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.

The industrial solvent trichloroethylene (TCE) and petroleum hydrocarbons (e.g., fuel oil) are among the most ubiquitous organic compounds found in subsurface contaminated environment. The developed treatment train system included the first stage of groundwater and surfactant flushing followed by the second stage of chemical oxidation such as potassium permanganate (KMnO4) and Fenton-like treatment. The third stage was the application of enhanced bioremediation for the further removal of residual contaminants after the first two treatment processes. The objectives of this study were to (1) assess the applicability of treatment train system for the remediation of organic compounds contaminated subsurface environment, (2) determine the optimal operational conditions of the three-stage treatment system, and (3) evaluate the effects of residual surfactant Simple GreenTM (SG) and hydrogen peroxide (H2O2) after chemical oxidation stage on the efficiency of bioremediation process. In this study, three different surfactants [SG, Triton X-100, and Tween 80] were evaluated in batch experiments for their feasibility on contaminants removal. Results from the surfactant biodegradation and microbial enumeration study indicate that SG was more biodegradable and was able to enhance the microbial activity of the intrinsic microorganisms. Thus, SG was applied in the following batch or column experiments of the treatment train system. Results from this study indicate that approximately 87.6% of TCE in the system (with initial concentration of 40 mg L-1) could be removed from the simulated dense non-aqueous-phase liquids (DNAPLs) system after groundwater flushing followed by biodegradable surfactant (1 g L-1 of SG) flushing, while the TCE concentrations dropped from 40 to 4.96 mg L-1 at the end of the flushing experiment. Moreover, approximately 10.7% of the remaining TCE could be removed from the system after the oxidation process using KMnO4 as the oxidant. Results from the oxidation process show that TCE was reduced from 4.96 to 0.69 mg L-1, and chloride concentation was increased from ND to 0.88 mg L-1 with the presence of 1 g L-1 of SG. The residual 1.7% of the TCE could be further remediated via the enhanced bioremediation stage, and the TCE concentrations dropped from 0.69 mg L-1 to below detection limit at the end of the bioremediation experiment. Results also indicate that the remaining KMnO4 had no significant inhibition on bacterial growth and TCE biodegradation. Thus, SG flushing and KMnO4 oxidation would not cause adverse effect on subsequent bioremediation process using intrinsic bacteria. Thus, complete TCE remediation was observed in this study using the three-stage treatment scheme. Results from the column experiment reveal that a complete TPH removal could be obtained after the application of three consecutive treatment processes. Results show that TPH concentration could be reduced from 50,000 mg kg-1 to below detection limit. This indicates that the treatment train system is a promising technology to remediate fuel-oil contaminated soils. Results from the column study indicate that approximate 80.3% of initial TPH in the soil could be removed after the SG [50 pore volumes (PVs)] followed by groundwater (30 PVs) flushing. The Fenton-like oxidation (with 6% of H2O2 addition) was able to remove another 15.0% of TPH. The observed first-order reaction rate constant of TPH oxidation was 2.74¡Ñ10-2 min-1, and the half-life was 25.3 min during the first 40 min of reaction. The residual 4.7% of the TPH could be further remediated via the aerobic bioremediation process. Thus, complete TPH removal was obtained in this study using the three-stage treatment scheme. The proposed treatment train system would be expected to provide a more efficient and cost-effective alternative to remediate chlorinated solvent and petroleum hydrocarbons contaminated sites.

Thesis (M.S.)--Mississippi State University. Department of Geosciences. / Title from title screen. Includes bibliographical references.

A standardized method to examine soil microbial health incorporating biomass, activity, and diversity measurements is currently lacking, limiting the use of this ecologically relevant endpoint in ecological risk assessments. The soil microbial health of a petroleum hydrocarbon-contaminated boreal forest soil, relative to a reference soil, was examined using a suite of tests. Microbial health impacts in the contaminated soil were observed using nitrification, organic matter decomposition, bait lamina, denaturing gradient gel electrophoresis, community level physiological profiling, and most enzyme assays. Results of heterotrophic plate count and respiration tests indicated higher culturable numbers and activity in the contaminated soil. A data integration technique was developed to incorporate the results from individual tests into an overall conclusion, indicating that soil contamination at the site moderately to severely impacted microbial health. The research presented lays the foundation for the development of a soil microbial health standardized method.

Following the 2010 Deepwater Horizon (DWH) spill, sediment cores were analyzed from marshes at various levels of oiling to determine how deeply oil penetrated sediment in these marsh environments, and if at these sites it had quantifiably affected benthic ecosystems. Minimum mixing depths were determined from penetration of the lithogenic radionuclide 234Th, which ranged from 0.25 to 4.5 cm. Sediment accumulation rates were determined using 210Pb, with verification from 137Cs in selected cores. Lead-210 profiles revealed long-term (decadal) mixing. Bay Jimmy, Louisiana was significantly affected by the DWH oil spill, as indicated by total polycyclic aromatic hydrocarbon concentrations of up to 21,913 ppb. This is far above the level at which adverse biological effects occur (4,022 ppb). Benthic foraminifera responded to the heavy oiling by decreases to standing stock and depth of habitation relative to unoiled sites, as well as exhibiting deformities. These data clearly show that oil can be quickly mixed into salt marsh sediments, with demonstrable impacts on indigenous benthos. Further, radioisotope inventories indicated that most of the sampled sites are in a net erosional state. Should marshes containing trapped DWH oil be submerged by rising sea level, there is a great potential for the remobilization of oil.

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.

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.

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.