Postos revendedores de combustíveis configuram-se como empreendimentos efetiva ou potencialmente poluidores e capazes de gerar impactos ambientais. Este estudo objetivou avaliar os procedimentos empregados no gerenciamento de áreas contaminadas por hidrocarbonetos em postos revendedores e a efetividade das práticas adotadas. A análise baseou-se nos documentos apensados aos Processos de Licenciamento Ambiental de três empreendimentos deste ramo de atividade. Os empreendimentos foram selecionados do Banco de Dados da FEPAM. Os três casos haviam concluído o processo de remediação e se encontravam na etapa de monitoramento para reabilitação. Verificou-se, em todos os casos analisados, que durante a investigação ambiental não foi realizada a delimitação horizontal e vertical das plumas de contaminação, com o estabelecimento do gradiente de concentração das substâncias químicas de interesse, tampouco foram realizadas análises do solo para verificar a demanda de oxidante pela matéria orgânica naturalmente presente. Nos Casos de Estudo 1 e 2, a contaminação ficou restrita à área do empreendimento e o sistema de remedição empregado foi operacionalizado até atingir os valores das referências normativas. No Caso de Estudo 3, ao contrário, a contaminação se estendeu para além dos limites do empreendimento, inclusive com a presença de produto em fase livre. Neste Caso, foi realizada a Análise de Risco à Saúde Humana, para verificar se as concentrações das substâncias químicas de interesse apresentavam riscos à saúde humana. Nos três casos estudados foi empregado o sistema de remediação ativa por oxidação química in situ com o reagente Fenton como oxidante. Salvo algumas oportunidades de melhoria identificadas, os sistemas de remediação empregados atingiram as metas de reabilitação pretendidas, mas deve-se ressalvar que em todos os casos as ações visando à identificação e eliminação do passivo ambiental não foram imediatas, estendendo-se ao longo do tempo, o que faz a ação do órgão ambiental assumir relevância no estabelecimento de prazos e metas. / Fuel stations are configured as enterprises effectively or potentially polluters and able to generate environmental impacts. This study aimed to evaluate the procedures employed in the management of areas contaminated with hydrocarbons in fuel stations and the effectiveness of the practices adopted. The analysis was based on documents attached to the Environmental Licensing Processes of three enterprises of this field of activity. The enterprises were selected from the database of FEPAM. The three cases had completed the remediation process and were in the monitoring stage for rehabilitation. In all the analyzed cases, it was found that during the environmental investigation the horizontal and vertical contamination plumes was not carried out, with the establishment of the concentration gradient of the chemicals of interest, and also the soil analysis to verify the oxidant demand for the organic matter naturally present was not performance. In Study Cases 1 and 2, contamination was restricted to the area of the enterprise and the remediation system operated to the normative reference values. In Case Study 3, on the other hand, a contamination extended beyond the limits of the enterprise, including the presence of product in free phase. In this case, a Human Health Risk Assessment was performed to verify if concentrations of the chemicals of interest presented risk to human health. In the three cases studied, it was employed the active remediation system for in situ chemical oxidation with Fenton reagent as oxidant. Except for some identified improvement opportunities, the remediation systems employed reached the intended rehabilitation goals, but it should be noted that the actions aiming at identifying and eliminating the environmental liabilities were not immediate, extending over time. This makes the action of the environmental agency to assume relevant importance in establishing deadlines and goals.

