Benzene (C 6H6) is the simplest member of the aromatic hydrocarbon group of chemical compounds. Minute amounts of benzene are naturally released into the environment during volcanic eruptions and forest fires. This extremely stable aromatic compound is also an important industrial chemical and is an integral component of many petroleum products. In fact, benzene is amongst the top 20 in production volume for chemicals produced in the United States. Therefore, it is not surprising that the major reason for environmental contamination through benzene is by anthropogenic sources. Benzene is relatively soluble in water and migrates very quickly in the soil after its entry. The Environmental Protection Agency (EPA) has classified benzene as a Class A carcinogen. Microorganisms play an integral role in the natural attenuation of benzene from the environment. Biodegradation of benzene by oxidation can occur under aerobic, anaerobic and microaerophilic conditions. Biooxidation of benzene under aerobic conditions is well-studied. However, oxygen is scarce in contaminated subsurface environments, and after the aerobic breakdown of benzene, oxygen is quickly depleted from the most heavily contaminated regions leading to the development of extensive anaerobic zones. As a result, there is increased focus on anaerobic benzene degradation as a potential bioremediation technique in anoxic subsurface environments. In aerobic and microaerophilic environments, monooxygenase and dioxygenase enzyme systems have been established to be involved in the breakdown of the benzene ring. However, the genes and enzymes involved in anaerobic benzene oxidation pathway are still unknown. In the present study, Dechloromonas aromatica strain RCB, capable of benzene oxidation with nitrate as the electron acceptor, was used as a model system to investigate the initial steps of the anaerobic benzene oxidation pathway. Strain RCB is capable of completely mineralizing benzene to carbon dioxide in denitrifying conditions. RNA-arbitrarily primed polymerase chain reaction (RAP-PCR), a differential gene expression technique used to randomly reverse-transcribe RNA into cDNA, was conducted to identify genes exclusively expressed during nitrate-dependent benzene oxidation. A total of seven genes were identified as differentially expressed in the presence of benzene using the RAP-PCR approach. Four differentially expressed genes were confirmed by a second method, semiquantitative reverse transcriptase PCR (RT-PCR). Microarray analysis was the second expression analysis technique conducted to identify genes expressed during benzene-oxidizing conditions. Based on fold induction and potential function, six genes were selected from the microarray data and their differential expression was confirmed by using semiquantitative RT-PCR. Interestingly, Daro1556, encoding a hypothetical protein, was identified by both RAP-PCR and microarray analysis. In order to verify the functions of the genes (selected from RAP-PCR and microarray analysis) in nitrate-dependent benzene oxidation, six deletion mutants were constructed in which the target gene was replaced by a tetracycline cassette. The correct insertion of the tetracycline cassette in the mutant genome was confirmed by PCR and Southern blotting. Microarray results were further analyzed by using an unsupervised clustering approach, k-means. A couple of genes (Daro1358 and Daro1359) obtained from cluster analysis were also verified by semiquantitative RT-PCR. These two genes, part of the same operon, encode a two-component monooxygenase system, which is a member of the Rieske non-heme iron aromatic ring-hydroxylating oxygenase family of proteins. In the present investigation, for the first time, involvement of a monooxygenase system (Daro1358 and Daro1359) during benzene oxidation with nitrate reduction was observed. Based on the results obtained from k-means cluster analysis, a model was hypothesized for anaerobic benzene oxidation with nitrate as the electron acceptor in Dechloromonas aromatica strain RCB.

