Orientador: Mara Akie Iritani, Sueli Yoshinaga Pereira / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociencias / Made available in DSpace on 2018-08-06T16:31:54Z (GMT). No. of bitstreams: 1 Couto_MariaLuizaTeixeira_M.pdf: 3706543 bytes, checksum: f150990d169a1b1034d761a8027c8f53 (MD5) Previous issue date: 2006 / Resumo: A metodologia de Avaliação do Risco é uma das ferramentas de gestão que possibilita encontrar uma solução sustentável considerando a proteção da saúde humana e a remediação de áreas contaminadas. A metodologia de Avaliação do Risco foi desenvolvida pela agência ambiental americana (U.S.EPA) e tem sido a base para aplicação em diversos outros países. Esta metodologia tem como princípio a determinação da probabilidade de ocorrência de efeitos adversos à saúde humana em função do cenário ao qual um receptor está exposto. Estabelece uma seqüência lógica de etapas a serem cumpridas e entre elas temos a quantificação dos riscos potenciais associados às características da população potencialmente exposta, denominadas de fatores de exposição. CETESB utilizou a metodologia de Avaliação do Risco para a determinação dos Valores de Intervenção para solos, que são valores de referência que orientam a classificação de uma área como contaminada. A CETESB, na ausência de dados característicos da população paulista e mesmo brasileira, utilizou fatores de exposição de fontes reconhecidas internacionalmente. Tendo como referência essas considerações, este trabalho foi idealizado em torno de três objetivos principais: (a) realizar uma revisão abrangente das informações recentes no campo de estudos geográficos nacionais e dados internacionais com a perspectiva de consolidar os fatores de exposição para a população paulista e, secundariamente, para a brasileira, (b) analisar a sensibilidade desses novos fatores de exposição frente aos Valores de Intervenção consolidados pela CETESB em 2001 para o Benzeno, Endrin e Níquel considerando os cenários de exposição agrícola, residencial e industrial, e (c) propor valores de fatores de exposição para utilização seja no calculo de novos Valores Orientadores do Estado de São Paulo como no processo de Avaliação do Risco à saúde humana aplicada as áreas contaminadas. Os fatores de exposição foram atualizados através da pesquisa em bancos de dados e literaturas e estimados com base em equações matemáticas especificas, quando pertinentes. A análise de sensibilidade foi realizada calculando-se as doses de ingresso e os valores de risco para as substâncias selecionadas, utilizando o modelo CSOIL e o mesmo procedimentos utilizado pela CETESB para derivação dos Valores de Intervenção. Os resultados mostraram que dentre os parâmetros de exposição avaliados, o peso corpóreo, a taxa de inalação e as taxas de ingestão de solo e água mostraram maior influência nos valores de risco final calculado. A magnitude da influência de cada fator depende das características físico-químicas e o compartimento alvo do contaminante. A avaliação do impacto destes fatores de exposição nos Valores de Intervenção mostra que não haveria alteração para o Benzeno e para o Níquel no cenário residencial. O maior impacto seria no cenário industrial. cujas concentrações aumentariam cerca de 50%. causado principalmente pela exclusão da criança como receptor. No cenário agrícola haveria um aumento de aproximadamente 10% em relação aos valores atuais de intervenção. Este estudo mostra que, apesar de não haver um impacto numérico nos valores de risco calculados, a variação dos fatores de exposição pode afetar de forma significativa os Valores de Intervenção, que foi o exemplo usado neste estudo, mas também nos estudos caso a caso e em outros valores de referência utilizados no gerenciamento de áreas contaminadas no Estado de São Paulo. Há a necessidade de reavaliação constante dos fatores de exposição sempre que forem publicados novos dados e, mais especificamente, para a população paulista, que possui comportamento e características distintas do restante do país / Abstract: The Risk Assessment methodology is a management toei which allows the finding of a sustainable solution considering human health and remediation of contaminated areas. The Risk Assessment methodology was developed by the Environment Protection Agency (EPA) of USA and has been the base for application in many other countries. This methodology is based on adverse effect occurrence probability's determination, given the scenario the that the receptor is exposed. It establishes a logical sequence of steps to be followed, among those, the potential risk quantification associated to the exposed population characteristics, called Exposure Factors. CETESB has used the Risk Assessment methodology to determine Intervention Values for soils, which are reference values to classify an area as contaminated. CETESB, faced a lack of data for São Paulo's and also Brazilian population characteristics, therefore used Exposure Factors of known international sources. Taking into account the mentioned considerations, this project was developed having 3 mains goals: (a) to make a broad revision of recent information in national geographic studies and international data, aiming to consolidate data for São Paulo's population, and secondarily for brazilian population; (b) to analyze these new factors' sensibility to Intervention Values consolidated by CETESB in 2001, to Benzene, Endrin and Nickel, considering agricultura!, residential and industrial scenarios, and (c) to propose Exposure Factors to be used in the new Orientation Values in the State of São Paulo as well as in the human health Risk Assessment process