmärkt PCDF och PCDD utsattes för samma behandling, frigjordes PCDD vid lägre temperatur än PCDF. Denna avhandling berör flera aspekter av problematiken kring klorerade organiska föroreningar som bildas vid sopförbränning, från provtagning till hur man ska hantera flygaskan. Avhandlingen belyser även olika typer av bildning och nedbrytning av POPs i varma processer kopplade till sopförbränning.

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.

This thesis contributes to an increased understanding of the formation of dioxins and dioxin-like compounds in combustion processes. Although emissions to air from waste incineration facilities have been greatly reduced by the use of efficient air pollution control measures, the resulting residues (ashes and filters) are highly toxic and are classified as hazardous waste. The main objective of the work underlying this thesis was to elucidate the formation and chlorination pathways of dioxins and dioxin-like compounds in waste combustion flue gases in the temperature range 640-200°C in a representative, well-controlled laboratory-scale reactor using artificial municipal solid waste. This could contribute to the reduction of harmful emissions to air and also reduce the toxicity of waste incineration residues, thus reducing or even eliminating the need for costly and potentially hazardous after-treatment. A comparison of four different quenching profiles showed that the formation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) was rapid and mainly occurred in the 640-400°C temperature region, with high dependency on sufficient residence time within a specific temperature region. Prolonged residence time at high temperatures (450/460°C) reduced the PCDD yields, even at lower temperatures along the post-combustion zone. PCDD, PCDF and PCN (polychlorinated naphthalene) isomer distribution patterns indicated contributions from chlorophenol condensation as well as chlorination reactions for all three classes of compounds. The formation of PCDDs was largely influenced by chlorophenol condensation and to some extent by chlorination reactions. For the PCDFs, chlorine substitution adjacent to the oxygen bridges was unfavoured, as demonstrated by the notably lower abundance of 1,9-substituted congeners. This was supported by bidirectional orthogonal partial least squares (O2PLS) modelling. The variable with the greatest influence on the distribution of PCDD congeners was the relative free energy (RΔGf). The O2PLS models displayed distinct clusters, dividing most of the homologues into two or three sub-groups of congeners which seemed to correspond to the probability of origination from chlorophenol condensation. The effects of injection of aromatic structures into the flue gas differed for each class of compounds. Injection of naphthalene increased the formation of monochlorinated naphthalene but the remaining homologues appeared to be unaffected. This was probably due to insufficient residence time at temperatures necessary for further chlorination. Injected dibenzo-p-dioxin was decomposed, chlorinated and re-condensated into PCDDs and PCDFs, whereas injection of dibenzofuran and fluorene reduced the PCDD levels in the flue gas.
Denna avhandling fokuserar på olika aspekter som kan bidra till en ökad förståelse av bildning av dioxiner och dioxin-lika föreningar i förbränningsprocesser. Även om utsläppen till luft från sopförbränningsanläggningar har minskat kraftigt tack vare effektiva rökgasreningsmetoder, så återstår problemet med mycket giftiga rökgasreningsprodukter (askor och filter), vilka klassificeras som farligt avfall. Det huvudsakliga syftet med arbetet bakom denna avhandling var att klarlägga bildnings- och kloreringsvägarna för dioxiner och dioxin-lika föreningar i temperaturintervallet 640-200°C i rökgaser från sopförbränning. Detta kan möjliggöra lösningar för ytterligare emissionsminskningar och en avgiftning av biprodukterna från avfallsförbränning, vilket minskar eller till och med eliminerar behovet av kostsam och riskfylld efterbehandling. Realistiska och välkontrollerade försök har utförts i en lab-skalereaktor där en artificiell hushållssopa har förbränts. En jämförelse av fyra olika temperatur- och uppehållstidsprofiler visade att bildning av polyklorerade dibenso-p-dioxiner (PCDD) och dibensofuraner (PCDF) sker snabbt och huvudsakligen inom temperaturintervallet 640-400°C. Bildningen var starkt beroende av en tillräckligt lång uppehållstid inom ett visst temperaturområde. En förlängd uppehållstid vid höga temperaturer (>450°C) resulterade i minskade halter av PCDD, vilka förhöll sig låga även senare i efterförbränningszonen. Isomermönstren av PCDD, PCDF och PCN (polyklorerade naftalener) visade alla tecken på att härröra från både klorfenolkondensation och kloreringsreaktioner. PCDD-mönstret visade tydliga indikationer på bildning från klorfenoler, och till mindre grad bildning via klorering. För PCDF var klorsubstitution i positioner angränsande till syrebryggan missgynnad, vilket bekräftades av multivariat modellering (O2PLS). Den variabel som starkast påverkade bildningen av PCDD var relativa fria energin (RΔGf). Modellerna visade på en distinkt gruppering av PCDD- och PCDF-kongenerna i två eller tre grupper för varje kloreringsgrad, och föreslås vara relaterad till sannolikheten för respektive kongen att bildas via klorfenolkondensation. Injektion av aromatiska kolstrukturer i rökgaskanalen gav upphov till skilda effekter. Injektion av naftalen ökade bildningen av monoklorerad naftalen medan resterande homologer inte verkade påverkas, sannolikt på grund av för kort uppehållstid för ytterligare klorering. Dibenso-p-dioxin spjälkades sannolikt till fenoliska fragment som klorerades och sedan återkondenserades till PCDD och PCDF, medan dibensofuran och fluoren kraftigt reducerade PCDD-koncentrationerna.