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

Os Planctomycetes são bactérias que possuem características peculiares, ainda pouco conhecidas. São bactérias de difícil cultivo, sendo descritas em diversos ambientes, mas frequentemente isoladas de ambientes marinhos, principalmente em associações com algas. Aqui apresentamos um amplo estudo deste grupo em solos de manguezais, e reportamos de maneira inovadora o isolamento dessas bactérias. A comparação das comunidades de Planctomycetes em manguezais com diferentes históricos de contaminação permitiu fazer inferências sobre a resposta da comunidade ao ambiente. A análise de sequências pertencentes a este filo, obtidas a partir de amostras dos manguezais - tanto sequências do gene 16S DNAr ou sequências metagenômicas - permitiu inferir sobre a diversidade e as funções destes grupos nos solos dos manguezais estudados. Destacam-se dentre estas o aumento da biodiversidade deste grupo em áreas contaminadas, e as evidências de sua participação na degradação de xenobióticos (demonstrada por predição metagenômica baseada em biblioteca de 16S rDNA, e análise de sequencias metagenômicas). Com estes resultados, foram encontrados em dados metagenômicos, a ocorrência de genes envolvidos na biodegradação de compostos intermediários centrais das vias de degradação. Adicionalmente, mesmo com a dificuldade no cultivo de membros desse grupo, foram obtidos 43 isolados afiliados filogeneticamente principalmente às espécies Blastopirellula marina, Rhodopirellula baltica e Planctomycetes sp. e Pirellula. Foram selecionados dois isolados (Rhodopirellula sp. MGV e Rhodopirellula baltica BR-MGV) para estudos genômicos e metabólicos (via análise de consumo de diferentes fontes de carbono-Biolog). Além disso, foi realizado teste de degradação de hidrocarbonetos com os 43 isolados aferindo as respostas ao contato com contaminantes como hexadecano, naftaleno, fenantreno e fenol. Cinco isolados mostraram a capacidade em degradar três diferentes hidrocarbonetos exceto fenantreno. Estes isolados (Blastopirellula cremea Hex-1 MGV, Blastopirellula marina Nap-Phe MGV, Blastopirellula cremea Hex-2 MGV, Blastopirellula cremea Hex PRIS-MGV e Blastopirellula marina Nap PRIS-MGV) foram enviados a uma análise genômica e suas anotações indicaram a presença de genes envolvidos em vias de degradação de hidrocarbonetos corroborando com o teste realizado em laboratório de degradação dos hidrocarbonetos. Além disso, foi observada através das anotações dos genomas desses microrganismos a ocorrência de síntese de metabólitos secundários, sendo os principais terpenos, bacteriocinas e resorcinol. / Planctomycetes are bacteria with peculiar characteristics and still little known. They are bacteria of difficult cultivation, being described in diverse environments, but often isolated from marine environments, mainly in associations with algae. Here we present an extensive study of this group in mangrove soils and report in an innovative way the isolation of these bacteria. The comparison of the communities of Planctomycetes in mangroves with different contamination histories allowed to make inferences about the response of the community to the environment. The analysis of sequences from this phylum, obtained from samples of the mangroves - both sequences of the 16S DNAr gene or metagenomic sequences - allowed to infer about the diversity and the functions of these groups in the mangrove soils studied. The highlights are the increase of this group\'s biodiversity in contaminated areas, and evidence of its participation in the degradation of xenobiotics (demonstrated by 16S rDNA library-based metagenomic prediction and metagenomic sequence analysis). With these results, the occurrence of genes involved in the biodegradation of central intermediates of the degradation pathways was found in metagenomic data. In addition, even with the difficulty in the cultivation of members of this group, 43 isolates belonging to this phylum were obtained phylogenetically, mainly the species Blastopirellula marina, Rhodopirellula baltica and Planctomycetes sp. and Pirellula. Two isolates (Rhodopirellula sp. MGV and Rhodopirellula baltica BR-MGV) were selected for genomic and metabolic studies (via consumption analysis of different sources of carbon-Biolog). Furthermore, a hydrocarbon degradation test was performed with this library of 43 isolates, assessing the responses to contact with contaminants such as hexadecane, naphthalene, phenanthrene and phenol. Five isolates showed the ability to degrade three different hydrocarbons except phenanthrene. These isolates (Blastopirellula cremea Hex-1 MGV, Blastopirellula marina Nap-Phe MGV, Blastopirellula cremea Hex-2 MGV, Blastopirellula cremea Hex PRIS-MGV and Blastopirellula marina Nap PRISMGV) were sent to a genomic analysis and their notes indicated the presence of genes involved in hydrocarbon degradation pathways, corroborating with the laboratory test for hydrocarbon degradation. In addition, the synthesis of secondary metabolites was evaluated through the annotations of the genomes of these microorganisms, being the main terpenes, bacteriocins and resorcinol.

