Comments and Discussion : Minoru Sawai

Pesticides are natural or artificial molecules aimed to kill, or mitigate any harmful organism. Although their use in agriculture provides us with an increased crop yield, remains of chemicals on the products creates health concerns in society. Organophosphates and carbamates are two groups of insecticides. Although they are far more lethal against insects and small animals, they can also cause poisoning in humans through the inhibition of acetylcholinesterase enzyme (AChE) that plays an important role in human nervous system. Therefore, the detection of these compounds is crucial. The conventional methods for the detection of these compounds are expensive, time-consuming and need expertise. In this study, a fast, disposable, cheap and accurate acetylcholinesterase biosensor was developed to detect organophosphate and carbamate-based pesticide residues. By means of adsorption method, AChE, the chromophore 5,5&#039 / -Dithio-bis(2-nitrobenzoic acid) (DTNB) and artificial substrate acetylthiocholine (ATCh) were immobilized on the supporting material. In optimization studies / from 3 to 15U/mL concentrations were experimented for AChE, 1 to 5mM DTNB and 1 to 5mM ATCh concentration gradients were used. v As a result of the optimization studies 12U/mL ACHE concentration, 5mM DTNB concentration and 5mM ATCh concentration were determined for constructing a pesticide biosensor. Detection limit of malathion, an organophosphate-based insecticide was found as 2.5ppm in 5% methanol solution. The biosensor conserved its integrity between pH 4 and 8, and gave false positive results after pH 10. Stability studies showed that, biosensor retained its activity for at least 60 days at 4&deg / C to discrimnate between positive and negative controls.

Perfluorinated compounds, non-degradable xenobiotics in many consumer products, can cause developmental toxicity in animals, and human exposure is associated with asthma symptoms. We tested the hypothesis that sustained chronic exposure to perfluorooctanoic acid (PFOA), fluorotelomer alcohol (FTOH) or perfluorooctanesulfonic acid (PFOS) induces lung dysfunction that exacerbates allergen-induced airway hyperresponsiveness (AHR) and inflammation. Mice were exposed to the chemicals from early gestation day to adulthood. Some pups were sensitized and challenged with ovalbumin. Serum PFOA was analyzed by liquid chromatograph-tandem mass spectrometry. Lung function was measured using a small animal ventilator. We assayed inflammatory cells in the lung, performed PCR for lung cytokines, and examined bronchial goblet cell hyperplasia by histology. Here we show that either PFOA or FTOH exposure can induce AHR, but neither one predisposes for exaggerated allergic lung inflammation or AHR. FTOH or PFOS exposure appears to suppress allergic lung inflammation, but does not affect allergic lung dysfunction.

Thesis (Ph.D.)--University of Florida, 2005. / Typescript. Title from title page of source document. Document formatted into pages; contains 277 pages. Includes Vita. Includes bibliographical references.

- / -

Abstract Organic derivatives of tin, lead, mercury are the most widely distributed organometallic ecotoxicants in the environment. While some of these organometallic compounds exist in the environment as a result of direct discharge, anthropogenic emissions alone cannot explain the ubiquity, for example, of the organomercury and organolead compounds in marine and fresh waters, sediments and biota. It is known that some organometallic compounds are formed via a bioconversion from the inorganic contaminants. Depending on the source, they can enter the environment in varied forms inorganic species of different stability. These can be bio-converted further by environmental biota; for instance metals such as tin and lead can be discharged into the environment in the form of organometallic species which can undergo further transformation. Determination of organometallics in environmental and biological samples is difficult due to matrix effect and their low concentrations. Separation and preconcentration is necessary to enhance final determination. Speciation studies are even more complicated. Speciation is an important aspect and gives information about bioavailability of the metal thus their toxicity. This work focused on the development of a method for speciation of organospecies of tin, lead and mercury. A new derivatisation agent has been synthesised and used successfully. SLM probe extraction has been exposed to a new matrix. Different environmental samples have been analysed for organo-species of tin and lead and their pathways predicted. The SLM probe extraction gives the advantage of carrying out several extractions, reduction of the amount of solvent used and avoidance of emulsion problems. A simple system has been developed and applied successfully on organotin and organolead extraction from aqueous environmental sample. For reproducibility of the results, pH, salinity, stirring rate and extraction time were optimized. An analytical method for simultaneous in situ ethylation, using new derivatisation agent bromomagnesium tetraethylborate (Et4BMgBr), of organotin and organomercury compounds in sediment samples was developed. The determination of mercury and tin compounds is achieved by species-specific isotope dilution, derivatisation and gas chromatography – inductively coupled plasma mass spectrometry (GC-ICP-MS). In derivatisation, pH and the amount of derivatisation agent were studied. Percentage recovery and accuracy of the method was confirmed by comparison of experimental results with sediment and plant certified reference material (IAEA 405 for sediment and CRM 279 for plant). Although organolead compounds as a gasoline additive are banned in most countries, in some regions, lead is still added to gasoline in varying proportions of different tetraalkyllead compounds and contamination by organolead compounds is still present at different places, e.g.: lead alkyl manufactures The use of both tetraalkyllead and butyltin is banned (tetraalkyllead as gasoline additive and butyltin in antifouling pints and PVC materials). This work focussed on their conversion in water and soil. This should provide an insight into their presence in the environment and an understanding of their degradation in the environment. A method for full speciation and determination of alkyl lead and inorganic lead (II) after the tetramethyllead degradation in aqueous samples has been developed. This was accomplished by in situ derivatisation with sodium tetraphenyllead borate NaB(Ph)4 derivative. The derivatisation was carried out directly in the aqueous sample and the derivatives were extracted using the supported liquid membrane probe extraction (SLMPE). The extracted analytes were then transferred to a GC/MS for separation and detection. This study focused on the transformation of tetramethyllead in aqueous media, at different concentration of major elements, K+,Na+,Ca++, Mg++,Cl-,SO4 --. Adsorption / desorption on soil of ionic organolead and organotin were also studied. As South Africa is one of the world’s major producers of coal, mercury should be monitored as it is a side product in coal combustion. The trend of inorganic mercury and methylmercury in sediment found in this work indicated a possible methylation of inorganic mercury to methylmercury in Klipriver sediments.