This project was a part of a study to evaluate natural attenuation (NA) as a viable remedial option for petroleum hydrocarbon (PHC) contamination at upstream oil- and gas-contaminated sites in Alberta, Canada. Laboratory mesocosms were set up using groundwater and sediment materials collected from two PHC contaminated sites (Site 1 and Site 3) in Alberta to investigate the enhancement of anaerobic PHC biodegradation by amendment of terminal electraon acceptors (TEAs, nitrate or sulfate) and/or nutrients (ammonium and phosphate). Multiple lines of evidence, including the removal of benzene, toluene, ethylbenzene and xylenes (BTEX) and CCME F1 fraction hydrocarbons (C6 to C10), rapid depletion of TEAs, the production of biogenic gases, and detection of the metabolites verified that anaerobic PHC biodegradation was occurring in both laboratory mesocosm studies. Selective biodegradation of PHCs under different reducing conditions was observed. However, there was no conclusive evidence that one reducing condition will universally favor the biodegradation of specific PHCs. In both studies, nutrient amendment showed no enhancement effects. The calculated first-order biodegradation rates in Site 1 mesocosm study ranged from 0.0032 to 0.033 d-1 for benzene, 0 to 0.028 d-1 for ethylbenzene, 0.0021 to 0.036 d-1 for m-, p-xylenes, and 0.0006 to 0.0045 d-1 for F1-BEX (F1 hydrocarbons exclduding BEX) under the tested conditions. The laboratory first-order biodegradation rates of BEX were higher than the estimated field rates, indicating the potential of enhanced anaerobic biodegradation in situ. However, when comparing the TEA amended mesocosms with the unamended controls (in which iron reduction might be the predominant process), the enhancement effects were less apparent and inconsistent. The calculated first-order biodegradation rates in Site 3 mesocosm study ranged from 0 to 0.0009 d-1 for benzene, 0 to 0.011 d-1 for ethylbenzene, 0 to 0.0016 d-1 for m- and p-xylenes, and 0 to 0.15 d-1 for o-xylene. Sulfate amendment significantly stimulated biodegradation of all xylenes and CCME F1 hydrocarbons. However, there was no definitive evidence that nitrate or sulfate amendment could enhance benzene or ethylbenzene biodegradation. / Environmental Engineering

No description available.

No description available.

This work focused on using a microbubble dispersion to deliver hydrogen and carbon dioxide to anaerobic consortia to stimulate their ability to reductively dehalogenate tetrachloroethylene all the way to ethene and ethane. A continuous flow system, consisting of six anaerobic soil column bioreactors, inoculated with sediments from Virginia Tech's Duck Pond, was used for this study. Two columns received microbubbles containing hydrogen and carbon dioxide, two received sodium propionate, and two were not fed a substrate. A 30 micromolar PCE solution was delivered to the consortia at 3 ml/min. Microbubbles containing a mixture of 90% hydrogen and 10% carbon dioxide were effectively produced in a closed spinning disk generator, and were acceptable for delivering the gases to the columns. After the biodegradation study was completed, the microbubbles were found to have a pH of 4.4, due to the carbon dioxide. Microbubbles amended with NaOH to 0.01 molar yielded pH neutral microbubbles with improved stability. Methane was measured in all six columns throughout the experiment, verifying that methanogens were present. Methane levels were highest in the propionate columns, showing the the methanogens there were more active. Methane levels in the microbubble columns were similar to those in the control columns. Propionate and acetate were not detected in the columns where propionate was fed, showing that proton reducers and acetoclastic methanogens were both active. Recovery of PCE and the degradation products was almost 90% in the microbubble and control columns where most of the PCE was recovered in the effluent. The predominant product in both systems was TCE, although some ethene was detected in all four columns. The control consortia produced TCE averaging about five micromolar while the microbubble columns averaged about two micromolar TCE. One of the components of the microbubbles probably caused the lowered amounts of PCE reduction. That some ethene was seen in the microbubble columns suggests different conditions can be found to stimulate the further reduction of PCE with hydrogen and carbon dioxide microbubbles. The product recovery in the propionate columns was about 64%. Over half of the injected PCE was dechlorinated to ethene and ethane. / Ph. D.