This research is about the development of a photocatalytic reactor design, Honeycomb, for in-situ groundwater remediation. Photocatalysis, typically a pseudo first order advanced oxidation process, is initiated via the illumination of UVA light on the catalyst, i.e. titanium dioxide (TiO2). In the presence of oxygen, highly reactive oxidising agents are generated such as superoxide (O2-), hydroxyl (OH.-) radicals, and holes (hvb+) on the catalyst surface which can oxidise a wide range of organic compounds. The target contaminant is methyl tert butyl ether (MTBE), a popular gasoline additive in the past three decades, which gives the water an unpleasant taste and odour at 20 μg L-1, making it undrinkable. This research consists of three major parts, i.e. (i) establishing a suitable catalyst immobilisation procedure, (ii) characterisation and evaluation of reactor models and (iii) scale up studies in a sand tank. TiO2 does not attach well onto many surfaces. Therefore, the first step was to determine a suitable immobilisation procedure by preparing TiO2 films using several potential procedures and testing them under the same conditions, at small scale. The coatings were evaluated in terms of photocatalytic activity and adhesion. The photocatalytic activity of the coatings was tested using methylene blue dye (MB), which is a photocatalytic indicator. A hybrid coating, which comprises a sol gel solution enriched with Aeroxide TiO2 P25 powder, on woven fibreglass exhibited the best adhesion and photocatalytic activity among samples evaluated. Thus, it was used to produce immobilised catalyst for this research. Consequently, the immobilisation procedure was scaled up to synthesize TiO2 coatings for the potential photocatalytic reactor design. The photocatalytic activity of the coatings produced from the scaled up immobilisation procedure were reasonably comparable to that produced at small scale. Due to the UVA irradiation and mass transfer limitations, photocatalytic reactors are typically compact in order to maximise their efficiency to accommodate high flows, particularly in water and wastewater treatment. In the case of groundwater, however, the treatment area can span up to meters in width and depth. Groundwater flow is significantly lower than that of water treatment, as the reactor design does not need to be compact. Considering both factors, a photocatalytic reactor design of hexagonal cross-section (Honeycomb) was proposed, in which the structures can be arranged adjacent to each other forming a honeycomb. A model was constructed and tested in a 4 L column (cylindrical) reactor, using the MB test to characterise the reactor performance and operating conditions. This was followed by a hydraulic performance study, which encompasses single and double pass flow studies. The single pass flow study involves the photocatalytic oxidation (PCO) of MB and MTBE, while the double pass flow study was focused on the PCO of MTBE only. The double pass can simulate two serially connected reactors. Single pass flow studies found that the critical hydraulic residence time (HRT) for the PCO of MB and MTBE is approximately 1 day, achieving up to 84 % MTBE removal. Critical HRT refers to the minimum average duration for a batch of contaminant remaining in the reactor in order to maintain the potential efficiency of the reactor. Double pass studies showed the reactor can achieve up to 95 % MTBE removal in 48 hours, and that reactor performance in the field of serially connected reactors can be estimated by sequential order of single pass removal efficiency. In groundwater, there are likely to be other impurities present and the effects of groundwater constituents on the reactor efficiency were studied. The MTBE PCO rate is affected by the presence of organic compounds and dissolved ions mainly due to the competition for hydroxyl radicals and the deactivation of catalyst surface via adsorption of the more strongly adsorbed organic molecules and ions. Despite the presence of organic compounds and dissolved ions, the reactor achieved about 80 % MTBE removal in 48 hours. A double pass flow study showed that the overall efficiency of the photocatalytic reactor in the field can be estimated via sequential order of its efficiency in a single pass flow study using the actual groundwater sample in the laboratory. A sand tank was designed for the simulation of the clean up of an MTBE plume from a point source leakage using the 200 mm i.d. Honeycomb I prototype. Honeycomb I achieved up to 88.1 % MTBE removal when the contaminated groundwater flowed through (single pass) at 14.6 cm d-1. The critical HRT for Honeycomb I was also approximately 1 day, similar to that in the column reactor. The response of MTBE removal efficiency towards flow obtained in the column reactor and sand tank was generic, indicating that the reactor efficiency can be obtained via testing of the model in the column reactor. The presence of toluene, ethylbenzene and o-xylene (TEo-X) decreased the MTBE removal efficiency in both the sand tank and column reactor. The same set of catalyst and 15 W Philips Cleo UVA fluorescent lamp was operated for a total of about 582 h (24 d) out of the cumulative 1039 h (43 d) sand tank experiments, achieving an overall MTBE removal efficiency of about 76.2 %. The experiments in the column reactor and sand tank exhibited the reliability of the immobilised catalyst produced in this research. This research demonstrates the potential of Honeycomb for in-situ groundwater remediation and also proposes its fabrication and installation options in the field.