applied in contaminated areas. The Exposure Factors were updated through research in databases and literature sources, and were estimated based on specific mathematic equations, when appropriate. The sensibility analysis was carried out calculating intake doses and Risk values for the selected substances, using the CSOIL model and the same procedures used by CETESB to derivate Intervention Values. The results show that among the assessed parameters, body weight, air intake rate, and water and soil intake rate have the greater influence at the values of the calculated final risk. The magnitude of each factor depends on physical-chemical characteristics and contaminant's target compartment. The impact assessment of these Exposure Factors shows that there would not be changes for Benzene and Nickel in residential scenarios. The greater impact would be in the Industrial scenario, which concentrations would raise around 50%, caused mainly by the exclusion of children as receptors. In the agricultural scenario, there would be a raise of approximately 10%, related to the current intervention values. This study shows that, despite there is no numeric impact on the calculated risk values, the Exposure Factors variation may affect in a significant way the Intervention Values, that was the example used in this study, and also in studies of specific cases and in other reference values used in the management of contamínated areas in the State of São Paulo. A constant reassessment for the exposure factors is needed, whenever new data are published, and more specific, for São Paulo's population, which has different characteristics and behaviors from the rest of Brazil / Mestrado / Administração e Politica de Recursos Minerais / Mestre em Geociências

The influence of crude oil-contaminated and remediated sites on agrifood production is not clearly understood. To address this knowledge gap, the research was divided into two stages involving: (1) assessment of the efficiency of two bioremediation strategies to support hydrocarbons degradation as well as agrifood production with the initial analysis of the experimental materials, and (2) evaluation of the effect of different crude oil remediation intervention values (CRIV) on selected vegetables (Brassica juncea, Brassica oleracea, Lactuca sativa and two different cultivars of Solanum lycopersicum). Results from the first stage showed that the crude oil used had a pristane/phytane ratio of 0.98 (within the 0.8 – 3.0 range of most crude oils), higher concentrations of C10 – C14, C15 – C20 and C21 – C27 alkanes than the C28 – C36 alkanes including higher concentrations of two of the US EPA priority pollutant polycyclic aromatic hydrocarbons (PAHs) - phenanthrene and anthracene. Four treatments were prepared in which weekly tillage enhanced the degradation of C15 – C20 and C21 - C27 alkanes in the Remediation by Enhanced Natural Attenuation (RENA) treatment. The two bioremediation strategies (RENA and bioaugmentation) enhanced PAHs degradation compared with the remediation-study control treatment while only RENA application among the two approaches supported the growth of B. juncea. Although there was no statistical significant difference (p > 0.05) between the major dietary mineral contents of samples from the various treatments compared with the control treatment samples, RENA application affected the Cr, Zn and Pb contents. Meanwhile, the Ca/P (> 1.0) and Na/K (< 0.60) ratios of all the harvested samples imply that they provide a good source of these minerals for bone formation and would not contribute to high blood pressure. The crude oil used also deterred the attack of juvenile caterpillars of cabbage white butterfly. Findings from the second stage revealed that the yield of the green leafy vegetables including one of the selected tomato cultivars (Micro-Tom), was in most cases impaired at CRIV ≥ 3,000 mg/kg total petroleum hydrocarbon (TPH). Compared with the control treatment samples’ composition, crude oil stress at 10,000 mg/kg TPH enhanced the concentration of K, Mn and crude protein of B. oleracea and L. sativa as well as the sucrose, total sugars, total phenolics and total flavonoids contents of the latter vegetable. Sucrose was also only detected in M82 tomato cultivar samples from the crude oil-containing treatments. The Cd content of B. oleracea, Pb contents of: L. sativa and M82 tomato harvested samples were all below the FAO/WHO Codex Alimentarius Commission 2015 recommended maximum levels. However, tartaric acid was only detected in B. oleracea and L. sativa samples from the 10,000 mg/kg TPH treatment as well as in M82 tomato cultivar samples from the treatment involving CRIV of 5,000 mg/kg TPH. Generally, the yield of these crops in response to crude oil contamination varied in which B. juncea had the least tolerance to crude oil stress among the green leafy vegetables tested. Most of the quality parameters in the two tomato cultivars were not affected by CRIV between 750 - 5,000 mg/kg TPH with p-xylene having the greatest toxic potential among the VOCs emitted from the 5,000 mg/kg TPH treatment. The research findings, under the experimental conditions, indicated the effectiveness of RENA for the degradation of low molecular weight PAHs and its agricultural benefits. They also suggest that crude oil-contaminated sites at ≤ 3,000 mg/kg TPH present a similar growing environment to a clean site for agrifood production and the possibility that crude oil stress at 10,000 mg/kg TPH could enhance crop quality. Nonetheless, the contribution of bio- accumulated PAHs in these crops to the food chain demands further investigation.