Oil sand deposits in the Athabasca Basin in Alberta represent one of the largest global oil reserves. The bitumen contents of oil sand shallow deposits are recovered by surface mining using modified version of the Clark hot water process. Extraction of bitumen results in extremely large volumes of process water, which are contaminated with naphthenic acids. Various ex-situ treatment techniques including ozonation, advanced oxidation, adsorption, and bioremediation have been evaluated for the treatment of these waters. Previous studies conducted by Paslawski et al. (2009) investigated aerobic biodegradation of naphthenic acids in properly designed and carefully operated bioreactors. In the current work, anaerobic biodegradation of naphthenic acids under denitrifying condition was examined as a potential approach to eliminate the aeration cost in ex-situ treatment and as an alternative for application of in-situ treatment of oil sand process water in stabilization ponds was examined. Using trans-4-methyl-1-cyclohexane carboxylic acid (trans-4MCHCA), a microbial mixed culture developed in earlier works (Paslawski et al., 2009), and nitrate as an electron acceptor, anaerobic biodegradation of trans-4MCHCA were studied in batch and continuous bioreactors: continuous stirred tank reactor (CSTR) and biofilm system. Effects of naphthenic acid concentration, temperature, and loading rate on biodegradation process were investigated. The batch studies showed that initial concentration of trans-4MCHCA influenced the biodegradation rate where the increase in initial concentration of trans-4MCHCA from 100 to 250 mg L-1 led to a higher rate but further increase in concentration did not have a marked effect. Moreover, batch experiments at temperatures ranging from 10° to 35°C demonstrated that the optimum temperature was in the range of 20 - 24°C. Continuous anaerobic biodegradation in the CSTR showed that increase in loading rate of trans-4MCHCA caused an increase in removal rate of both trans-4MCHCA and nitrate. Rates were decreased as the system approached the cell washout. The maximum biodegradation rate and nitrate removal rate, achieved at trans-4MCHCA loading rate of 157.8 mg L-1 h-1, were 105.4 mg L-1 h-1 and 144.5 mg L-1 h-1, respectively. A similar dependency between the loading and removal rates was also observed in the biofilm reactor. The maximum removal rate of trans-4MCHCA and nitrate in the biofilm reactor, operated at room temperature (24 ± 2ºC) were 2,028.1 mg L-1 h-1 and 3,164.7 mg L-1 h-1, respectively and obtained at trans-4MCHCA loading rate of 2,607.9 mg L-1 h-1. Comparison of the results from aerobic batch systems obtained by Paslawski et al. (2009) and the current results showed similar profile where increase in initial concentration of naphthenic acid increased the biodegradation rate of trans-4MCHCA. As far as the effect of temperature is concerned, room temperature (20 - 24ºC) was identified as optimum temperature regardless of mode of biodegradation. Under continuous mode of operation (CSTR and biofilm reactors), anaerobic biodegradation was much faster than its aerobic counterpart. For instance the maximum anaerobic removal rate of trans-4MCHCA in the CSTR was 105.4 mg L-1 h-1, while the highest removal rate achieved in the aerobic CSTR was 9.6 mg L-1 h-1. Similarly, anaerobic biofilm reactor achieved a higher maximum removal rate of 2,028.1 mg L-1 h-1 compared to a 924.4 mg L-1 h-1 removal rate in the aerobic biofilm reactor. The overall finding indicated that biodegradation of trans-4MCHCA can be achieved effectively under anaerobic condition with the rates markedly higher than those for aerobic system.