Current prices and demand for petroleum hydrocabons have generated an increase of oil spills around the country and the world. Health and environmental impacts associated to these organic pollutants represent a huge concern for the general public, leading the public and private sector to develop new technologies and methods to minimize or eliminate those risks. Ex-Situ bioremediation through biopiles, as a main remediation technique to treat a wide range of hydrocarbons, has been a topic of considerable research interest over the last years. It provides an economical and environmental solution to restore the environment to background levels. Nevertheless, successful bioremediation under cold climate conditions is of considerable concern in countries like Canada, as low temperatures can delay the rate of bioremediation of oil hydrocarbons, thus limiting the operation of soil treatment facilities to certain times of the year. Recent research has found out that bioremediation could be conducted even at low or cold temperatures with larger periods of times. And even more, the addition of petroleum degrading microorganisms (bioaugmentation) and nutrients or biosurfactants (biostimulation) could enhance the process in some cases. In the present study, a comprehensive assessment of bioaugmentation and biostimulation strategies for ex-situ bioremediation of petroleum contaminated soil under cold climate conditions is proposed. Field scale biopiles were constructed and subjected to different concentrations of commercial microbial consortia and mature compost, as bioaugmentation and biostimulation strategies, in a soil treatment facility at Moose Creek, Ontario over a period of 94 days (November 2012 to February 2013). Assessment and comparison of the biodegradation rates of total petroleum hydrocarbons (TPH) and their fractions were investigated. Furthermore, a response surface methodology (RSM) based on a factorial design to investigate and optimize the effects of the microbial consortia application rate and amount of compost on the TPH removal was also assessed. Results showed that biopiles inoculated with microbial consortia and amended with 10:1 soil to compost ratio under aerobic conditions performed the best, degrading 82% of total petroleum hydrocarbons (TPHs) with a first-order kinetic degradation rate of 0.016 d_1, under cold temperature conditions. The average removal efficiencies for TPHs after 94 days for control biopiles, with no amendments or with microbial consortia or compost only treatments were 48%, 55%, and 52%, respectively. Statistical analyses indicated a significant difference (p < 0.05) within and between the final measurements for TPHs and a significant difference between the treatment with combined effect, and the control biopiles. On the other hand, the modeling and optimization statistical analysis of the results showed that the microbial consortia application rate, compost amendment and their interactions have a significant effect on TPHs removal with a coefficient of determination (R2) of 0.88, indicating a high correlation between the observed and the predicted values for the model obtained. The optimum concentrations predicted via RSM were 4.1 ml m-3 for microbial consortia application rate, and 7% for compost amendment to obtain a maximum TPH removal of 90.7%. This research contributes to provide valuable knowledge to practitioners about cost-effective and existing strategies for ex-situ bioremediation under cold weather conditions.

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.

No Brasil, a contaminação do solo por derramamentos de combustíveis representa um dos mais graves problemas ambientais e o impacto da introdução de novas misturas como diesel/biodiesel na matriz energética requer investigação quanto a tecnologias apropriadas de remediação. O presente estudo teve por objetivo avaliar diferentes estratégias de biorremediação no tratamento de solo contaminado experimentalmente com óleo diesel B5. Foram conduzidos três experimentos. No primeiro, quatro microcosmos em duplicata, contendo 500 g de solo e 5% (p/p) de óleo diesel B5, todos suplementados com oxigênio através de revolvimento manual e com ajuste de umidade, tiveram como tratamentos: bioestímulo com ajuste de pH (BE1); bioestímulo com ajuste de pH e nutrientes (BE2); bioaumento com ajuste de pH, nutrientes e adição de consórcio microbiano comercial KMA (BAM) e; controle abiótico, com ajuste de pH e solo esterilizado em autoclave (PA). Paralelamente, foi conduzido tratamento por bioaumento com ajuste de pH e nutrientes, suplementação de oxigênio e consórcio KMA, em solo contaminado apenas por diesel a 5% (BAD). A população microbiana foi monitorada através da contagem de UFC e os tratamentos, avaliados pela remoção de carbono orgânico e de hidrocarbonetos de petróleo (n-alcanos C10-C36). No segundo experimento, o metabolismo microbiano aeróbio foi avaliado através da produção de CO2 em respirômetros de Bartha (triplicatas), em solo contaminado com 5% (p/p) de óleo diesel B5, ajustado para pH e umidade, nas seguintes condições: solo com adição do consórcio KMA; solo com adição de cultura microbiana obtida a partir de outro solo proveniente de um posto de combustível com histórico de vazamento de tanques (RES) e; solo esterilizado por adição de azida de sódio a 0,3% (p/p). Como controle, solo sem contaminação, com sua população microbiana autóctone. No terceiro experimento, a capacidade da microbiota autóctone (EX), assim como do consórcio KMA e da cultura RES, em biodegradar óleo diesel B5, diesel e biodiesel de soja foi testada através do uso de indicadores de oxirredução DCPIP e TTC. Os experimentos em microcosmos indicam que houve uma complementaridade metabólica entre a população nativa e o consórcio comercial de microorganismos KMA, cuja presença promoveu um decaimento mais rápido de n-alcanos nas primeiras semanas do experimento. No entanto, após 63 dias de experimento, os tratamentos BAM, BAD e BE2 apresentaram, respectivamente, em média, 92,7%, 89,4% e 81,7% de remoção dos hidrocarbonetos n-alcanos C10-C36, sendo tais diferenças, sem significância estatística. Nos respirômetros, o bioaumento com cultura microbiana RES apresentou a maior produção de CO2 e a maior remoção de hidrocarbonetos (46,2%) após 29 dias. Tanto nos ensaios em microcosmos quanto nos respirométricos, não foi possível estimar a contribuição dos processos abióticos, tendo em vista evidências da existência de atividade microbiana no solo esterilizado térmica ou quimicamente. Os ensaios com os dois indicadores redox mostraram que apenas a microbiota nativa do solo em estudo e a cultura microbiana RES apresentaram potencial para degradar óleo diesel B5, biodiesel de soja ou diesel, quando colocadas em meio mineral contendo tais combustíveis como única fonte de carbono. / In Brazil, the contamination of soils due to spill of fuels is one of the most serious environmental problems. The impact of introducing new fuel mixtures in the energy matrix, such as diesel/biodiesel requires investigation regarding appropriate remediation technologies. The objective of this study was to assess different bioremediation strategies for treatment of soil spiked with diesel B5 (diesel plus 5% of biodiesel w/w). Three experiments were carried out. In the first, four microcosms (in duplicate), with 500g of soil and 5% (w/w) of diesel B5 each, being all of them supplied with oxygen by manual stirring and with moisture, performed the following treatments: bio-stimulation with pH adjustment (BE1); bio-stimulation with pH and nutrients (N, P) adjustment (BE2); bio-augmentation with pH and nutrients adjustment and addition of a commercial consortium of microorganisms KMA (BAM); abiotic processes control with pH adjustment and soil that underwent thermal sterilization (PA). As a control of the effect of biodiesel, a bio-augmentation treatment was carried out with pH and nutrients adjustment, oxygen supply and addition of KMA consortium, in soil contaminated only with diesel at 5% (w/w) (BAD). The microorganisms populations were monitored through colony-forming units CFU, and the treatment efficiency was estimated based on removal of total organic carbon (TOC) and petroleum hydrocarbon (n-alkanes C10-C36). In the second experiment, the microorganisms aerobic metabolism was assessed through measurement of the CO2 production in Barthas respirometers in triplicates, pH and moisture adjustment, under the following conditions: Contaminated soil inoculated with KMA consortium; contaminated soil inoculated with a microorganisms culture obtained from another soil excavated from a gas station with leaking from the tanks (RES); contaminated soil sterilized with sodium azide 0.3% (w/w) (PA). As a control, soil with no contamination and its indigenous microbiota was monitored. In the third experiment, the capacity of the indigenous microbiota (EX), as well as the consortia KMA and RES in biodegrading diesel B5 and pure biodiesel from soil-beans were assessed by using the oxi-reduction indicators DCPIP and TTC. The experiments in microcosms showed a higher percentage of decay in n-alkanes C10-C36 during the first weeks, in those microcosms where commercial consortium KMA was added, suggesting metabolic complementation between the indigenous and the KMA microbiota. However, after 63 days, the treatments BAM, BAD and BE2 showed respectively the average removal of 92.7%, 89.4% and 81.7% of n-alkanes C10-C36, been the differences statistically not significant. In both experiments (microcosms and Bartha respirometers) it was not possible to estimate the contribution of the abiotic processes alone, due to clear indication of microbiological activity in the soils that underwent thermal or chemical sterilization. In the Bartha respirometers, bio-augmentation with the RES culture presented higher CO2 production and the highest hydrocarbons removal (46.2%) after 29 days. The assays with the redox indicators showed that both the native microbiota of the soil and the RES microbial culture presented potential to degrade diesel B5, biodiesel and diesel, when placed in mineral media with these fuels as the only carbon source.

