Esta pesquisa tem por objetivo contemplar as variáveis inerentes aos compostos, mais precisamente hidrocarbonetos totais de petróleo em função de sua disposição no meio ambiente, relacionando o comportamento associado ao seu risco toxicológico e de forma inovativa, verificar a influência de se considerar toda a gama de hidrocarbonetos de petróleo na avaliação de risco, quantificando o erro e incerteza de uma avaliação de risco clássica. O escopo de trabalho contemplou a definição da potenciometria local, definição de contaminantes de interesse, modelagens de transporte e para estes contaminantes e definição do programa de gerenciamento da área em função da inclusão de um modelo de risco toxicológico. A área encontra-se inserida em um pacote sedimentar que confere condutividades hidráulicas entre 10-4 e 10-5 cm/s. O modelo de fluxo é radial, e a velocidade linear de fluxo foi definida entre 0,5 e 8,6 m/ano. Os resultados obtidos nas campanhas sistemáticas de monitoramento indicaram que a grande maioria dos poços apresentou concentrações abaixo dos padrões ambientais. Obteve-se a constatação de contaminação efetiva nas áreas compreendidas pela Oxiteno (OXI) e Petroflex (PTX). As simulações de risco efetuadas somente para os compostos BTEX indicaram valores acima dos limites preconizados pelos órgãos ambientais somente em um cenário hipotético de utilização de água captada em área próxima ao poço PPTX 070 (Petroflex). Os demais cenários apresentam riscos dentro dos limites aceitáveis. A quantificação do risco toxicológico associado a toda a gama de hidrocarbonetos de petróleo apresentou valores mais restritivos do que as avaliações executadas para a mesma amostra quando considerou-se somente os compostos padronizados etilbenzeno, tolueno e xilenos, As variações foram de até duas ordens de grandeza no quociente de risco. A definição de metas de remediação e adoção de um programa de gestão específico deve considerar toda a gama de hidrocarbonetos de petróleo e não somente compostos padronizados. / This research aims to consider all the inherent variables to the compounds due to their disposal in the environment, relating their fate associated to their toxicological risk and verify the influence of considering all the petroleum hydrocarbons range in the risk evaluation, quantifying the uncertainty of a classic risk evaluation. The study scope considered the potenciometric trend of the site, definition of compounds of interest; fate and transport modelling for these compounds and finally the definition of the site management program associated to a model of toxicological risk. The potenciometric map illustrates a radial flow for the groundwater, with hydraulic conductivities ranging from 10-4 to 10-5 cm/s. The lineal flow velocity of groundwater was determined between 0,5 m/year and 8,69 m/year. The results obtained in the systematic monitoring campaigns indicated that the great majority of the wells presented concentrations below the environmental standards. It was verified effective contamination in the areas comprehended by Oxiteno (OXI) and Petroflex (PTX). The risk simulations performed for the BTEX compounds indicated values above the limits accepted by the environmental agencies only for a hypothetical scenery regarding explotation of water nearby the PPTX 070 well area. The other scenaries presented acceptable risk limits. The quantification of the toxicological risk associated to all the petroleum hydrocarbons range presents more restrictive values than the evaluations performed for the same water sample, when it was considered only the standardized compounds ethilbenzene, toluene and xilenes, The variations went up to two greatness orders in the risk quotient. The definition of remediation goals and adoption of a specific management program must consider all the petroleum hydrocarbons range and not only standardized compounds.