Large numbers of samples often need to be prepared and analysed in surveys of organic pollutants in the environment, but while the methods commonly used in such surveys can provide abundant detail they are generally costly, time-consuming and require large amounts of resources, so there is a need for simpler techniques. The work underlying this thesis assessed the potential utility of more convenient sample preparation and bioanalytical techniques for rapidly screening various environmental matrices that could be useful complements to higher resolution methods. Initially, the utility of a simplified extraction technique followed by an enzyme-linked immunosorbent assay (ELISA) for detecting polycyclic aromatic hydrocarbons (PAHs) in authentic (i.e. unspiked) contaminated soils was explored. The results showed that there are relationships between the structure and cross-reactivity among compounds that often co-occur with target PAHs. However, their potential contribution to deviations between estimates of total PAH contents of soils obtained using ELISA and gas chromatography-mass spectrometry (GC-MS) based reference methods were limited. Instead, the cross-reactivity of target PAHs and the failure to extract all of the PAHs prior to the ELISA determinations were the main reasons for these deviations. Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were detected in food and feed matrices, as well as in authentic contaminated soils using different bioanalytical techniques – ELISA and two cell-based bioassays: CAFLUX and CALUX (chemically activated fluorescent/luciferase gene expression) assays. In addition, enhanced sample preparation techniques based on accelerated solvent extraction (ASE) were developed. ASE with integrated carbon fractionation (ASE-C) in combination with CAFLUX produced estimates of PCDD and PCDF contents in fish oil and fish meal that agreed well with results obtained using reference methods. Furthermore, results from ELISA and GC-high resolution MS analyses of extracts of PCDD- and PCDF-contaminated soil samples obtained using an adjusted ASE-C technique were strongly correlated. Finally, the thesis reports the first experiments in which the results of CAFLUX, CALUX, and ELISA determinations of PCDDs and PCDFs in extracts of authentic contaminated soil samples were evaluated and compared to those obtained using a reference method. All of the bioanalytical techniques were found to be sufficiently sensitive, selective, and accurate for use in screening in compliance with soil quality assessment criteria. Overall, the improved sample preparation and bioanalytical techniques examined proved to be useful potential complements to conventional methods, enhancing the analytical framework for PAHs, PCDDs, and PCDFs. However, further validation has to be undertaken before they are applied on a large-scale.

We consider the problem of Adaptive Control of finite-dimensional, stable, Linear Time Invariant (LTI) plants. Amongst such plants, the subclass regarding which an upper bound on the order is not known or which are known to be nonminimum phase (zeros in the unstable region) pose formidable problems in their own right. On one hand, if an upper bound on the order of the plant is not known, adaptive control usually involves some form of order estimation. On the other hand, when the plant is allowed to be either minimum phase or nonminimum phase, the adaptive control problem, as is well-known, becomes considerably-less tractable. In this study, the class of unknown plants considered is such that no information is available on the upper bound of the plant order and, further, the plant may be either minimum phase or nonminimum phase. Albeit known to be stable, such plants throw myriads of challenges in the context of adaptive control. Adaptive control involving such plants has been addressed [79] in a Model Reference Adaptive Control (MRAC) framework. There, the inputs and outputs of the unknown plant are the only quantities available by measurement in terms of which any form of modeling of the unknown plant may be made. Inputs to the reference model have been taken from certain restricted classes of bounded signals. In particular, the three classes of inputs considered are piecewise continuous bounded functions which asymptotically approach • a nonzero constant, • a sinusoid, and • a sinusoid with a nonzero shift. Moreover, the control law is such that adaptation is carried out at specific instants separated by progressively larger intervals of time. The schemes there have been proved to be e-optimal in the sense of a suitably formulated optimality criterion. If, however, the reference model inputs be extended to the class of piecewise continuous bounded functions, that would compound the complexity of the adaptive control problem. Only one attempt [78] in adaptive control in such a setting has come to our notice. The problem there has been tackled by an application of the theory of Pade Approximations to time moments of an LTI system. Based on a time moments estimation procedure, a simple adaptive scheme for Single-Input Single-Output (SISO) systems with only a cascade compensator has been reported. The first chapter is essentially meant to ensure that the problem we seek to address in the field of adaptive control indeed has scope for research. Having defined Adaptive Control, we selectively scan through the literature on LTI systems, with focus on MRAC. We look out in particular for studies involving plants of which not much is known regarding their order and systems which are possibly nonminimum phase. We found no evidence to assert that the problem of adaptive control of stable LTI systems, not necessarily minimum phase and of unknown upper bound on the order, was explored enough, save two attempts involving SISO systems. Taking absence of evidence (of in-depth study) for evidence of absence, we make a case for the problem and formally state it. We preview the thesis. We set two targets before us in Chapter 2. The first is to review one of the existing procedures attacking the problem we intend to address. Since the approach is based on the notion of time moments of an LTI system, and as we are to employ Pade Approximations as a tool, we uncover these concepts to the limited extent of our requirement. The adaptive procedure, Plant Command Modifier Scheme (PCMS) [78], for SISO plants is reported in some detail. It stands supported on an algorithm specially designed to estimate the time moments of an LTI system given no more than its input and output. Model following there has been sought to be achieved by matching the first few time moments of the reference model by the corresponding ones of the overall compensated plant. The plant time moment estimates have been taken to represent the unknown plant. The second of the goals is to analyze PCMS critically so that it may serve as a forerunner to our work. We conclude the chapter after accomplishing these goals. In Chapter 3, we devise a time moment estimator for SISO systems from a perspective which is conceptually equivalent to, yet functionally different from, that appropriated in [78]. It is a recipe to obtain estimates of time moments of a system by computing time moment estimates of system input and output signals measured up to current time. Pade approximations come by handy for this purpose. The lacunae exposed by a critical examination of PCMS in Chapter 2 guide us to progressively refine the estimator. Infirmities in the control part of PCMS too have come to light on our probing into it. A few of these will be fixed by way of fabricating two exclusively cascade compensators. We encounter some more issues, traceable to the estimator, which need redressal. Instead of directly fine-tuning the estimator itself, as is the norm, we propose the idea of 'estimating' the lopsidedness of the estimator by using it on the fully known reference model. This will enable us to effect corrections and obtain admissible estimates. Next, we explore the possibility of incorporating feedback compensation in addition to the existing cascade compensation. With output error minimization in mind, we come up with three schemes in this category. In the process, we anticipate the risk of instability due to feedback and handle it by means of an instability preventer with an inbuilt instability detector. Extensive simulations with minimum and rionminimum phase unknown plants employing the various schemes proposed are presented. A systematic study of simulation results reveals a dyad of hierarchies of progressively enhanced overall performance. One is in the sequence of the proposed schemes and the other in going for matching more and more moments. Based on our experiments we pick one of the feedback schemes as the best. Chapter 4 is conceived of as a bridge between SISO and multivariable systems. A transition from SISO to Multi-Input Multi-Output (MIMO) adaptive control is not a proposition confined to the mathematics of dimension-enhancement. A descent from the MIMO to the SISO case is expected to be relatively simple, though. So to transit as smoothly and gracefully as possible, some issues have to be placed in perspective before exploring multivariable systems. We succinctly debate on the efforts in pursuit of the exact vis-a-vis the accurate, and their implications. We then set some notations and formulate certain results which serve to unify and simplify the development in the subsequent three chapters. We list a few standard results from matrix theory which are to be of frequent use in handling multivariable systems. We derive control laws for Single-Input Multi-Output (SIMO) systems in Chapter 5. Expectedly, SIMO systems display traits of observability and uncontrollability. Results of illustrative simulations are furnished. In Chapter 6, we formulate control laws for Multi-Input Single-Output (MISO) systems. Characteristics of unobservability and controllability stand out there. We present case studies. Before actually setting foot onto MIMO systems, we venture to conjecture on what to expect there. We work out all the cascade and feedback adaptive schemes for square and nonsquare MIMO systems in Chapter 7. We show that MIMO laws when projected to MISO, SIMO and SISO cases agree with the corresponding laws in the respective cases. Thus the generality of our treatment of MIMO systems over other multivariable and scalar systems is established. We report simulations of instances depicting satisfactory performance and highlight the limitations of the schemes in tackling the family of plants of unknown upper bound on the order and possibly nonminimum phase. This forms the culmination of our exercise which took off from the reported work involving SISO systems [78]. Up to the end of the 7th chapter, we are in pursuit of solutions for the problem as general as in §1.4. For SISO systems, with input restrictions, the problem has been addressed in [79]. The laws proposed there carry out adaptation only at certain discrete instants; with respect to a suitably chosen cost, the final laws are proved to be e>optimal. In Chapter 8, aided by initial suboptimal control laws, we finally devise two algorithms with continuous-time adaptation and prove their optimality. Simulations with minimum and nonminimum phase plants reveal the effectiveness of the various laws, besides throwing light on the bootstrapping and auto-rectifying features of the algorithms. In the tail-piece, we summarize the work and wind up matters reserved for later deliberation. As we critically review the present work, we decant the take-home message. A short note on applications followed by some loud thinking as a spin-off of this report will take us to finis.

