京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22758号 / 工博第4757号 / 新制||工||1744(附属図書館) / 京都大学大学院工学研究科都市社会工学専攻 / (主査)教授 CRUZ Ana Maria , 教授 堀 智晴, 准教授 横松 宗太 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Submitted by Angélica Vieira de Souza null (angelicaviso@hotmail.com) on 2018-01-09T18:55:39Z No. of bitstreams: 1 SouzaLopes_AngelicaVieiraDOC.pdf: 10321700 bytes, checksum: 4ba6df8d0f4c9b90967437b8b728a72f (MD5) / Approved for entry into archive by Adriana Aparecida Puerta null (dripuerta@rc.unesp.br) on 2018-01-10T17:14:47Z (GMT) No. of bitstreams: 1 souzalopes_av_dr_rcla.pdf: 10321692 bytes, checksum: 59f8d46531ef1e32b00f1bccaa895cda (MD5) / Made available in DSpace on 2018-01-10T17:14:47Z (GMT). No. of bitstreams: 1 souzalopes_av_dr_rcla.pdf: 10321692 bytes, checksum: 59f8d46531ef1e32b00f1bccaa895cda (MD5) Previous issue date: 2017-11-22 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A presente Tese de Doutorado teve como escopo avaliar as ocorrências dos acidentes com produtos químicos no estado de São Paulo. Apesar da utilização de novas tecnologias que visam a minimizar ou eliminar a ocorrência dos acidentes com tais produtos, houve aumento no número de acidentes com esses produtos, no período de 1980 – 2009, no estado de São Paulo. Um acidente com produto químico pode contaminar as águas e solos, devido ao vazamento de substâncias químicas, acarretando danos irreparáveis ao meio ambiente; além de ocasionar, por conseguinte, graves danos aos seres humanos, inclusive com óbitos. Conforme dados coletados, 72,2% do total dos acidentes com produtos químicos, ocorridos no estado de São Paulo, no período de 1980-2009, foram registrados nas atividades, relacionados aos riscos industriais e riscos tecnológicos. Nas atividades referentes aos riscos industriais: armazenamento, descarte, indústria, postos e sistemas retalhistas de combustíveis, ocorreram 22,6% do total de acidentes; nas atividades referentes aos riscos tecnológicos: transportes aquaviário, ferroviário, por duto e rodoviário, ocorreram 49,6% do total dos acidentes. Tais dados sobre os acidentes com produtos químicos só foram possíveis de serem devidamente analisados e interpretados porque foram espacializados. Nesse sentido, o uso do software Arc Gis foi importante para visualizar o total de acidentes, causas e meios atingidos no estado de São Paulo e, posteriormente, a distribuição espacial desses acidentes com produtos químicos por Região Administrativa, foi de grande valia para a compreensão dos acidentes pesquisados. A pesquisa revelou, também, que a legislação ambiental brasileira e paulista apresenta um histórico de atribuição de regulamentos referentes à preservação ambiental, relacionado ao desenvolvimento econômico desde a década de 1970. A tese a ser defendida, portanto, é a seguinte: apesar do emprego de novas tecnologias, da consciência ambiental e da legislação ambiental existente, muitos acidentes com produtos químicos têm ocorrido, ainda, no estado de São Paulo, demandando estudos sobre esses acidentes e a necessidade de fiscalização na aplicação das leis ambientais. / The purpose of this PhD thesis was to evaluate the occurrence of chemical accidents in the São Paulo state. Despite the use of new technologies aimed at minimizing or eliminating the occurrence of accidents with such products, there was an increase in the number of accidents with these products, from 1980 to 2009, in the São Paulo state. A chemical accident can contaminate water and soil due to the release of chemicals, causing irreparable damage to the environment; besides causing, consequently, serious damages to the human beings, even with deaths. According to data collected, 72.2% of the total number of chemical accidents occurred in the São Paulo state during the period 1980-2009 were recorded in activities related to industrial risks and technological risks. In activities related to industrial risks: storage, disposal, industry and gas stations, there were 22.6% of total accidents; in activities related to technological risks: waterway, rail, duct and road transportation, 49.6% of all accidents occurred. Such data on chemical accidents were only possible to be properly analyzed and interpreted because they were spatialized. In this sense, the use of the Arc Gis software was important to visualize the total number of accidents, causes and means reached in the São Paulo state and, later, the spatial distribution of these accidents with chemical products by Administrative Region, was of great value for the understanding of the accidents investigated. The research also revealed that Brazilian and São Paulo environmental legislation presents a history of the attribution of regulations regarding environmental preservation, related to economic development since the 1970s. The thesis to be defended, therefore, is the following: despite employment new technologies, environmental awareness and existing environmental legislation, many accidents with chemical products have also occurred in the São Paulo state, demanding studies on these accidents and the need for enforcement in the application of environmental laws.