[pt] O presente trabalho avaliou a eficácia da dessorção térmica in situ em remediar materiais contaminados por hidrocarbonetos de petróleo em refinarias. Paralelamente, foi projetado e construído um novo sistema modular para ser empregado sob dutovias para remediação de britas contaminadas. Os resultados do programa experimental revelaram ser possível a remediação de pavimentos de concreto contaminados por óleo combustível. A aplicação de calor na superfície do pavimento reduziu em até 65 por cento a sua resistência, porém propiciou a restauração de sua cor original. Verificou-se que os resíduos do processo, após análises mineralógicas por difração de raios X e químicas por espectroscopia de fluorescência, apresentavam uma composição muito semelhante ao solo empregado como material de construção dos aterros da refinaria, sugerindo que o resíduo possa ser advindo de transporte eólico. O sistema desenvolvido no presente trabalho apresentou um desempenho satisfatório. Verificou-se a necessidade de aeração do material remediado para eliminar a produção de coque. Adicionalmente, observou-se a importância de um bom isolamento térmico para minimizar o consumo energético e impedir a propagação de calor e das emissões para a atmosfera. As emissões geradas pelo aquecimento consistiam de olefinas e parafinas que podem ser devidamente tratadas pelo oxidador térmico. / [en] This dissertation assessed the adequacy of in situ thermal desorption (istd) in cleaning oil contaminated debris from Refineries. A new modulated istd system was designed and built in order to remediate oiled cobbles under pipeways. The experimental results revealed the possibility of cleaning concrete pavements contaminated by heavy oil. The thermal desorption process restored their original color but reduced their resistance up to 65 percent. It was observed that the resulting debris, after mineralogical analyses by X-ray diffraction and chemical analysis by X-Ray fluorescence, have a similar composition to the soil employed in the fills throughout the Refinery, indicating that the debris could well have been transported by the wind. The system devised here had a satisfactory performance. It was observed the necessity of aeration during the treatment in order to avoid the production of coke. Additionally, it was also observed the importance of a good thermal insulation in order to minimize power consumption and the propagation of heat and gas emissions to the atmosphere. The gases emissions consisted mainly of olefins and paraffins that had been reasonably been treated by the thermal oxidizer devised herein.

No Brasil, a contaminação do solo por derramamentos de combustíveis representa um dos mais graves problemas ambientais e o impacto da introdução de novas misturas como diesel/biodiesel na matriz energética requer investigação quanto a tecnologias apropriadas de remediação. O presente estudo teve por objetivo avaliar diferentes estratégias de biorremediação no tratamento de solo contaminado experimentalmente com óleo diesel B5. Foram conduzidos três experimentos. No primeiro, quatro microcosmos em duplicata, contendo 500 g de solo e 5% (p/p) de óleo diesel B5, todos suplementados com oxigênio através de revolvimento manual e com ajuste de umidade, tiveram como tratamentos: bioestímulo com ajuste de pH (BE1); bioestímulo com ajuste de pH e nutrientes (BE2); bioaumento com ajuste de pH, nutrientes e adição de consórcio microbiano comercial KMA (BAM) e; controle abiótico, com ajuste de pH e solo esterilizado em autoclave (PA). Paralelamente, foi conduzido tratamento por bioaumento com ajuste de pH e nutrientes, suplementação de oxigênio e consórcio KMA, em solo contaminado apenas por diesel a 5% (BAD). A população microbiana foi monitorada através da contagem de UFC e os tratamentos, avaliados pela remoção de carbono orgânico e de hidrocarbonetos de petróleo (n-alcanos C10-C36). No segundo experimento, o metabolismo microbiano aeróbio foi avaliado através da produção de CO2 em respirômetros de Bartha (triplicatas), em solo contaminado com 5% (p/p) de óleo diesel B5, ajustado para pH e umidade, nas seguintes condições: solo com adição do consórcio KMA; solo com adição de cultura microbiana obtida a partir de outro solo proveniente de um posto de combustível com histórico de vazamento de tanques (RES) e; solo esterilizado por adição de azida de sódio a 0,3% (p/p). Como controle, solo sem contaminação, com sua população microbiana autóctone. No terceiro experimento, a capacidade da microbiota autóctone (EX), assim como do consórcio KMA e da cultura RES, em biodegradar óleo diesel B5, diesel e biodiesel de soja foi testada através do uso de indicadores de oxirredução DCPIP e TTC. Os experimentos em microcosmos indicam que houve uma complementaridade metabólica entre a população nativa e o consórcio comercial de microorganismos KMA, cuja presença promoveu um decaimento mais rápido de n-alcanos nas primeiras semanas do experimento. No entanto, após 63 dias de experimento, os tratamentos BAM, BAD e BE2 apresentaram, respectivamente, em média, 92,7%, 89,4% e 81,7% de remoção dos hidrocarbonetos n-alcanos C10-C36, sendo tais diferenças, sem significância estatística. Nos respirômetros, o bioaumento com cultura microbiana RES apresentou a maior produção de CO2 e a maior remoção de hidrocarbonetos (46,2%) após 29 dias. Tanto nos ensaios em microcosmos quanto nos respirométricos, não foi possível estimar a contribuição dos processos