碩士
國立中正大學
機械系
89
KEYWORD:Medical waste,incinerator,pyrolysis,dioxin,furan We discuss mainly the of Dioxin (PCDDs) and Furan (PCDFs) when the medical waste is on fire .And study and confer the combustible method and control of medical waste our country and foreign developed country counter ,and the prevention and reduction of the production presently . Analyze the condition of pyrolysis when medical waste in the incinerator, and compare with experiments and the production of different composition of gas under different operational conditions. And to build the analyzed models of theory, wish to understand the formation mechanism of Dioxin and Furan while medical waste pyrolysed in incinerator. And then find better and economic method to handle to achieve the goal to reduce harmful waste gas. We analyzed the models of chemical reaction and chemical equilibrium in order to build combustion analysis model , and use the relationship between equilibrium constant(Kc),temperature(K),emissions of hydrogen chloride(HCl) and excess air(γ) then to find the ways of controlling.

碩士
中興大學
環境工程學系所
95
The Nantou County locates on the eastern site of Taichung city and on the western site of Central Mountain Range. Thus, it is easily to accumulate dioxin in Nantou with the air parcel transferred from western sources. Additionally, several incinerators have already operated in west Taiwan recently, and these also are important dioxins sources. For understanding dioxins characters and sources in the Nantou County, this study analyzes impact range and dioxins characters of near incinerators by measurement and GTx modeling. We considered eight major categories of PCDD/Fs emission sources and three different locations, to cover a wide range of sourcecharacteristic, PCDD/Fs congener profiles, meteorological conditions and terrain configurations. The atmospheric dioxins concentrations in suburban site, traffic arteries site and background station were 0.11, 0.17 and 0.0095 pg I-TEQ/m3, respectively. Moreover, the dioxins concentrations of the grass cut frequently were 0.18, 0.9 and 0.15 pg WHO-TEQ/g, and the dioxins concentrations of the grass cut ifnfrequently were 0.33, 1.5 and 0.13 pg WHO-TEQ/g with a moisture content of 12 %. The characteristic index and model simulations could be founded that suburban site was not only impacted by incinerators, electric arc furnaces and traffic source, but also impacted by copper and aluminum smelters. For traffic arteries station, the main sources were metropolitan solids wastes incinerators, medical wastes incinerators, sinter plants, electric arc furnaces, copper smelters, diesel-fueled vehicles and unleaded gas-fueled vehicles. The model also showed that pollutants were easily transferred into Chushan in north and northeast wind system. Therefore, the north wind system would facilitate the dioxins transporting into Chushan and Shuili, and leaded the dioxins concentrations increasing. This study showed that using the GTx model, atmospheric monitoring data, the pasture examination data and PCDD/Fs congener profiles can explicitly understand the relationship of PCDD/Fs between the source and the receptor.