The ingrained economic, political, and cultural structures in society create difficulties for people to change consumption habits because they have existed in society for a long time where individuals’ social networks affect consumption. The purpose of this research has been to highlight and analyze the effect of the connection between social network and consumption and to reflect on how one's social network affects consumption habits. A quantitative survey using the 2018 Living Costs and Food Survey dataset with 5000 respondents was conducted for this reason. Social cost was used as a measure to highlight the effect it has on consumption. The result highlighted that material products acted as symbolic capital that the respondents consumed to strengthen their social ties that existed within their social networks.

Submitted by Andrea Pereira (andrea.pereira@unipampa.edu.br) on 2017-03-13T17:19:12Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) dissertacao_artur_mestrado_engenharia.pdf: 3325844 bytes, checksum: b863f8afcb5e72944fca004924293530 (MD5) / Approved for entry into archive by Andrea Pereira (andrea.pereira@unipampa.edu.br) on 2017-03-13T17:20:18Z (GMT) No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) dissertacao_artur_mestrado_engenharia.pdf: 3325844 bytes, checksum: b863f8afcb5e72944fca004924293530 (MD5) / Made available in DSpace on 2017-03-13T17:20:18Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) dissertacao_artur_mestrado_engenharia.pdf: 3325844 bytes, checksum: b863f8afcb5e72944fca004924293530 (MD5) Previous issue date: 2015-12-03 / O descarte de efluentes industriais e residenciais em corpos hídricos ganha cada vez mais atenção da fiscalização dos órgãos ambientais. Assim, é crescente a contribuição de grupos de pesquisas científicas em desenvolver novas tecnologias que contribuam para que esses descartes sejam menos prejudiciais à natureza. A indústria têxtil contribui com uma grande geração de poluentes que quando não são devidamente tratados se tornam agravante problema ambiental. Uma das matérias primas da indústria têxtil é a lã de ovinos. Devido às condições como são criadas as ovelhas, para o processamento industrial dessa lã é indispensável a retirada da maior parte possível de impurezas por meio da lavagem, para então ser transformada em fio pelo processo de cardar e por fim ser fiada e tingida. A alta temperatura e pH que são utilizados na lavagem contribuem significativamente para a geração dos lodos como efluente e a alta quantidade de água utilizada faz com que este efluente fique bastante úmido. O método mais comum de tratamento desse tipo de efluente se dá por meio da decantação ou sedimentação através de tratamento biológico via sistema de lodos ativados. Apesar de apresentar uma boa eficiência, esse método não é suficiente para remoção de compostos orgânicos dissolvidos, além de produzir grande volume de lodo. Algumas opções como a secagem ou hidrociclonagem, contribuem para o espessamento dos lodos gerados durante o tratamento do efluente. Os parâmetros geométricos dos hidrociclones dependem da família a qual ele pertence, as configurações da família Rietema e Bradley são os que aparecem com mais frequência nos trabalhos da literatura quando se trata de equipamentos com boa eficiência para separação de sólido-líquido. O Rio Grande do Sul, dentre os estados brasileiros, se destaca tanto na produção têxtil como no cenário da pecuária, em especial na produção de lãs de ovinos, por isso o objetivo desse trabalho foi projetar, analisar e simular a fluidodinâmica de hidrociclones do tipo Rietema e Bradley para o espessamento do lodo produzido por uma indústria têxtil da cidade de Bagé – RS. Primeiro, foi realizado a caracterização física do lodo do efluente através da obtenção da temperatura, da massa específica da fase fluida e da parte sólida, da sua viscosidade, da sua concentração de sólidos, e da sua distribuição do tamanho médio de partículas. Também foi feita a caracterização química através das medidas do pH, da DQO, da quantidade de matéria orgânica e condutividade elétrica. Com base nesses resultados e nas equações que relacionam a eficiência com diâmetro de corte e com o diâmetro da secção cilíndrica do hidrociclone, foi possível projetar e analisar o comportamento das eficiências dos hidrociclones de configuração Rietema e Bradley. Também foi verificado com base nas relações de Euler e Reynold qual dos hidrociclones tem menor gasto energético para uma mesma faixa de eficiência. Por fim, foi realizada a análise numérica por meio de simulação computacional, por CFD utilizando o programa ANSYS para descrever os perfis de velocidade, pressão e o comportamento da fase líquida e sólida no interior dos hidrociclones. Os resultados da caracterização física demostraram que o lodo possui massa específica de 1000,05 kg/m3 e o sólido contido no lodo possui uma massa específica de 1002,64 kg/m3 e diâmetro de partícula de 586 