abióticos, tendo em vista evidências da existência de atividade microbiana no solo esterilizado térmica ou quimicamente. Os ensaios com os dois indicadores redox mostraram que apenas a microbiota nativa do solo em estudo e a cultura microbiana RES apresentaram potencial para degradar óleo diesel B5, biodiesel de soja ou diesel, quando colocadas em meio mineral contendo tais combustíveis como única fonte de carbono. / In Brazil, the contamination of soils due to spill of fuels is one of the most serious environmental problems. The impact of introducing new fuel mixtures in the energy matrix, such as diesel/biodiesel requires investigation regarding appropriate remediation technologies. The objective of this study was to assess different bioremediation strategies for treatment of soil spiked with diesel B5 (diesel plus 5% of biodiesel w/w). Three experiments were carried out. In the first, four microcosms (in duplicate), with 500g of soil and 5% (w/w) of diesel B5 each, being all of them supplied with oxygen by manual stirring and with moisture, performed the following treatments: bio-stimulation with pH adjustment (BE1); bio-stimulation with pH and nutrients (N, P) adjustment (BE2); bio-augmentation with pH and nutrients adjustment and addition of a commercial consortium of microorganisms KMA (BAM); abiotic processes control with pH adjustment and soil that underwent thermal sterilization (PA). As a control of the effect of biodiesel, a bio-augmentation treatment was carried out with pH and nutrients adjustment, oxygen supply and addition of KMA consortium, in soil contaminated only with diesel at 5% (w/w) (BAD). The microorganisms populations were monitored through colony-forming units CFU, and the treatment efficiency was estimated based on removal of total organic carbon (TOC) and petroleum hydrocarbon (n-alkanes C10-C36). In the second experiment, the microorganisms aerobic metabolism was assessed through measurement of the CO2 production in Barthas respirometers in triplicates, pH and moisture adjustment, under the following conditions: Contaminated soil inoculated with KMA consortium; contaminated soil inoculated with a microorganisms culture obtained from another soil excavated from a gas station with leaking from the tanks (RES); contaminated soil sterilized with sodium azide 0.3% (w/w) (PA). As a control, soil with no contamination and its indigenous microbiota was monitored. In the third experiment, the capacity of the indigenous microbiota (EX), as well as the consortia KMA and RES in biodegrading diesel B5 and pure biodiesel from soil-beans were assessed by using the oxi-reduction indicators DCPIP and TTC. The experiments in microcosms showed a higher percentage of decay in n-alkanes C10-C36 during the first weeks, in those microcosms where commercial consortium KMA was added, suggesting metabolic complementation between the indigenous and the KMA microbiota. However, after 63 days, the treatments BAM, BAD and BE2 showed respectively the average removal of 92.7%, 89.4% and 81.7% of n-alkanes C10-C36, been the differences statistically not significant. In both experiments (microcosms and Bartha respirometers) it was not possible to estimate the contribution of the abiotic processes alone, due to clear indication of microbiological activity in the soils that underwent thermal or chemical sterilization. In the Bartha respirometers, bio-augmentation with the RES culture presented higher CO2 production and the highest hydrocarbons removal (46.2%) after 29 days. The assays with the redox indicators showed that both the native microbiota of the soil and the RES microbial culture presented potential to degrade diesel B5, biodiesel and diesel, when placed in mineral media with these fuels as the only carbon source.

La bio-remédiation in situ est une technique de réhabilitation couramment utilisée pour le traitement des sols et des nappes contaminés, notamment par les hydrocarbures pétroliers. Si démontrer la pertinence de ce type de traitement constitue un préalable incontournable pour chacun des sites où il est mis en œuvre, l’efficacité du traitement dépend de ses conditions de mise en œuvre dans le contexte spécifique d’un site. Le suivi et le contrôle des différents processus qui gouvernent les phénomènes de biodégradation est complexe, et leur optimisation constitue un élément clé de la réussite du traitement tant au plan technique qu’économique. La démarche générale du travail de thèse porte sur le développement d’une méthodologie permettant d’employer la modélisation dans une démarche de gestion (au sens des textes de 2007) d’un site contaminé par des hydrocarbures pétroliers traité par biodégradation in situ. L’originalité du travail de thèse porte sur l’utilisation de la modélisation comme outil de compréhension des mécanismes et d’aide à la décision à chaque étape du traitement : (i) Dimensionnement de l’installation : définir la meilleure option envisageable, (ii) suivi de l’efficacité du traitement : optimiser le procédé et (iii) prédiction et justification de l’arrêt du traitement : sécuriser en termes de garantie de résultat. Les données d’un site d’étude servent de support dans la définition de l’approche méthodologique de modélisation. A chaque étape d’un projet de bio-remédiation in situ peut être associée une étape de modélisation qui fera appel à des moyens plus ou moins sophistiqués avec des exigences de précision variables. Le premier outil développé