Relatório de Estágio do Mestrado Integrado em Ciências Farmacêuticas apresentado à Faculdade de Farmácia
O presente relatório de estágio em farmácia comunitária, tem como objetivo descrever e avaliar o estágio curricular, realizado na Farmácia Nova da Penteada, na Região Autónoma da Madeira, através de uma análise SWOT. Esta análise contempla os pontos fortes, os pontos fracos, as oportunidades e as ameaças, inerentes ao estágio.O presente relatório de estágio em farmácia hospitalar, tem como objetivo descrever e avaliar o estágio curricular, realizado no Serviço de Saúde da Região Autónoma da Madeira, E.P.E., através de uma análise SWOT. Esta análise contempla os pontos fortes, os pontos fracos, as oportunidades e as ameaças inerentes ao estágio.As dibenzodioxinas (PCDDs) e os dibenzofuranos (PCDFs) são poluentes orgânicos persistentes (POPs), ambientalmente estáveis. São subprodutos de várias reações químicas e térmicas, e acumulam-se na cadeia alimentar por serem compostos lipofílicos. Os PCDD/Fs são tóxicos para o organismo humano e armazenam-se nos reservatórios de gordura. O leite materno é utilizado como biomarcador dos níveis de resíduos, porque reflete a carga corporal maternal de poluentes e a exposição potencial dos lactentes. Além disso, o leite materno é rico em lipídos, é um método não-invasivo e fácil de ser recolhido. Vários estudos em diferentes países apresentam os níveis de equivalente de toxicidade (EQTs) no leite materno, permitindo assim, obter uma análise sobre a exposição da população. As implicações para a saúde das crianças dependem das concentrações de resíduos a que estão expostas. São observadas alterações no crescimento e imunológicas, perturbações endócrinas e no desenvolvimento neurológico das crianças. Os PCDD/Fs são extraídos, purificados, detetados e quantificados por várias metodologias analíticas. O principal método de deteção e quantificação é a cromatografia gasosa de alta resolução/espetrometria de massa de alta resolução (CGAR/EMAR). Apesar da ingestão de PCDD/Fs pela amamentação ter efeitos deletérios nas crianças, a amamentação tem inúmeras vantagens que provavelmente se sobrepõem aos aspetos negativos.
The present internship report on community pharmacy, aims to describe and evaluate the curricular internship, performed at “Farmácia Nova da Penteada”, through a SWOT analysis. This analysis considers the strengths, weaknesses, opportunities and threats associated with the internship.The present internship report on hospital pharmacy, aims to describe and evaluate the curricular internship, performed at “Serviço de Saúde da Região Autónoma da Madeira, E.P.E.”, through a SWOT analysis. This analysis considers the strengths, weaknesses, opportunities and threats associated with the internship.Dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are persistent organic pollutants (POPs), environmentally stable. They are by-products from several chemical and thermal reactions and accumulate in the food chain because they are lipophilic compounds. PCDD/Fs are toxic to the human body and are stored in the fat reservoirs. Breast milk is used as a biomarker of lipophilic residues levels because it reflects the maternal body burden of pollutants and the potential exposure of infants. Furthermore, breast milk is rich in lipids and can be collected easily and non-invasively. Several studies in different countries present toxic equivalents (TEQs) levels in breast milk, thus allowing an analysis of the exposure of the population. The health implication of children depends on the concentration of residues to which they are exposed. Growth and immune changes, endocrine disorders and neurological development of children are observed. PCDD/Fs are extracted, purified, detected and quantified by several analytical methodologies. The main method of detection and quantification is high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). Although the ingestion of PCDD/Fs through breastfeeding has deleterious effects on children, breastfeeding has numerous advantages that are likely to overlap with negative aspects.

碩士
國立臺灣大學
職業醫學與工業衛生研究所
98
Background and Purpose: Polychlorinated biphenyls (PCBs) and Polychlorinated dibenzofurans (PCDFs) are lipophilic pollutants and are known to cause multiple health outcomes in exposed animals and humans. In 1979, approximately 2000 people in central Taiwan were exposed to rice oil contaminated with PCBs and their heat-degradation products, mainly PCDFs, and many manifested by fatigue, skin disorder, abnormal liver function, and other symptoms. No study has documented the health-related quality of life among people exposed to PCBs/PCDFs in the past 30 years. Objectives: This study aimed to determine whether quality of life (QOL) was affected in people exposed to PCBs/PCDFs, as compared to the QOL obtained from background population selected from the National Health Interview Survey (NHIS) in 2001 in Taiwan. Methods: A total of 1,231 exposed subjects with previous PCBs/PCDFs exposure were invited to assess their quality of life by WHO quality of life-BREF (WHOQOL- BREF) Taiwanese version Questionnaire in 2008. Similar survey was done in 2001 in the NHIS study. For those exposed subjects satisfactorily completed the QOL questionnaire, comparisons were obtained from the QOL results randomly sampled from those background individuals matched for age, sex, and county using 1:3 match. Results: A total of 279 exposure subjects (23%) satisfactorily completed the questionnaire. Between the exposed and unexposed referents, the scores of overall QOL were 52.4±8.9, 58.2±6.1. As for individual domains, those of physical health were 14.0±2.3, 15.5±1.9, those of psychological health 12.7±2.8, 14.2±1.9, those of social relationships 13.0±2.5, 14.7±1.9, and those of environment 12.6±2.3, 13.9±1.8. In overall and individual domain scores, exposed people were significantly lower than those of the background population. After adjusted for age, education, gender, occupation, marriage, smoking and drinking, the exposed scored lower than the background in all overall health and individual domains; as well as the following QOL question items: energy, sleep, work capacity, ability to concentrate, bodily appearance, respected/feeling of acceptance, sexual life, and lacking of discomfort/pain. Conclusion: Exposure to PCBs/PCDFs 29 years ago seemed to have adverse effects on overall score of quality of life, as well as on various aspects of quality of life, namely, physical, psychological, social, and environmental domains.

碩士
國立臺灣大學
職業醫學與工業衛生研究所
97
Polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-furans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) are all important endocrine disrupting chemicals and also persistent organic pollutants. Among them, 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) is known to cause most significant health effects in humans. The PCDFs have similar structure and toxicity as PCDDs. Approximately 2000 people were exposed to rice oil contaminated with polychlorinated biphenyls (PCBs) and their heat-degradation products, mainly polychlorinated dibenzofurans (PCDFs) in central Taiwan in 1979. CYP1A2 activity was found to be induced by such exposure in exposed individuals. The aryl hydrocarbon receptor (AhR) pathway was known to be critical in mediating such enzyme induction. Aryl hydrocarbon receptor nuclear translocator (ARNT) and AhR repressor (AhRR) played important roles in transcriptional regulation of AhR. In order to determine whether the ARNT and AhRR polymorphisms are associated with individual inducibility of CYP1A2. We examined the people exposed to PCBs and PCDFs and their community controls, 173 previously participated in a study on CYP1A2 activity as measured by caffeine metabolic rate, which was in turn found to be positively associated with serum 2,3,7,8-TCDD toxic equivalency (TEQ). Genotyping was done for the following SNPs：AhRR(rs2292596)(C/G), ARNT(rs7517566)(A/G), ARNT(rs3820541)(C/G), ARNT(rs3768016)(C/T), and ARNT(rs2228099)(C/G). The allele frequencies of AhRR (rs2292596) were 0.62 for allele C, 0.38 for allele G; those for ARNT (rs7517566) were 0.79 for allele A, and 0.21 for allele G, ARNT (rs3820541) 0.82 for allele C and 0.18 for allele G, ARNT (rs3768016) 0.58 for allele C and 0.42 for allele T, and ARNT (rs2228099) 0.59 for allele C and 0.42 for allele G. At a similar TEQ dose range, those subjects with AhRR GG genotype had the highest induced CYP1A2 activity, followed by those with CG genotype. Those with CC genotypes had lowest inducibility (p<0.05). ARNT(rs3768016) CC genotype had highest inducibility, followed by CT, and TT genotypes. ARNT (rs2228099) GG genotype had highest inducibility, followed by CG, and CC genotypes. We conclude that AhRR and ARNT genotypes might interact with PCBs and PCDFs in cytochrome P450 enzyme induction effects.