The objectives of this study are to use phytoremediation ecotechnology to improve the long-term soil pollution contaminated by petroleum and its refined products, and to explore the influence of environmental factors to the effective degradation of TPH.This study is divided into three stages.First, we selected the biofuel crops seeds to test their diesel fuel pollution tolerance.The crops include soybean¡Bsunflower¡Bcanola and corn.This four Taiwanese common energy crops were selected to manually configure three levels of diesel fuel pollution(1000¡B5000¡B10000 mg kg-1)in soil test the seed tolerance experiments.The experimental results in the first stage exhibited that the best energy crop species and non-edible crop(Jatropha),are selected in second phase for contaiminated soil degradation experiment to explore the possible influence of enviromented factors,such as soil moisture¡BpH¡Btotal plate¡Ketc,and to explore the applied fertilizer to increase soil nutrients,whether it will affect the degradation of diesel pollution.Finally, in the third phase, the energy crops were used in the oil-contaminated site to assess their decontamination efficiency. From June 2011 to November 2011, the experimental results shown in the first phase of seed tolerance test, for a period of 30 days showed that the soybean diesel-contaminated soil presented the best tolerance.Although the germination rate was increased with the concentration from 80% to 27%, it showed the best growth conditions.Therefore, in the second phase of test run, the speices of soybean and jatropha were selected prepared with concentrations of 1745¡B6271 and 10072 mg kg-1 dry soil. After 90 day for phytoremediation, soybean group(S) were found that the residual concentrations in soil were measured equal to 524¡B809 and 1913 mg kg-1 dry soil,with the removal rates of 69.97%¡B87.09% and 81.01% respectively.The concentration level of 10000 ppm was found not reach our control standard of 1000 ppm. The soil planted by jatropha(J) showed that residual concentration in soils equial to 303¡B1864 and 4837 mg kg-1 dry soil, with removal rates equal to 82.61%¡B70.27% and 51.98% respectively.Through statistical regression analytical results, the soybean can handle up to a concentration of 5300 mg/kg for diesel, while jatropha can handle up to 2170 mg/kg in this system. Except for the concentration level of 1000 ppm can reach our control standards, the other two groups were found below the control standard. To improve the removal efficieneies, it was suggested that phyto remediation time can be extended.

This study focuses on the Kaohsiung industrial pier sediment survey, assessment and feasibility study of the approach. In this study, field monitoring operations, including the close Salt Water River mouth area of the industrial port (area A), the far Salt Water River mouth area of the industrial port (area B) and for the factories and shipyards at the junction of the terminal area (area C), The sampling of sediments of three core and three surface sediments of area A that used as treating test at laboratory. The survey results show that the industrial pier some heavy metals in the sediment concentration is higher than the quality indicators in the sediment above the limit (ULV), especially copper and zinc. In addition, the concentration of heavy metals of industrial pier area A, B and C of the sediment at least one of them is than current soil control standard. Among them, the frequency of exceeding control standards of copper concentration is the highest, the surface sediments of area A, B and C were about 75%, 42% and 0% respectively, while the core sediments were about 20%, 90% and 15%. These results indicate that the industrial pier sediment required to carry out appropriate pre-treatment to reclamation land to recycling. After investigation, simulation and estimation, the required appropriate treatment sediment in order to landfill volume of industrial pier area A and B (Salt Water River mouth) were approximately 40,000 and 36,400 cubic meters, the total approximately 76,400 cubic meters. Industrial pier is located in the Salt Water River mouth, and therefore withstand the effects of pollutants of the upstream sources flowed in, and than the sediment quality was poor. Sediments were accumulated in the bottom should be removed and sediments at the upstream Salt Water River should be treated too, the remediation and pollution source control for the future to improve the sediment quality is the most important work in Taiwan. In this study, chemical washing and chemical oxidation of the two treatment technology for industrial pier sediment organic pollutants (total petroleum hydrocarbons (TPH) as the target pollutants) to deal with the feasibility test. Sediment to be processed was collected neart the industrial pier, the pH value of approximately 7.1, the moisture content was 43.9%, 20.1% organic matter content, while the particle size composition of mainly fine particles (silt + clay) to about 84.3% handling may be more difficult. The sediments of the TPH concentration of 8,691 mg / kg. Three surfactants Simple Green (SG), Triton X-100 (TX-100) and Tween 80 (TW80) were used at sediment washing test,washing with 60 pv and 5% (v / v) SG could remove 97.3% TPH at the end of the mud; 0.5% (v / v) TX-100 could remove 96.8% TPH; washing with 30 pv, 1% (v / v) TX-100 could remove 94.6% the TPH; washing with 10 pv, 5% (v / v) TX-100 could remove 96.7% TPH; but TW80 leaching ineffective. Oxidation processing, applied 6% H2O2 reaction 180 min, 58.2% of TPH could be removed. Connection of washing and oxidation treatment process, could be removed total of 86% of TPH. The sediment surface morphology before and after treatment were observed by SEM were not significantly different, no surfactant emulsion was left at sediment after treated, this result revealed the connection of washing and oxidation treatment process could remove most of TPH and less harmful to the environment was an available technique.