The production and processing of various chemicals and raw materials all around the world currently exceeds hundreds of millions of tonnes a year and is constantly growing. In addition, the spectre of produced materials is increasing, including relatively toxic compounds. It is absolutely clear that such production volumes lead to a risk of accidents with the leakage of chemical toxicants, and {--} depending on the toxicity of the relevant substances {--} these accidents represent a serious threat for human health, animals and the environment.Disasters involving chemicals drew public attention already in the 20th century, when ways were sought to guarantee the safety of production, storage and transportation of hazardous materials. This is also an essential prerequisite for the occurrence of an accident involving the leakage of chemical toxicants {--} the presence of such toxicants in the production, processing, storage or transportation.Whether during wars or in peacetime, there are situations when large numbers of people can be exposed to the effects of a wide spectre of hazardous chemical substances (NCHL). These situations include military operations, campaigns by the integrated rescue system (IZS), industrial accidents or acts of terror. In developed industrial countries, the capacities used for the production, storage, processing and transportation of NCHL are usually localized in urban industrial zones. The high concentrations of these hazardous chemical substances within these zones represent a potential health risk for the people nearby. Chemical safety is a challenge and a must. I find this issue attractive and therefore decided to analyse, in my thesis, the causes of mass chemical intoxication and their consequences on the affected population. The objective of this diploma thesis is to compare the forms of protection and liquidation of the consequences of such accidents and try to find, structure and unify the recommendations regarding the solution of emergencies associated with mass chemical intoxications. Another objective was to verify the hypothesis that regulations and existing procedures regarding the solution of emergencies associated with mass chemical intoxications do not correspond with today{\crq}s standards and the on-going development of chemical noxious agents.

Nowadays the number of produced chemicals is increasing very rapidly. However, technological processes are gradually improving and safety of handling chemicals is increasing. Unfortunately, even today, chemical accidents can happen. To alleviate results or to prepare for protection of humans, extensive knowledge is necessary to estimate the course of a chemical accident. One of the means of accident mitigation are modern modelling programs that will help us to clarify the implications and consequences of the course of chemical accidents. Based on the results of such modelling, different organizational and safety measures (preventive, oppressive, protective, rescue and relief character) can be taken to increase readiness for disasters and especially to reduce vulnerability of population.

A maior parte de desastres químicos no estado de São Paulo é gerada por acidentes com transporte rodoviário de cargas perigosas (cerca de 40%). A coleta de informações ambientais das áreas atingidas depende de vistoria emergencial que muitas vezes traz riscos e dificuldades às equipes de atendimento envolvidas. O objetivo principal da pesquisa foi verificar a aplicabilidade de sensoriamento remoto por VANTs para auxílio na avaliação e monitoramento de impactos ambientais causados por acidentes envolvendo transportes de cargas perigosas em rodovias. Para isso, foram caracterizados os principais projetos de sensoriamento remoto por VANTs existentes e em desenvolvimento e identificadas evoluções e tendências de aplicações, em especial, civis, com maior detalhamento dos projetos brasileiros. Identificaram-se os benefícios que a tecnologia pode oferecer para a aplicação desejada. Definiu-se a parametrização técnica de VANTs mais adequados para viabilizar a aplicação em análise. Foi indicado um VANT da classe Mini ou Close Range. Foram identificados os cenários ambientais possíveis em situações emergenciais pós acidentes com transporte rodoviário de cargas perigosas. A partir das informações levantadas, estudou-se a viabilidade técnica, econômica e legal da aplicação por meio de hipóteses e deduções. Os resultados mostram que imagens aéreas podem auxiliar as equipes a avaliarem remotamente a situação ambiental, de forma mais rápida e segura e com geração de melhores informações. Além disso, a tecnologia pode trazer vantagens econômicas para os responsáveis pelo acidente. Conclui-se que atualmente as plataformas VANTs e sensores passíveis de serem transportados por elas são aplicáveis e podem servir adequadamente de tecnologia para sensoriamento remoto, com foco para o uso proposto. Porém, faz-se a ressalva que do ponto de vista legal, atualmente há restrições para a atividade de VANTs no Brasil que podem inviabilizar a utilização em foco. / The most part of chemical disaster in the São Paulo state is generated by accidents involving hazardous cargo highway transportation (40%). The acquisition of environmental information in these areas depends of an emergency survey that often brings risks and difficulties for care teams involved. The main objective of the research was to verify the applicability of UAV remote sensing to assist evaluation and monitoring environmental impacts caused by accidents involving hazardous materials transport on highways. The major UAV remote sensing projects existing were characterized and trends of applications were identified. Brazilian and civil projects were detailed. The benefits offered by technology for desired applications were identified and a technique parameterization of adequate UAVs, for application under considerations, was defined. A Mini or Close Range UAV was appointed. The possible environmental scenarios in post emergency situations, involving accidents caused by road transportation of dangerous cargoes, were identified. From the information gathered, technical feasibility, economic and legal aspects were studied, through assumptions and deductions The results show that aerial images can help teams remotely assess the environmental situations, generating better, faster and safer information. Moreover, technology can bring economic advantages to those responsible for the accidents. We conclude that currently, UAV platforms and sensors are applicable and constitute an adequate remote sense technology for its intended use. However, there are legal restrictions for the UAV activity in Brazil that can derail its utilization.