碩士
國立臺灣大學
職業醫學與工業衛生研究所
100
Background: In 1979, approximately 2000 people in central Taiwan were accidentally exposed polychlorinated biphenyls (PCBs) and dibenzofurans (PCDFs) due to ingest the contaminated rice oil. Children born to exposed mothers after the exposure event were thus prenatally exposed. We followed up these children for health effects and found poorer neurocognitive development. The effect is still presence in the prenatal exposed child after the event about 7~12 years. We would like to know the adult IQ of the prenatal exposed second generation, and assess the neurocognitive effect of second generation comprehensively. The study aim is：1. Whether the dose - effect relationship was found between IQ and predicted PCBs/PCDFs concentration? 2. Whether PCBs/PCDFs exposure could affect the nerve conduction potential situation? 3. Whether PCBs/PCDFs exposure was associated with activation changes in specific brain regions of cortical? Method: The study sample is prenatal exposed people and their matched controls. In the study aim 1, there are 110 prenatal exposed people and 124 matched controls. Assess the relationship between the predicted PCBs/PCDFs concentration and the child IQ. In the study aim 2 and 3, among the 304 prenatal exposed people that we follow up regularly, and the age range from19 to 32 years, we select 10 young men and their matched controls 11 volunteer. We propose to utilize the recently advanced neuroimaging technologies, namely, functional magnetic resonance imaging (fMRI) to examine the functional activations. In addition, Wechsler Adult Intelligence Scale (WAIS) and contact heat evoke potential (CHEP) used to follow the participants’ neurocognitive functioning. Result: Among Yucheng children, males and females were affected rather differently in IQ. Some subscales of WISC-R were negatively related to mothers’ serum levels of PCB congeners 138, 153, 157, and 180. Among adults, Wechsler intelligence scores were lower in Yucheng boys as compared to their controls. The amplitudes of the contact heat evoke potential in legs of Yucheng men was found to be lower than those in the controls (p=0.03). In functional MRI, the parietal activation with picture task (p<0.001) was found in both groups. Yucheng men had higher activation in cerebellum than their controls in the contrast results (p<0.001), and had lower activation in hippocampus, amygdala than their controls (p<0.001). We conclude that IQ was affected in the second generation of Yucheng women. These effects were dose-related to maternal exposure levels. Reduced evoke potential amplitude induced by heat exposure was seen in Yucheng second generation. Using functional activation studies, different regions of activation were seen in Yucheng and their controls. Further studies with larger number of participants are warranted to confirm this finding.

碩士
國立中央大學
環境工程學系
86
In this study, fly ashes were sampled from three large-scale MSW (municipal solid waste) incinerators in Taiwan for analysis of dioxin contents. In addition to the investigation of dioxin contents of fly ash from MSW incinerators, our study also look into dioxin formation within the MSW incineration system via a laboratory-scale reactor. In this study, the effects of the reaction time, temperature, oxygen content in the gas stream and carbon content of fly ash on PCDD/Fs formation on fly ash were investigated. Three MSW incinerators investigated are equipped with different air pollution control device (APCD). Preliminary results indicated that 2,3,7,8-PCDD/Fs homologue patterns of various types of fly ash were quite similar for three MSW incinerators. The concentrations of higher chlorinating degree congeners of PCDDs and PCDFs were obviously higher than that of lower chlorinating degree congeners. The content of dioxin in fly ash would increase as the fly ash passed through APCD zone. In other words, the environment of APCD may actually increase the content of dioxin in fly ash. Dioxin concentration in fly ash for three MSW incinerators was MSW-C＜MSW-A＜MSW-B. About the formation experiments for dioxins in this study, the optimum temperature of dioxin formation for various fly ashes was different. The optimum temperatures was 350℃ for boiler ash, 300℃ for cyclone ash and 250℃ for ESP ash, respectively. Preliminary results indicated that the optimum temperature would increase with decreasing particle size. The dioxin content of fly ash was not significantly correlated with reaction time. As the O2 concentration was varied between 0~100％, the optimum oxygen content for dioxin formation was found at 7.5﹪for cyclone ash, and the PCDD/PCDF ratio increased with increasing (O2(. Therefore, the formation of PCDDs which contains two oxygen atoms are affected more significantly by (O2( than PCDF which contains only one oxygen atom. Dioxins formation was observed even for the gas containing no oxygen was passed through the fly ash. As a result, other formation routes which do not need O2 occur on fly ash, for example, the Ullmann condensation reaction, or O2 was provided from the precursor (oxygen-complex compound) originally existed in fly ash. The carboncontent in fly ash is varied between 0~20﹪in this study, and the results showed that the maximum formation was found at 5％. The dioxin formation rates with and without gas stream were compared, the latter process resulted in the larger amount of PCDD/Fs. In all experiments of this study, the concentration of dioxin is ESP ash＞cyclone ash＞boiler ash. The precursors were not injected into the fly ash or gas stream in all formation experiments, however, dioxin was still formed in fly ash. In other words, other chlorinated routes may exist on the fly ash surface in addition to Deacon reactions.Keywords： Dioxin, PCDD, PCDF, APCD, Temperature, Oxygen, Carbon content

Thesis (Ph. D.)--University of Notre Dame, 2005.
Thesis directed by Robert L. Irvine for the Department of Civil Engineering and Geological Sciences. "March, 2005." Includes bibliographical references (leaves 132-140).