Esta pesquisa tem por objetivo contemplar as variáveis inerentes aos compostos, mais precisamente hidrocarbonetos totais de petróleo em função de sua disposição no meio ambiente, relacionando o comportamento associado ao seu risco toxicológico e de forma inovativa, verificar a influência de se considerar toda a gama de hidrocarbonetos de petróleo na avaliação de risco, quantificando o erro e incerteza de uma avaliação de risco clássica. O escopo de trabalho contemplou a definição da potenciometria local, definição de contaminantes de interesse, modelagens de transporte e para estes contaminantes e definição do programa de gerenciamento da área em função da inclusão de um modelo de risco toxicológico. A área encontra-se inserida em um pacote sedimentar que confere condutividades hidráulicas entre 10-4 e 10-5 cm/s. O modelo de fluxo é radial, e a velocidade linear de fluxo foi definida entre 0,5 e 8,6 m/ano. Os resultados obtidos nas campanhas sistemáticas de monitoramento indicaram que a grande maioria dos poços apresentou concentrações abaixo dos padrões ambientais. Obteve-se a constatação de contaminação efetiva nas áreas compreendidas pela Oxiteno (OXI) e Petroflex (PTX). As simulações de risco efetuadas somente para os compostos BTEX indicaram valores acima dos limites preconizados pelos órgãos ambientais somente em um cenário hipotético de utilização de água captada em área próxima ao poço PPTX 070 (Petroflex). Os demais cenários apresentam riscos dentro dos limites aceitáveis. A quantificação do risco toxicológico associado a toda a gama de hidrocarbonetos de petróleo apresentou valores mais restritivos do que as avaliações executadas para a mesma amostra quando considerou-se somente os compostos padronizados etilbenzeno, tolueno e xilenos, As variações foram de até duas ordens de grandeza no quociente de risco. A definição de metas de remediação e adoção de um programa de gestão específico deve considerar toda a gama de hidrocarbonetos de petróleo e não somente compostos padronizados. / This research aims to consider all the inherent variables to the compounds due to their disposal in the environment, relating their fate associated to their toxicological risk and verify the influence of considering all the petroleum hydrocarbons range in the risk evaluation, quantifying the uncertainty of a classic risk evaluation. The study scope considered the potenciometric trend of the site, definition of compounds of interest; fate and transport modelling for these compounds and finally the definition of the site management program associated to a model of toxicological risk. The potenciometric map illustrates a radial flow for the groundwater, with hydraulic conductivities ranging from 10-4 to 10-5 cm/s. The lineal flow velocity of groundwater was determined between 0,5 m/year and 8,69 m/year. The results obtained in the systematic monitoring campaigns indicated that the great majority of the wells presented concentrations below the environmental standards. It was verified effective contamination in the areas comprehended by Oxiteno (OXI) and Petroflex (PTX). The risk simulations performed for the BTEX compounds indicated values above the limits accepted by the environmental agencies only for a hypothetical scenery regarding explotation of water nearby the PPTX 070 well area. The other scenaries presented acceptable risk limits. The quantification of the toxicological risk associated to all the petroleum hydrocarbons range presents more restrictive values than the evaluations performed for the same water sample, when it was considered only the standardized compounds ethilbenzene, toluene and xilenes, The variations went up to two greatness orders in the risk quotient. The definition of remediation goals and adoption of a specific management program must consider all the petroleum hydrocarbons range and not only standardized compounds.