A utilização do metano (CH4) presente no biogás gerado através da degradação anaeróbica de resíduos orgânicos depositados em aterros sanitários como fonte de energia é uma tecnologia em expansão, principalmente nos países em desenvolvimento. Para assegurar um melhor aproveitamento do CH4 e a viabilidade econômica do projeto de exploração energética é necessário que estes empreendimentos avaliem sua capacidade de produzir este gás com o passar dos anos, mesmo após o encerramento da deposição de resíduos. O potencial de geração é comumente estimado a partir de modelos cinéticos de primeira ordem propostos por conceituadas instituições, entretanto, estudos recentes apontam alto grau de incerteza e diferenças relevantes entre os resultados obtidos com cada metodologia. Este trabalho tem por objetivo analisar a variação dos resultados das estimativas de emissão de metano dos modelos recomendados pela USEPA, Banco Mundial (Scholl Canyon) e IPCC utilizando tanto dados e informações disponibilizadas do aterro sanitário Moskogen, localizado em Kalmar, Suécia, que foi operado entre 1977 e 2008. Além de estimar a capacidade de geração de CH4, objetiva-se identificar qual o modelo cujas estimativas mais se aproximam dos dados de biogás efetivamente medidos e quanto gás ainda pode ser extraído do aterro. O estudo ainda avaliou como valores diferentes para os parâmetros principais dos modelos afetam a estimativa de geração final. O modelo IPCC mostrou-se o mais confiável dentre os analisados, estimando que o aterro Moskogen produza mais de 102 milhões de m de CH4 entre 1977 e 2100, sendo 39,384 milhões passíveis de extração de 2012 a 2100. Os demais modelos apresentaram premissas inadequadas com a realidade do aterro sanitário estudado. Contudo, mesmo com a superioridade do modelo proposto pelo IPCC, maiores estudos são necessários no local, que levantem outras informações de campo como a vazão passiva de gás pela camada de cobertura do aterro e uma melhor estimativa do percentual de material orgânico biodegradável presente em cada fração de resíduos depositada em Moskogen. / The use of methane (CH4) present in the biogas generated by the anaerobic degradation of organic wastes in landfills as an energy source is an expanding technology, especially in developing countries. To ensure a proper utilization of CH4 and the economic feasibility of the energy recovery project it is necessary that these landfills evaluate their capability to produce this gas over the years, even after the end of waste disposal. The generation potential is commonly estimated from first-order kinetic models proposed by reputable institutions, however, recent studies indicate a high level of uncertainty and significant differences between the results obtained with each method. This study aims to analyze the variation of the results of methane generation estimatives, from the models recommended by the USEPA, the World Bank (Scholl Canyon Model) and the IPCC using field data and information provided by Moskogen landfill, located in Kalmar, Sweden, which was operated from 1977 to 2008. In addition to estimating the CH4 generation potential, the objective is to identity which model whose results are closer to the data of the amount of biogas effectively measured and to discover how much gas still can be extracted from the landfill. The study also evaluated how different values to the model main parameters affect the final generation estimative. The IPCC model proved to be the most reliable among the others analyzed, estimating that Moskogen will produce over 102 million m of CH4 between 1977 and 2100, which 39.384 can be extracted from 2012 to 2100. The other models presented inadequate assumptions in comparison to the reality of the studied landfill. Nevertheless, despite the fact that the model proposed by the IPCC has been judged as the most faithful, larger studies are needed on the area, in order to identify more field data, such as the occurrence of passive gas flow through the top covering layers of the landfill and a better estimative of the amount of degradable organic compounds in each fraction of waste disposed in Moskogen.