碩士
國立中央大學
環境工程研究所
92
Polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) are very toxic compounds mainly emitted from municipal solid waste incinerators(MSWI). These compounds will affect human health when inhaled. Activated carbon injection (ACI) and SCR decompostition are two major end-of-pipe pollution control technologies currently used. It is proved that addition of inhibitors (such as sulfur, SO2, urea, alkaline materials) could decrease formation of dioxins. Experimental results indicate that addition of sulfur in incineration process can reduce PCDD/F formation. PCDD/F formation can be effectively reduced when S/Cl molar ratio is about 2. Dioxins decrease dramatically at SO2/HCl ratio as 0.55. The sulfur component will react with Cl2 and convent it into HCl. In addition, S or SO2 affect dioxin formation by vulcanizating phenolic precursors and catalysis metal, thus inhibiting chlorination reaction. Calcium hydroxide can reduce dioxin formation by more than 90﹪when Ca/Cl molar ratio is over 0.5. Addition of urea can also reduce PCDD/F formation about 50~87﹪when N/Cl mole ratio is about 0.1. The role of urea is to block catalysis metal and to form complex compounds with Cu and to prevent Ullmann reaction. Inhibition of dioxins formation will be the best way to reduce dioxin emissions. The cost of applying inhibitors for reducing dioxin formation is considerably lower than that of using activated carbon injection (ACI) and SCR decompostition. Adding inhibitors technology has a good potential for controling dioxins formation and emission in the future.

碩士
國立成功大學
環境醫學研究所
90
Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are broadly distributed environmental contaminants. PCDDs/PCDFs/PCBs are highly stable in the environment. They are lipophilic and can be bioaccumulated via food chain into human bodies with long half-lives of elimination. The adipose tissue, blood, and breast milk are usually analyzed for the assessment of human exposure to PCDDs/PCDFs/PCBs. Among these three types of specimen, analysis of breast milk for exposure assessment provides two specific advantages. First, the collection of breast milk is noninvasive. Second, the analytical data can be used to assess the exposure of both the mother and the infant. The objectives of the study are (1) to measure the PCDDs/PCDFs/PCBs levels in breast milk samples collected in Tainan area, and (2) to utilize these data to evaluate infant’s exposure via breast-feeding. 　　The samples were collected from NCKU, Sin-Lau, and Chi-Mei hospitals in Tainan city. Breast milk samples were collected from 41 volunteers in these hospitals in years 2000 and 2001. Breast milk lipids were extracted by ethanol and n-hexane, followed by sulfuric acid digestion. For the analysis of 17 PCDDs/PCDFs, the extracts were fractionated with ion exchange (SCX), silica (Si), and Florisil solid phase extraction columns, and the fraction containing dioxins and furans were analyzed by gas chromatography-high resolution mass spectrometry (GC-HRMS). For the analysis of PCBs, only Florisil column fractionation was used, and 36 PCB congeners were analyzed by gas chromatography electronic capture detector (GC-ECD). 　　The average age of the subjects in this study was 30 years (N = 37, SD = 3.6 yrs). The total concentration of 17 dioxin congeners in the breast milk was 213 �b 141 pg/g-lipid. The concentration can be expressed as 12.7 �b 8.40 pg-I-TEQ/g-lipid when the international toxic equivalences (I-TEQs) of 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TCDD) is calculated, or 14.6 �b 9.26 pg-WHO-TEQ/g-lipid using WHO toxic equivalences (WHO-TEQs). The total concentration of 36 PCB congeners in breast milk was 96.8 �b 96.0 ng/g-lipid. The data represent these mothers’ exposure, and infants’ exposure through breast-feeding nursing can be estimated. Assuming that the breast milk intakes per day for an infant are 805 mL in the first two months after birth, 810 mL in the third month, and 925 mL from the 4th to the 6th month respectively, with an absorption efficiency of 95 %, the average infant’s dioxin/furan exposure was estimated to be 216 �b 129 pg-I-TEQ/day (or 250 �b 148 pg-WHO-TEQ/day). Due to the weight difference between boys and girls, these values translate into 34.9 �b 20.7 pg-I-TEQ/kg/day (40.5 �b 23.8 pg-WHO-TEQ/kg/ day) for boys, and 40.1 �b 23.8 pg-I-TEQ/kg/day (46.5 �b 27.3 pg-WHO-TEQ/kg/ day) for girls. Using the same model, the average infant’s exposure to 36 PCBs was estimated to be 2671 �b 2526 ng/day, or 431 �b 408 ng/kg/day for boys and 495 �b 465 ng/kg/day for girls.

碩士
國立成功大學
環境醫學研究所
93
The objective of this study was to determine the concentrations of serum PCDD/F/Co-PCBs of operation workers, the concentrations of airbrone PCDD/Fs of working environment, and the relationship between serum PCDD/F/Co-PCBs levels and health index of workers in secondary copper smelting plant. The personal exposure data and time activity pattern were collected with questionnaires. And thirteen blood biochemistry examinations, immunological index and five hormones were examined. All the results were integrated to conduct the PCDD/F/Co-PCBs exposure assessment of workers. 46 blood samples and 4 air samples were collected and analyzed in this study. The highest TEQ levels of airborne PCDD/Fs was 34.8 pg WHO-TEQ/Nm3 sampled in the casting area at plant A, and lowest was in the casting area at plant B. The partitioning of gas/particle data showed the PCDD/Fs in particle phase was higher than gas phase. All workers were grouped to foreign and local workers, then local workers were grouped to high and low-level groups by the median of serum PCDD/Fs (29.5 pg WHO98-TEQDF/g lipid). The average serum PCDD/F/Co-PCBs levels in high, low-level and foreign groups were 41.0、20.9 and 20.4 pg-WHO-TEQ/g-lipid respectively. The TEQ levels of serum PCDD/F/Co-PCBs of all workers （28.6 pg WHO98-TEQDF/g lipid）was higher than that of general populations in Taiwan. Besides the abnormal rates of glucose in low-level group and GGT in foreign group were marginally significant lower than the high-level group, there were no significant differences of blood biochemistry, hormone, and immunological index among three groups. The dominating homologue of PCDD/Fs in blood and air samples are both PeCDFs and HxCDFs, it meant that the workers were potentially exposure to higher levels of PCDD/Fs emitted from secondary copper plant. The major congeners of Co-PCBs were PCB77, PCB169 and PCB126. The regression data showed serum PCDD/F/Co-PCBs were highly correlated with seniority and the exposure indices .The lifetime average daily does （LADD） of workers were met the range of WHO daily tolerance dose. The usage of personal protective measures was suggested to effectively reduce the exposure of PCDD/F/Co-PCBs.