Introdução. Acidentes ambientais envolvendo vazamentos de combustíveis automotivos em Postos e Sistemas Retalhistas no Estado de São Paulo, representam 9,6% (522) do total de acidentes ambientais registrados (5.413), no CADAC - Cadastro de Acidentes Ambientais da Companhia de Tecnologia de Saneamento Ambiental - CETESB, de 1978 a 2003. Dentre as inúmeras razões para explicar o crescente aumento dessas ocorrências, nos últimos anos, destaca-se o envelhecimento de tanques, tubulações e acessórios. A realização de uma avaliação rápida por parte das equipes de atendimento à emergência é fundamental para identificar os eventuais riscos de explosão e de efeitos adversos à saúde pública, bem como para a identificação da(s) fonte(s) causadora(s) do problema. Objetivo. Definir os procedimentos técnicos e os recursos humanos e materiais necessários bem como a seqüência de ações a serem executadas por equipes de atendimento emergencial nos vazamentos e/ou derramamentos de combustíveis automotivos em postos e sistemas retalhistas. Metodologia. A metodologia empregada nesse trabalho é do tipo descritiva, desenvolvida a partir da pesquisa bibliográfica, em agências ambientais nacionais e internacionais, catálogos de fabricantes de equipamentos portáteis de detecção de gases e vapores tóxicos e inflamáveis, normas técnicas internacionais sobre vazamentos de substâncias líquidas inflamáveis e de práticas recomendáveis para atendimento envolvendo materiais perigosos, bem como da experiência do autor em doze anos de atuação como químico do Setor de Operações de Emergência da CETESB. Resultados. A definição da seqüência mínima de ações, dos recursos humanos e materiais, dos procedimentos técnicos a serem adotados no atendimento emergencial de vazamentos de combustíveis automotivos e a consolidação dessas informações na forma de um protocolo. Conclusões. Este protocolo apresenta-se como um instrumento importante para garantir eficiência dos atendimentos emergenciais, não apenas minimizando os riscos para a saúde da população do entorno destes empreendimentos, como também os danos ambientais decorrentes e os custos envolvidos nas operações de emergência. / Introduction: Environmental accidents involving leakage of automotive fuels at Gas Stations and Retailing Systems in the State of São Paulo account for 9.6% (522) of the total number of registered environmental accidents (5,413), according to CADAC - Environmental Accidents Register of the Environmental Sanitation Technology Company (CETESB) in the period between 1978 and 2003. Among the spate of reasons to explain the increase in these occurrences over the past few years, the aging of tanks, tubings and accessories stands out. A rapid evaluation by the teams which attend to emergencies is fundamental in the identification of eventual risks of explosions and adverse effects on public health, as well as the identification of the causative source(s) of the problem. Objective: To define the technical procedures, human resources and necessary materials, as well as the sequence of actions to be executed by teams for emergency response to accidents involving leakage and/or spillage of automotive fuels at gas stations and retaliling systems. Methodology: The methodology employed in this work is of the descriptive type, developed from bibliographic research at national and international environmental agencies, catalogues of manufacturers of portable toxic and inflammable gases and vapors detectors, international technical norms on leakages of various liquid and flammable substances and from practices recommended for the attending to hazardous materials, as well as the author\'s twelve years of experience in action as a chemist for the Emergency Operations Sector of CETESB. Results: The definition of the minimum sequence of actions, the human resources and materials, the technical procedures to be followed in response to emergency in automotive fuel leakage and the consolidation of this information in a protocol. Conclusions. This protocol is an important instrument in guaranteeing a better efficiency in these emergency responses, not only minimizing the risks to public health upon the failure of these ventures, but also the resulting environmental damage and involved costs in the emergency operation.