Made available in DSpace on 2014-06-11T19:27:22Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-11-30Bitstream added on 2014-06-13T20:35:47Z : No. of bitstreams: 1 abreuneto_ms_me_jabo.pdf: 1673746 bytes, checksum: f710855d25440c302ba5cd9d3ff6e36a (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho avaliou-se o desempenho de processo anaeróbio em dois estágios composto por reator compartimentado (ABR) e reator de fluxo ascendente com manta de lodo (UASB), instalados em série, em escala-piloto (volumes de 530 e 120 L, respectivamente), tratando águas residuárias de suinocultura com concentrações de sólidos suspensos totais de 4.591 a 13.001 mg L-1, submetidos a tempos de detenção hidráulica (TDH) de 60 a 24 h no primeiro reator e de 13,6 a 5,4 h no segundo reator. As eficiências médias de remoção de DQOtotal variaram de 69 a 88% no reator ABR e de 34 a 58% no reator UASB, resultando em valores médios de 87 a 95% para o sistema de tratamento anaeróbio em dois estágios (ABR+UASB) com carga orgânica volumétrica (COV) de 11,51 a 21,12 g DQOtotal (L d)-1 no reator ABR, e de 4,21 a 13,29 g DQOtotal (L d)-1 no reator UASB. As eficiências de remoção de SST e SSV variaram de 86 a 96% e 88 a 97% no sistema de tratamento (ABR+UASB). A produção volumétrica de metano máxima de 0,455 m3 CH4 (m3 reator d)-1 ocorreu no reator ABR, com COV de 13,42 g DQOtotal (L d)-1 e TDH de 48 h. Obtiveram-se eficiências médias de remoção de 62 a 95% para Cu, Fe, Mn e Zn e de 30 a 71% para NTK e P-total. Houve remoção de coliformes totais e fecais de 91,935 a 99,667% porém, foram observados nos efluentes número de coliformes fecais acima de 1,5 x 105 NMP/100 mL, o que restringe sua aplicação para a irrigação de plantas... / In this work it was evaluated the performance of two stage anaerobic process constituted of anaerobic baffled reactor (ABR) and an upflow sludge blanket reactor (UASB) installed in series, in pilot scale testing (volumes of 530 and 120 L, respectively) treating swine wastewater with total suspended solid (TSS) concentration of 4591 a 13001 mg L-1 on and with hydraulic detention times (HDT) of 60 to 24 h in the first reactor and 13,6 to 5,4 h in the second reactor. The mean CODtotal removal efficiency varied from 69 to 88% in ABR and from 34 to 58% in UASB reactor, resulting in average values ranging from 87 to 95% for the two stage anaerobic treatment system (ABR+UASB) under organic volumetric load (OVL) of 11.51 to 21.12 g CODtotal (L d)-1 in ABR and 4.21 to 13.29 g CODtotal (L d)-1 in UASB reactor. The TSS and VSS removal efficiency varied from 86 to 96% and 88 to 97% in anaerobic treatment system (ABR+UASB). The maximum volumetric methane production of 0.455 m3 CH4 (m3 reactor d)-1 occurred in ABR reactor with OVL of 13.42 g CODtotal (L d)-1 and HDT of 48 h. The average mean removal efficiencies of 62 to 95% for Cu, Fe, Mn and Zn and of 30 to 71% for NTK and P-total. There was removal efficiency of total and fecal coliforms of 91,935 to 99,667% however, a number of fecal coliforms above 1,5 x 105 NMP/100 mL was observed on the effluents, which restricts its use for crop irrigation ...(Complete abstract, click electronic access below)

A utilização do metano (CH4) presente no biogás gerado através da degradação anaeróbica de resíduos orgânicos depositados em aterros sanitários como fonte de energia é uma tecnologia em expansão, principalmente nos países em desenvolvimento. Para assegurar um melhor aproveitamento do CH4 e a viabilidade econômica do projeto de exploração energética é necessário que estes empreendimentos avaliem sua capacidade de produzir este gás com o passar dos anos, mesmo após o encerramento da deposição de resíduos. O potencial de geração é comumente estimado a partir de modelos cinéticos de primeira ordem propostos por conceituadas instituições, entretanto, estudos recentes apontam alto grau de incerteza e diferenças relevantes entre os resultados obtidos com cada metodologia. Este trabalho tem por objetivo analisar a variação dos resultados das estimativas de emissão de metano dos modelos recomendados pela USEPA, Banco Mundial (Scholl Canyon) e IPCC utilizando tanto dados e informações disponibilizadas do aterro sanitário Moskogen, localizado em Kalmar, Suécia, que foi operado entre 1977 e 2008. Além de estimar a capacidade de geração de CH4, objetiva-se identificar qual o modelo cujas estimativas mais se aproximam dos dados de biogás efetivamente medidos e quanto gás ainda pode ser extraído do aterro. O estudo ainda avaliou como valores diferentes para os parâmetros principais dos modelos afetam a estimativa de geração final. O modelo IPCC mostrou-se o mais confiável dentre os analisados, estimando que o aterro Moskogen produza mais de 102 milhões de m de CH4 entre 1977 e 2100, sendo 39,384 milhões passíveis de extração de 2012 a 2100. Os