e uma concentração volumétrica de sólidos de 4,2 %. Na sensibilidade paramétrica, os hidrociclones de configuração Rietema e Bradley se comportaram de maneira bastante semelhante. Os resultados das simulações auxiliaram no conhecimento e na interpretação gráfica de como ocorre o movimento do fluido e a separação das fases no interior do hidrociclone. Na visualização dos perfis de velocidade tangencial, foi observado que esta é maior na região central do hidrociclone, onde retornará por movimento helicoidal ascendente, à fase menos densa. As correntes de pressão mostraram que essa variável é maior próxima nas paredes do hidrociclone, o que provoca a separação das fases. Para análise da eficiência foi utilizado o modelo Lagrangeano com curva de dispersões de sólido em água com mediana de distribuição de 586 . Ambos hidrociclones projetados apresentaram uma eficiência de separação de 74 %. / The disposal of industrial and residential wastewater into water bodies has gained increasing attention of surveillance of environmental agencies. So it is increasing the contribution of scientific research groups to develop new technologies to help ensure that these discharges are less harmful to nature. The textile industry contributes a great generation of pollutants that are not properly treated when they become aggravating environmental problem. One of the raw materials of the textile industry is the sheep wool. Due to the sheep conditions are created for the industrial processing of such wool is essential that the largest possible removal of impurities by washing, then to be transformed into yarn by carding process and finally be spun and dyed. The high temperature and pH which are used in the wash contribute significantly to the generation of effluent and sludge as high amount of water used makes this effluent becomes moist enough. The most common method of treatment of this effluent is through decantation or sedimentation through biological treatment through activated sludge system. Despite presenting a good efficiency, this method is not sufficient for removing dissolved organic compounds, besides being very susceptible to the effluent composition and produce large amounts of sludge. Some options like, drying or hydrocycloning, contribute to the thickening of sludges generated during treatment of the effluent. The geometric parameters of hydrocyclones depend on the family to which it belongs, Rietema and Bradley Family settings are appearing more frequently in the work of literature when it comes to equipment with good efficiency for solid-liquid separation. The Rio Grande do Sul, among the Brazilian states, it is so prominent in the textile production and in livestock scenario, especially in wool production of sheep, so the aim of this study was to design, analyze and simulate the fluid dynamics of hydrocyclones type Rietema and Bradley for sludge thickening produced by a textile city of Bage - RS. First the physical characterization was carried effluent sludge by raising the temperature, the density of the fluid phase and the solid part of its viscosity, its solids concentration and its distribution of the average particle size. Also the chemical characterization was done by raising the pH, COD, the amount of organic matter and conductivity. Based on these results and the equations that relate efficiency with cutting diameter and the diameter of the cylindrical section of the hydrocyclone, it was possible to design and analyze the behavior of the efficiencies of Rietema and Bradley configuration hydrocyclones. It also found based on the relationship of Euler and Reynold which the hydrocyclones has lower energy expenditure for the same range of efficiency. Finally, a numerical analysis was carried out through computer simulation by CFD ANSYS software to describe the velocity profile, pressure and performance of liquid and solid phase within the hydrocyclones. The results of the physical characterization showed that the sludge has a specific weight of 1000.05 kg / m3 and the solid contained in the sludge has a specific weight of 1002.64 kg / m3 and a particle diameter of 586 m and a volume concentration of 4 ,2 %. In parametric sensitivity, the configuration hydrocyclones Rietema and Bradley behaved in much the same way. The simulation results helped in knowledge and graphic interpretation of how occurs the fluid motion and phase separation inside the hydrocyclone. In view of the tangential velocity profiles, it was observed that this is higher in the central region of the hydrocyclone, which returns ascending helical movement, the less dense phase. The pressure currents shown that this variable is greater near the walls of the hydrocyclone, which causes phase separation. To analyze the efficiency we used the Lagrangian model with solid dispersions curve in water with a median of distribution of 586 micrometers. Both hydrocyclones designed showed a 74% separation efficiency.