abstract: Petroleum contamination is ubiquitous during extraction, transportation, refining, and storage. Contamination damages the soil’s ecosystem function, reduces its aesthetics, and poses a potential threat to human beings. The overall goals of this dissertation are to advance understanding of the mechanisms behind ozonation of petroleum-contaminated soil and to configure an effective integrated bioremediation + ozonation remedial strategy to remove the overall organic carbon. Using a soil column, I conducted batch ozonation experiments for different soils and at different moisture levels. I measured multiple parameters: e.g., total petroleum hydrocarbons (TPH) and dissolved organic carbon (DOC), to build a full understanding of the data that led to the solid conclusions. I first demonstrated the feasibility of using ozone to attack heavy petroleum hydrocarbons in soil settings. I identified the physical and chemical hurdles (e.g., moisture, mass transfer, pH) needed to be overcome to make the integration of chemical oxidation and biodegradation more efficient and defines the mechanisms behind the experimental observations. Next, I completed a total carbon balance, which revealed that multiple components, including soil organic matter (SOM) and non-TPH petroleum, competed for ozone, although TPH was relatively more reactive. Further experiments showed that poor soil mixing and high soil-moisture content hindered mass transfer of ozone to react with the TPH. Finally, I pursued the theme of optimizing the integration of ozonation and biodegradation through a multi-stage strategy. I conducted multi-stages of ozonation and bioremediation for two benchmark soils with distinctly different oils to test if and how much ozonation enhanced biodegradation and vice versa. With pH and moisture optimized for each step, pre-ozonation versus post-ozonation was assessed for TPH removal and mineralization. Multi-cycle treatment was able to achieve the TPH regulatory standard when biodegradation alone could not. Ozonation did not directly enhance the biodegradation rate of TPH; instead, ozone converted TPH into DOC that was biodegraded and mineralized. The major take-home lesson from my studies is that multi-stage ozonation + biodegradation is a useful remediation tool for petroleum contamination in soil. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2018

This thesis presents a model for developing site-specific contingency plans to be used during spill response, remediation, and post-spill monitoring using the Strategic Petroleum Reserve's Bryan Mound site as a case study. Bird and vegetation observations provide baseline data for biological conditions, and sediment sampling for total petroleum hydrocarbons serves as a chemical component of the model. Results demonstrate previously unknown conditions that would hinder remediation and affect the persistence of petroleum contaminants. Results also established previously unmapped dominant bird and vegetation types likely to be impacted by a spill at the site. This model points to a reconsideration of individual facilities' responsibilities when planning for large-scale disasters and protecting the sensitive ecosystems surrounding their sites.

Orientador: Rodrigo Sequinel / Coorientador: Danilo Luiz Flumignan / Banca: Edilene Cristina Ferreira / Banca: Erica Regina Filletti Nascimento / Banca: Mária Cristina Breitkreitz / Banca: Heron Dominguez Torres da Silva / Resumo: Segundo dados, de 2017, da Companhia Ambiental do Estado de São Paulo (CETESB), os postos de combustíveis são responsáveis pela contaminação ambiental de 72% das 5942 áreas contaminadas cadastradas no estado de São Paulo. A contaminação de solos e águas subterrâneas por combustíveis fósseis causam imensos danos ambientais devido à alta toxicidade dos constituintes destes combustíveis, além de apresentarem propriedades carcinogênicas e elevada permanência no solo. O monitoramento ambiental em áreas de risco potencial de contaminação, como postos de combustíveis, é realizado através da análise de hidrocarbonetos totais do petróleo (TPH), entre outros hidrocarbonetos individuais. Estas análises são realizadas através de métodos cromatográficos em fase gasosa que requerem etapas de extração com solventes halogenados, purificação e, muitas vezes, pré-concentração. O elevado custo e o tempo demandado para a quantificação de TPH em solo tornam-se barreiras para o crescimento do monitoramento e acompanhamento de processos de remediação das áreas contaminadas. Desta forma, este trabalho objetivou o desenvolvimento de métodos analíticos mais rápidos e de menor custo para a identificação e quantificação de TPH em solo através da espectroscopia na região do infravermelho próximo (NIR). Três métodos NIR foram desenvolvidos: (i) sem preparo de amostra; (ii) após extração por hexano; e (iii) após extração por etanol. Os modelos de classificação foram desenvolvidos pelo método de análise dis... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: According to the Environmental Company of the State of São Paulo (CETESB), the gas stations are responsible for the environmental contamination of 72% of the 5942 contaminated areas registered in the state of São Paulo. Contamination of soils and groundwater by fossil fuels causes immense environmental damages due to their high toxicity, carcinogenic properties and high permanence in the soil. Environmental monitoring in areas of potential contamination risk, such as gas stations, is carried out through the analysis of total petroleum hydrocarbons (TPH), among other individual compounds. These analyzes are performed by gas chromatographic methods which require some sample preparation steps, such as extraction with halogenated solvents, purification, and often preconcentration. The high cost and time demanded for the quantification of TPH in the soil become barriers for the growth of the monitoring program and remediation processes of the contaminated areas. Therefore, this work aimed at the development of faster and lower cost analytical methods for the identification and quantification of TPH in soil through near-infrared spectroscopy (NIR). Three NIR methods were developed: (i) without sample preparation; (ii) after hexane extraction; and (iii) after extraction with ethanol. The classification models were developed by partial least squares discriminant analysis (PLS-DA) method and the calibration models by partial least squares (PLS) method. In the development of the models... (Complete abstract click electronic access below) / Doutor