碩士
國立成功大學
環境工程學系
103
The aim of this study is to solve the problem of extremely high polychlorinated diphenyl ethers (PCDEs) concentrations and formation during cold-start procedure of municipal solid waste incinerators (MSWIs). In this study, we proposed control technologies, including shortening the heating time of combustion between 200-450°C and advancing the injecting times of activated carbon and lime, to abate high emissions of combustion-originated PCDEs during the cold-start procedure. PCDE emissions of two MSWIs, one adopting proposed control technologies (MSWI-A) and the other with standard start-up procedure (MSWI-B), were compared to evaluate the effect of reduction on PCDEs. Stack flue gases sampling were carried on the incinerator 3 and 2 of MSWI-A during cold-start trials and a total of four (sample A–D) and six samples (sample A–F) were collected, respectively. The results showed that the total PCDE concentrations rose in the middle stage of two cold-start trials of MSWI-A. At that time the temperature of combustion chamber reached 231°C–406°C, which was in the temperature region of de novo synthesis (250°C–450°C). After that, the waste feeding resulted in the incomplete combustion condition, causing the drastic elevation of total PCDE concentrations (0.0994 ng/Nm3 for incinerator 3 and 0.134 ng/Nm3 for incinerator 2). Furthermore, the temperatures in the inlet of superheater and economizer were also in the temperature region of de novo synthesis, which may resulted in the formation of PCDEs. After calculating, the estimated PCDE emission quantities of MSWI-A during the first and the second start-up trials were 0.0664 mg and 0.0486 mg, respectively. By adopting the control technologies, the highest PCDE concentrations and PCDE emission quantities of MSWI-A during two cold-start trials were reduced by 98.7–99.0% and 98.4–98.4%, respectively, compared to those of MSWI-B. This study was carried out at the MSWI which is in operation. The adopted measures can be practically applied without modifying any hardware facilities. Cleaning stoppage of auxiliary fuel nozzle and advancing the injecting times of activated carbon and lime will not affect the operational cost. Furthermore, the furnaces and air pollution control devices (APCDs) of MSWI-A are similar to those of other MSWIs in Taiwan. Therefore, the control technologies proposed in this study can be applied to other MSWIs in the future.

碩士
國立成功大學
環境醫學研究所
88
Polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzo-p-furans (PCDFs) are among the most widespread environmental pollutants. Accumulation in human tissues with these lipophilic compounds is often considered as a potential threat to human health. Livers are the most sensitive organs observed in toxicological animal studies and consequential liver damages caused by the toxins are commonly observed. Several epidemiological studies have shown that occupational and non-occupational human exposures of PCBs, PCDDs and PCDFs, such as those of PCBs in transformer/capacitor factories and PCDDs/PCDFs in an industrial accident occurring in Seveso, Italy, were linked to abnormalities in liver function. In these studies, levels of total PCBs/PCDDs/PCDFs, rather than levels of specific PCB/PCDD/PCDF congeners, in the blood samples are often used to study their association with the health effects. Abnormalities in liver function and liver cirrhosis were also reported in the Yu-cheng patients in Taiwan. A nested case-control design was used within a cohort of subjects, 2061 Yu-cheng patients in Taiwan, which has been followed up by Guo and his co-workers since 1991. The study aims to investigate the relationship between blood levels of PCB/PCDD/PCDF congeners and observed abnormal liver function in Yu-cheng patients by measuring the concentrations of specific congeners in the blood samples. Gas chromatography-electron capture detection (GC-ECD) and gas chromatography-high resolution mass spectrometry (GC-HRMS) are utilized for the congener-specific measurements. PCB/PCDD/PCDF congener levels in the blood of 41 Yu-cheng patients were analyzed. The average concentration of the total PCDDs/PCDFs of the blood samples was found to be 6893 pg/g-lipid and the concentration of 1,2,3,4,7,8-HxCDF (1741pg/g-lipid) was the highest among seventeen PCDD/PCDF congeners determined in the blood samples. The average total PCBs concentration in the blood samples was found to be 2921 pg/mg-lipid and the concentration of PCB 28/31 (397pg/mg-lipid) was the highest among thirty-four PCB congeners. After adjustment for cholesterol and body mass index (BMI), there were statistically significant positive correlations between liver function and some PCB levels (PCB 28/31, 44, and 189).