- 4 - Abstract The aim of this study was to carry out phytoextraction experiments using corn plants (Zea mays) and determine the phytoextraction efficiency for specific non-steroidal anti- inflammatory drugs and carbamazepine and their combinations. After 10 days of growth, a nutrient solution containing ibuprofene, naproxene, diclofenac and carbamazepine in concentrations ranging from 5 to 10 mg/L was added to hydrophonically cultivated plants. Nutrient solution samples were taken every 24 hours and the samples were then analysed using a HPLC/DAD system. At the end of the experiment, the experimental plants and roots were analysed for extractable residua using HPLC/DAD + FLD. The greatest phytoextraction efficiency was found for ibuprofene. The second and third most effective extraction was observed for naproxene and diclofenac, depending on the evaluation criteria. The lowest phytoextraction efficiency was observed for carbamazepine. With multi-component experiments, lower phytoextraction efficiency was found out for all substances with the exception of ibuprofene in combination with diclofenac and carbamazepine. The toxic impact of ibuprofene on plant transport mechanisms was also proven. The extractable residua analysis confirmed the ibuprofene's toxicity on plant transport mechanisms and also the...

Interferentes endócrinos são substâncias que podem causar efeitos deletérios na saúde, crescimento e capacidade reprodutiva dos organismos, e colocam em risco a continuidade de várias espécies. Suas fontes são as mais variadas possíveis, sendo possível detectá-los em alguns alimentos, produtos farmacêuticos, produtos químicos e seus respectivos subprodutos de degradação. Também vêm sendo detectados em várias matrizes ambientais, tais como o ar, solo, água e sedimentos. Devido as suas capacidades de ação sinérgica, aditiva e antagônica é extremamente complexa a determinação da relação dose-resposta, informação esta necessária para a definição de limites de padrões de qualidade e medidas de controle e monitoramento. A partir da avaliação do estado da arte relativa ao tema foram apresentados os mais atuais instrumentos de gestão ambiental e suas respectivas aplicações. Finalmente, foi realizado teste visando detectar a eventual presença de efeito estrogênico em amostras de dois sistemas de grande importância para a Região Metropolitana de São Paulo: a água da Represa Guarapiranga e o efluente da Estação de Tratamento de Esgotos Barueri. Os testes realizados foram do tipo in vivo, onde peixes machos da espécie Cyprinus carpio foram expostos a amostras destes dois sistemas e foi investigada a presença da proteína vitelogenina no plasma sanguíneo em concentrações anômalas. Verifica-se a necessidade premente de maiores estudos que foquem o efeito dos interferentes endócrinos na saúde e no meio ambiente, através de ensaios biológicos, de forma a municiar a sociedade de informações que permitam definir medidas estratégicas de atuação para minimização do impacto desta poluição. / Endocrine disrupters are substances that can play a role of deleterious efects in organisms health, growth and reproductive capability. They can be found in food, pharmaceuticals, chemical products and by-products and in diverse environmental matrixes, as air, soil, water and sediments. Because their ability to sinergistic, additive and antagonistic action, it is difficulty to determine the dose-response relationship, which is necessary for establishment of quality standards and monitoring measures. From the assessment of state-of-art about endocrine disrupters were present the most current environmental tools and applications. Finally, one test was performed to detect the possible presence of estrogenic effect in samples of two systems located in Metropolitan Region of São Paulo, from Guarapiranga Reservoir and the effluent from Wastewater Treatment Plant in Barueri. The tests in vivo were with male fish of the species Cyprinus Carpio, and investigated the presence of protein vitellogenin in blood plasma and in anomalous concentrations. There is a need for more studies that focus on the effect of endocrine disrupters on human health and the environment, by means of biological tests, in order to arm the society with informations to set strategic measures of performance for minimizing the impact of this kind of pollution.