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Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-10-15T23:53:48Z No. of bitstreams: 1 ADNA DE ALCÂNTARA E SOUZA BANDEIRA - DISSERTAÇÃO PPGEQ 2010..pdf: 10337833 bytes, checksum: 8e5aa72a95f83ae8223a787549af0b73 (MD5) / Made available in DSpace on 2018-10-15T23:53:48Z (GMT). No. of bitstreams: 1 ADNA DE ALCÂNTARA E SOUZA BANDEIRA - DISSERTAÇÃO PPGEQ 2010..pdf: 10337833 bytes, checksum: 8e5aa72a95f83ae8223a787549af0b73 (MD5) Previous issue date: 2010-11-30 / A indústria petrolífera tem se desenvolvido muito rapidamente nos últimos anos devido aos avanços na descoberta e perfuração de poços cada vez mais profundos. Os resíduos dessas indústrias são classificados pela Associação Brasileira de Normas Técnicas ABNT (2004) como perigosos (Classe I). A Estabilização por Solidificação tem se mostrado uma tecnologia eficiente e bastante utilizada para atenuar e tratar resíduos perigosos além realizar o pré-tratamento dos resíduos antes da disposição em aterro industrial. O objetivo principal desse trabalho foi atenuar Hidrocarbonetos Totais de Petróleo e Óleos e Graxas presentes na borra oleosa de petróleo usando Estabilização por Solidificação. Este trabalho foi realizado no Laboratório de Gestão Ambiental e Tratamento de Resíduos que pertence à Unidade Acadêmica de Engenharia Química da Universidade Federal de Campina Grande. Foi dividido em quatro etapas. Na primeira etapa foi realizado o planejamento experimental. Foi utilizado o fatorial 22 com três pontos centrais. Os fatores adotados foram percentual de borra (10, 15 e 20%) e temperatura de cura (0, 20 e 40°C). Na segunda etapa foi feita a caracterização e classificação da borra de petróleo. Na terceira etapa foi realizada a avaliação dos materiais submetidos à estabilização por solidificação, utilizando uma mistura de cimento Portland simples e argila organofílica como aglomerantes, usando critérios de integridade/durabilidade e imobilização dos contaminantes. Na quarta etapa foi realizada a análise estatística e o balanço de massa do processo. Com esse trabalho, foi possível verificar que a capacidade de absorção de água nos corpos de prova influencia na sua resistência à compressão e, posteriormente, na lixiviação. O teor de óleos e graxas na borra de petróleo é um indicativo de contaminação. Com o tratamento, conseguiu-se uma redução de 86,7% no teor de óleos e graxas, mostrando que a Estabilização por Solidificação pode ser aplicada como pré-tratamento de resíduos perigosos antes de serem dispostos adequadamente em aterros sanitários industriais e/ou como forma de efetuar a atenuação dos contaminantes. Observou-se também que a temperatura não influenciou no processo e que apenas a percentagem de borra pode influenciar nos resultados de óleos e graxas. / The oil industry has developed very rapidly in recent years due to advances in the discovery and drilling wells deeper and deeper. Waste is classified by the Brazilian Association of Technical Standards (ABNT, 2004) as hazardous (Class I). The stabilization by solidification technology has proved an effective and widely used to alleviate and treat hazardous waste in addition carry out pre-treat waste before disposal in landfill. The main objective of this study was to soften Total Petroleum Hydrocarbons and oils/greases present in oily sludge using oil stabilization by solidification. This work was performed at the Laboratory of Environmental Management and Waste belonging to the Academic Department of Chemical Engineering, Federal University of Campina Grande. It was divided into four stages. In the first stage we carried out the experimental design. We used the 2 factorial with three central points. The factors used were the percentage of sludge (10, 15 and 20%) and curing temperature (0, 20 and 40 0 C). The second step was the characterization and classification of oil sludge. The third step was performed to evaluate the materials submitted to the stabilization by solidification using a simple mixture of Portland cement and organoclay as binders, using criteria of integrity/durability and immobilization of contaminants. The fourth stage was performed statistical analysis and mass balance of the process. With this work, we observed that the capacity of water absorption in the specimens influences the compressive strength and the later leaching. The content of oils and greases in the oil sludge is an indicator of contamination. With treatment, achieved a reduction of 86.7% in the concentration of oils and greases, showing that the stabilization by solidification can be applied as a pretreatment of hazardous waste before being appropriately disposed of in landfills and industrial and/or as how to make the attenuation of contaminants. We also observed that the temperature did not influence the process and that only the percentage of sludge can influence the results of oils and greases.