Introdução. Acidentes ambientais envolvendo vazamentos de combustíveis automotivos em Postos e Sistemas Retalhistas no Estado de São Paulo, representam 9,6% (522) do total de acidentes ambientais registrados (5.413), no CADAC - Cadastro de Acidentes Ambientais da Companhia de Tecnologia de Saneamento Ambiental - CETESB, de 1978 a 2003. Dentre as inúmeras razões para explicar o crescente aumento dessas ocorrências, nos últimos anos, destaca-se o envelhecimento de tanques, tubulações e acessórios. A realização de uma avaliação rápida por parte das equipes de atendimento à emergência é fundamental para identificar os eventuais riscos de explosão e de efeitos adversos à saúde pública, bem como para a identificação da(s) fonte(s) causadora(s) do problema. Objetivo. Definir os procedimentos técnicos e os recursos humanos e materiais necessários bem como a seqüência de ações a serem executadas por equipes de atendimento emergencial nos vazamentos e/ou derramamentos de combustíveis automotivos em postos e sistemas retalhistas. Metodologia. A metodologia empregada nesse trabalho é do tipo descritiva, desenvolvida a partir da pesquisa bibliográfica, em agências ambientais nacionais e internacionais, catálogos de fabricantes de equipamentos portáteis de detecção de gases e vapores tóxicos e inflamáveis, normas técnicas internacionais sobre vazamentos de substâncias líquidas inflamáveis e de práticas recomendáveis para atendimento envolvendo materiais perigosos, bem como da experiência do autor em doze anos de atuação como químico do Setor de Operações de Emergência da CETESB. Resultados. A definição da seqüência mínima de ações, dos recursos humanos e materiais, dos procedimentos técnicos a serem adotados no atendimento emergencial de vazamentos de combustíveis automotivos e a consolidação dessas informações na forma de um protocolo. Conclusões. Este protocolo apresenta-se como um instrumento importante para garantir eficiência dos atendimentos emergenciais, não apenas minimizando os riscos para a saúde da população do entorno destes empreendimentos, como também os danos ambientais decorrentes e os custos envolvidos nas operações de emergência. / Introduction: Environmental accidents involving leakage of automotive fuels at Gas Stations and Retailing Systems in the State of São Paulo account for 9.6% (522) of the total number of registered environmental accidents (5,413), according to CADAC - Environmental Accidents Register of the Environmental Sanitation Technology Company (CETESB) in the period between 1978 and 2003. Among the spate of reasons to explain the increase in these occurrences over the past few years, the aging of tanks, tubings and accessories stands out. A rapid evaluation by the teams which attend to emergencies is fundamental in the identification of eventual risks of explosions and adverse effects on public health, as well as the identification of the causative source(s) of the problem. Objective: To define the technical procedures, human resources and necessary materials, as well as the sequence of actions to be executed by teams for emergency response to accidents involving leakage and/or spillage of automotive fuels at gas stations and retaliling systems. Methodology: The methodology employed in this work is of the descriptive type, developed from bibliographic research at national and international environmental agencies, catalogues of manufacturers of portable toxic and inflammable gases and vapors detectors, international technical norms on leakages of various liquid and flammable substances and from practices recommended for the attending to hazardous materials, as well as the author\'s twelve years of experience in action as a chemist for the Emergency Operations Sector of CETESB. Results: The definition of the minimum sequence of actions, the human resources and materials, the technical procedures to be followed in response to emergency in automotive fuel leakage and the consolidation of this information in a protocol. Conclusions. This protocol is an important instrument in guaranteeing a better efficiency in these emergency responses, not only minimizing the risks to public health upon the failure of these ventures, but also the resulting environmental damage and involved costs in the emergency operation.