Incineration with energy recovery is the main disposal strategy for waste that cannot be reused or recycled, and a well-established source of energy in Europe, especially in Sweden where 2.2 Mtonnes of waste including domestic and imported municipal solid waste (MSW) and waste wood (WW) were combusted during 2015. However, owing to its inherent heterogeneous composition, inclusion of such waste in Waste-to-energy (WtE) technologies is challenging. These heterogeneities may lead to operationally-related issues in the WtE facilities and contribute to toxic emissions, which can be reduced by waste pre-treatment technologies.    This thesis examines the variations in the composition of MSW and WW streams used as a fuel supply in WtE facilities after undergoing waste pre-treatment technologies, and the effect of fuel composition on its combustion behaviour and formation of persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). The overall objective is to contribute to a more thorough understanding of the selection of waste pre-treatment technologies to mitigate harmful emissions into the atmosphere when waste fuels are combusted in WtE facilities.    This thesis describes the high variability of contaminants in domestic and imported WW and suggests adaptation of WW pre-treatment techniques to produce fuels with a low potential for generating pollutants. A comparison of mechanical solid waste pre-treatments revealed that screening and shredding is more efficient than extrusion for reducing emissions of pollutants such as PCDDs and PCDFs in combustion. The evaluation of the combustion behaviour of MSW-based fuels showed a three-stage oxidative decomposition, and an acceleration of the decomposition of the MSW compared to the lignocellulosic materials, which may be attributed to the presence of food waste and plastics in the MSW. Combustion tests of fuel blends containing WW and MSW-based fuels with different food waste content suggested that WW, not food waste content, is the key factor for the formation of PCDDs, PCDFs, and polychlorinated biphenyls (PCB), benzenes (PCBzs) and phenols (PCPhs). Torrefaction may be a suitable technology for improving the properties of waste as a fuel e.g. due to its low PCDD and PCDF emissions.
Förbränning med energiåtervinning är det huvudsakliga sättet att ta hand om avfall som inte kan återanvändas eller återvinnas. Det är en väletablerad energikälla i Europa och särskilt i Sverige där 2,2 miljoner ton avfall, däribland inhemskt och importerat hushållsavfall och returträ, förbrändes under 2015. På grund av den heterogena sammansättningen hos hushållsavfall och returträ är förbränning av dessa material i anläggningar med energiåtervinning (så kallade WtE-anläggningar) förknippade med en del driftsrelaterade utmaningar. Det kan även ge upphov till miljöfarliga utsläpp, som dock kan reduceras genom förbehandling av avfallet. I denna avhandling har variationer i sammansättningen hos hushållsavfall och returträ som förbränns i WtE-anläggningar undersökts. Effekten av bränslemixens sammansättning och ev förbehandling på bränslets förbränningsegenskaper samt bildning av långlivade organiska föroreningar (så kallade POPar) såsom polyklorerade dibenso-p-dioxiner och polyklorerade dibensofuraner vid förbränning har utvärderats. Det övergripande målet är att bidra till en djupare förståelse av hur valet av förbehandlingsteknik för avfall kan bidra till att minska skadliga utsläpp till luft när avfallsbränslen förbränns i WtE-anläggningar. Denna avhandling beskriver den stora variabiliteten av metall- och materialföroreningar i inhemskt och importerat returträ och föreslår förbehandlingstekniker för att producera bränslen med låg potential att generera föroreningar. En jämförelse av mekaniska förbehandlingstekniker visade att mekanisk sönderdelning och separering (krossning och siktning) är mer effektivt än s.k. högtrycks-pressning för att minska utsläppen av föroreningar som dioxiner och furaner vid förbränning. Utvärderingen av bränslemixar innehållande hushållsavfall uppvisade en oxidativ nedbrytning i tre steg vid förbränning, och en accelererad nedbrytning av avfallsmaterialet jämfört med vedmaterialet i bränslet, troligen som effekt av innehållet av matavfall och plast i hushållsavfallet. Förbränningsförsök med bränsleblandningar av returträ och hushållsavfall med olika innehåll av matavfall visade att mängden returträ, och inte mängden matavfall, är den viktigaste faktorn för bildning av dioxiner, furaner, klorbifenyler, klorbensener, och klorfenoler. Torrefiering kan vara en lämplig teknik för att förbättra avfallets bränsleegenskaper, t.ex. på grund av dess låga emissioner.

Rapid economic development has occurred during the past few decades in China with the Yangtze River Delta (YRD) area as one of the most progressive areas. The urbanization, industrialization, agricultural and aquaculture activities result in extensive production and application of chemicals. Organohalogen contaminants (OHCs) have been widely used as i.e. pesticides, flame retardants and plasticizers. They are persistent, bioaccumulative and pose a potential threat to ecosystem and human health. However, limited research has been conducted in the YRD with respect to chemicals environmental exposure. The main objective of this thesis is to investigate the contamination level, distribution pattern and sources of OHCs in the YRD. Wildlife from different habitats are used to indicate the environmental pollution situation, and evaluate selected matrices for use in long term biomonitoring to determine the environmental stress the contamination may cause. In addition, a method is developed for dicofol analysis. Moreover, a specific effort is made to introduce statistic power analysis to assist in optimal sampling design. The thesis results show extensive contamination of OHCs in wildlife in the YRD. The occurrences of high concentrations of chlorinated paraffins (CPs) are reported in wildlife, in particular in terrestrial species, (i.e. short-tailed mamushi snake and peregrine falcon). Impurities and byproducts of pentachlorophenol products, i.e. polychlorinated diphenyl ethers (PCDEs) and hydroxylated polychlorinated diphenyl ethers (OH-PCDEs) are identified and reported for the first time in eggs from black-crowned night heron and whiskered tern. High concentrations of octachlorodibenzo-p-dioxin (OCDD) are determined in these samples. The toxic equivalents (TEQs) of polychlorinated dibenzo-p-dioxin (PCDDs) and polychlorinated dibenzofurans (PCDFs) are at mean levels of 300 and 520 pg TEQ g-1lw (WHO2005 TEQ) in eggs from the two bird species, respectively. This is two orders of magnitude higher than European Union (EU) regulation limit in chicken eggs. Also, a novel pattern of polychlorinated biphenyls (PCBs) with octa- to decaCBs, contributing to as much as 20% of total PCBs therein, are reported in birds. The legacy POPs shows a common characteristic with relatively high level of organochlorine pesticides (i.e. DDT, hexacyclohexanes (HCHs) and Mirex), indicating historic applications. In contrast, rather low concentrations are shown of industrial chemicals such as PCBs and polybrominated diphenyl ethers (PBDEs). A refined and improved analytical method is developed to separate dicofol from its major decomposition compound, 4,4’-dichlorobenzophenone. Hence dicofol is possible to assess as such. Statistic power analysis demonstrates that sampling of sedentary species should be consistently spread over a larger area to monitor temporal trends of contaminants in a robust manner. The results presented in this thesis show high CPs and OCDD concentrations in wildlife. The levels and patterns of OHCs in YRD differ from other well studied areas of the world. This is likely due to the extensive production and use of chemicals in the YRD. The results strongly signal the need of research biomonitoring programs that meet the current situation of the YRD. Such programs will contribute to the management of chemicals and environment in YRD, with the potential to grow into the human health sector, and to expand to China as a whole.

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 5: Submitted. Paper 6: Manuscript.