concerne l’estimation des incertitudes prédictives dans les modèles mis en œuvre. Cet aspect est fondamental, dès lors que l’on souhaite utiliser la modélisation dans un processus d’aide à la décision. Les processus de bio-remédiation in situ impliquent des relations complexes et incertaines entre la biomasse, les contaminants et les mesures de contrôle appropriées. Prévoir la performance du traitement (en termes de réduction du flux et/ou de la masse) constitue un défi en raison des incertitudes liées aux propriétés du milieu, de la source et aux incertitudes liées aux mécanismes de bio-remédiation. L’étude de la contribution des incertitudes paramétriques dans la prédiction de la performance du traitement est réalisée avec la méthode du « Null Space Monte Carlo » (NSMC) implémentée dans l’outil PEST. Le second outil utilisé concerne l’optimisation du design et/ou du monitoring d’un procédé de bio-traitement in situ. Dans ce contexte, deux objectifs peuvent être envisagés à savoir la réduction du flux de contaminants d’une part, et l’élimination de la masse à la zone source d’autre part. L’outil utilisé est un algorithme d’optimisation mathématique dénommé “Particle Swarm Optimisation” (PSO). Le choix de la fonction objectif à optimiser est particulièrement important et s’avère lié au comportement spécifique hydrogéochimique du site considéré. Cette étude montre que les outils NSMC et PSO s’avèrent appropriés dans l'utilisation de modèles de transport réactif dans la gestion environnementale. Les temps de calcul de ces modèles hautement paramétrés et non linéaires limitent encore l'utilisation de la modélisation comme outil d’aide à la décision. Malgré ces limites, l’approche proposée pour gérer la bio-remédiation in situ des eaux souterraines sur site réel peut être efficace pour fournir un soutien dans la gestion du traitement d’une pollution, étendant ainsi le domaine d’application de la modélisation numérique. Cette approche permet aussi de mettre en évidence des difficultés dues aux spécificités du site ou à la technique même de traitement choisie, permettant d’alerter à temps les gestionnaires. / In-situ bioremediation is a commonly used remediation technology to clean up the subsurface of petroleum-contaminated sites. Although demonstrating the relevance of this type of treatment is an essential prerequisite for each site where it is implemented, the effectiveness of the treatment depends on its implementation conditions in the site-specific context. The monitoring and control of different processes that govern biodegradation phenomena is complex, and optimization is a key element of successful treatment both technically and economically. The general approach of the thesis is the development of a methodology for using modelling in a management approach (as defined in the French regulatory text) of petroleum-contaminated site treated by in situ biodegradation. The work focuses on the use of modelling as a tool for understanding mechanisms and for decision support at every stage of treatment: • System design: defining the best possible option.• Monitoring the effectiveness of treatment: process optimization.• Prediction and justification of stopping treatment: analysis of the uncertainty on the treatment result. Data from two study sites are used to define the modelling methodology. At each stage of the bio-remediation project (design, conception, monitoring and optimization) may be associated a modelling stage that will be more or less sophisticated depending on accuracy requirements. The first tool developed involved predictive uncertainty analysis, which is crucial when modelling is used as a decision support tool, and can be used at the design process step or for predicting the effectiveness of treatment. The process of in-situ bioremediation involves complex and uncertain relationships among biomass, contaminants and appropriate control actions. Forecasting remedial performance (in terms of flux and mass reduction) is a challenge due to uncertainties associated with (i) the medium and source properties and (ii) the efficiency of concentration reducing mechanisms. Parametric uncertainty contributions involved in forecasting treatment performance is carried out with the “Null-Space Monte Carlo” (NSMC) method implemented in the PEST tool. The second tool relates design and / or monitoring optimization of the bio-treatment method. In this context, two purposes can be considered: the reduction of contaminants flux or mass in the source zone. The tool used is a mathematical optimization algorithm called "Particle Swarm Optimization" (PSO). The choice of the objective function to be optimized is particularly important and appears to be related to hydrogeochemical site-specific behavior. This study showed that the NSMC and PSO methods are suitable tools for an efficient use reactive transport models in environmental management. The computation time of these highly parameterized and nonlinear models still limit the use of modelling as a decision support tool. Despite these limitations, the proposed approach for managing the bioremediation in-situ groundwater on actual site can be effective to provide support in managing the treatment of pollution, extending the field of application of numerical modelling. This approach also allows to highlight difficulties due to site-specific behavior or to the treatment technique applied, and to inform decision support managers in consequence.