The increasing mass and complexity of chemicals being produced and transported has resulted in more rigorous demands on both authorities as well as chemical-handling industries to assess the risks involved. The Environment-Accident Index (EAI), has been proposed as a planning tool created as an equation in which chemical properties (variables describing the chemical involved) are combined with site-specific properties (variables describing the accident site). The EAI is intended to facilitate assessment of the environmental effects related to chemical accident scenarios and hence assist the organisation of preventative programs. The main objective of the work described in this thesis was to evaluate, develop and improve the proposed EAI. The steps involved in the development process included I) evaluation of the feasibility of the EAI approach, II) selection of a representative and diverse set of chemical accidents to be used in the development III) the use of questionnaires and expert judgements to develop response values for environmental effects of a chemical accident, and IV) to create a new EAI model using multivariate modelling (PLS). The EAI approach proved to be useful in the work to protect the environment in case of a chemical accident. A representative set of accidents was selected by means of statistical multivariate design (PCA) based on assembled data related to a set of 55 chemical accidents. The selection generated a set of accidents representing a diverse spectrum of chemical accident scenarios. To develop a measure of environmental effects of the chemical accidents i.e. responses, an expert panel was asked to judge their environmental effects (such as effects on animal life in the aquatic or terrestrial environment). The results showed that the judgements give a rough estimate of environmental effects that could be used as responses in the development of the EAI. The developed responses were then related to the chemical and site-specific properties to create a new EAI model. This resulted in a PLS-based EAI connected to a new classification scale. The advantages of the new EAI are that it can be calculated without the use of tables; it can estimate the effects for all included responses, and make a rough classification of chemical accidents according to the new classification scale. Finally, the new EAI is a more stable model than the previously proposed EAI, and it is founded on a valid base of accident scenarios, making its use for a variety of chemicals and situations more reliable since it covers a broader spectrum of accident scenarios. The new EAI can be expressed as a regression model to facilitate calculation of the index for people that do not have access to PLS. The highest priorities for further refining the new EAI in the future are: external validation of the EAI; further refinement of the formula’s structure; adjustment of the new classification scale; and real-life evaluation of the EAI.

A maior parte de desastres químicos no estado de São Paulo é gerada por acidentes com transporte rodoviário de cargas perigosas (cerca de 40%). A coleta de informações ambientais das áreas atingidas depende de vistoria emergencial que muitas vezes traz riscos e dificuldades às equipes de atendimento envolvidas. O objetivo principal da pesquisa foi verificar a aplicabilidade de sensoriamento remoto por VANTs para auxílio na avaliação e monitoramento de impactos ambientais causados por acidentes envolvendo transportes de cargas perigosas em rodovias. Para isso, foram caracterizados os principais projetos de sensoriamento remoto por VANTs existentes e em desenvolvimento e identificadas evoluções e tendências de aplicações, em especial, civis, com maior detalhamento dos projetos brasileiros. Identificaram-se os benefícios que a tecnologia pode oferecer para a aplicação desejada. Definiu-se a parametrização técnica de VANTs mais adequados para viabilizar a aplicação em análise. Foi indicado um VANT da classe Mini ou Close Range. Foram identificados os cenários ambientais possíveis em situações emergenciais pós acidentes com transporte rodoviário de cargas perigosas. A partir das informações levantadas, estudou-se a viabilidade técnica, econômica e legal da aplicação por meio de hipóteses e deduções. Os resultados mostram que imagens aéreas podem auxiliar as equipes a avaliarem remotamente a situação ambiental, de forma mais rápida e segura e com geração de melhores informações. Além disso, a tecnologia pode trazer vantagens econômicas para os responsáveis pelo acidente. Conclui-se que atualmente as plataformas VANTs e sensores passíveis de serem transportados por elas são aplicáveis e podem servir adequadamente de tecnologia para sensoriamento remoto, com foco para o uso proposto. Porém, faz-se a ressalva que do ponto de vista legal, atualmente há restrições para a atividade de VANTs no Brasil que podem inviabilizar a utilização em foco. / The most part of chemical disaster in the São Paulo state is generated by accidents involving hazardous cargo highway transportation (40%). The acquisition of environmental information in these areas depends of an emergency survey that often brings risks and difficulties for care teams involved. The main objective of the research was to verify the applicability of UAV remote sensing to assist evaluation and monitoring environmental impacts caused by accidents involving hazardous materials transport on highways. The major UAV remote sensing projects existing were characterized and trends of applications were identified. Brazilian and civil projects were detailed. The benefits offered by technology for desired applications were identified and a technique parameterization of adequate UAVs, for application under considerations, was defined. A Mini or Close Range UAV was appointed. The possible environmental scenarios in post emergency situations, involving accidents caused by road transportation of dangerous cargoes, were identified. From the information gathered, technical feasibility, economic and legal aspects were studied, through assumptions and deductions The results show that aerial images can help teams remotely assess the environmental situations, generating better, faster and safer information. Moreover, technology can bring economic advantages to those responsible for the accidents. We conclude that currently, UAV platforms and sensors are applicable and constitute an adequate remote sense technology for its intended use. However, there are legal restrictions for the UAV activity in Brazil that can derail its utilization.

The master's thesis focuses on the toxicological aspects of chemical accidents. The aim is to determine the main acute risk of dangerous toxic chemical substances that can be escape in chemical accidents and determine their impact on life and damage to the health of the population and characterize the factors affecting the spread of these dangerous chemicals. The practical part focuses on the toxicological aspects of selected industrial pollutants.