demais modelos apresentaram premissas inadequadas com a realidade do aterro sanitário estudado. Contudo, mesmo com a superioridade do modelo proposto pelo IPCC, maiores estudos são necessários no local, que levantem outras informações de campo como a vazão passiva de gás pela camada de cobertura do aterro e uma melhor estimativa do percentual de material orgânico biodegradável presente em cada fração de resíduos depositada em Moskogen. / The use of methane (CH4) present in the biogas generated by the anaerobic degradation of organic wastes in landfills as an energy source is an expanding technology, especially in developing countries. To ensure a proper utilization of CH4 and the economic feasibility of the energy recovery project it is necessary that these landfills evaluate their capability to produce this gas over the years, even after the end of waste disposal. The generation potential is commonly estimated from first-order kinetic models proposed by reputable institutions, however, recent studies indicate a high level of uncertainty and significant differences between the results obtained with each method. This study aims to analyze the variation of the results of methane generation estimatives, from the models recommended by the USEPA, the World Bank (Scholl Canyon Model) and the IPCC using field data and information provided by Moskogen landfill, located in Kalmar, Sweden, which was operated from 1977 to 2008. In addition to estimating the CH4 generation potential, the objective is to identity which model whose results are closer to the data of the amount of biogas effectively measured and to discover how much gas still can be extracted from the landfill. The study also evaluated how different values to the model main parameters affect the final generation estimative. The IPCC model proved to be the most reliable among the others analyzed, estimating that Moskogen will produce over 102 million m of CH4 between 1977 and 2100, which 39.384 can be extracted from 2012 to 2100. The other models presented inadequate assumptions in comparison to the reality of the studied landfill. Nevertheless, despite the fact that the model proposed by the IPCC has been judged as the most faithful, larger studies are needed on the area, in order to identify more field data, such as the occurrence of passive gas flow through the top covering layers of the landfill and a better estimative of the amount of degradable organic compounds in each fraction of waste disposed in Moskogen.

Orientador: Roberto Alves de Oliveira / Banca: Edson Aparecido Abdul Nour / Banca: Maria Bernadete Amâncio Varesche / Resumo: Neste trabalho avaliou-se o desempenho de processo anaeróbio em dois estágios composto por reator compartimentado (ABR) e reator de fluxo ascendente com manta de lodo (UASB), instalados em série, em escala-piloto (volumes de 530 e 120 L, respectivamente), tratando águas residuárias de suinocultura com concentrações de sólidos suspensos totais de 4.591 a 13.001 mg L-1, submetidos a tempos de detenção hidráulica (TDH) de 60 a 24 h no primeiro reator e de 13,6 a 5,4 h no segundo reator. As eficiências médias de remoção de DQOtotal variaram de 69 a 88% no reator ABR e de 34 a 58% no reator UASB, resultando em valores médios de 87 a 95% para o sistema de tratamento anaeróbio em dois estágios (ABR+UASB) com carga orgânica volumétrica (COV) de 11,51 a 21,12 g DQOtotal (L d)-1 no reator ABR, e de 4,21 a 13,29 g DQOtotal (L d)-1 no reator UASB. As eficiências de remoção de SST e SSV variaram de 86 a 96% e 88 a 97% no sistema de tratamento (ABR+UASB). A produção volumétrica de metano máxima de 0,455 m3 CH4 (m3 reator d)-1 ocorreu no reator ABR, com COV de 13,42 g DQOtotal (L d)-1 e TDH de 48 h. Obtiveram-se eficiências médias de remoção de 62 a 95% para Cu, Fe, Mn e Zn e de 30 a 71% para NTK e P-total. Houve remoção de coliformes totais e fecais de 91,935 a 99,667% porém, foram observados nos efluentes número de coliformes fecais acima de 1,5 x 105 NMP/100 mL, o que restringe sua aplicação para a irrigação de plantas ...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work it was evaluated the performance of two stage anaerobic process constituted of anaerobic baffled reactor (ABR) and an upflow sludge blanket reactor (UASB) installed in series, in pilot scale testing (volumes of 530 and 120 L, respectively) treating swine wastewater with total suspended solid (TSS) concentration of 4591 a 13001 mg L-1 on and with hydraulic detention times (HDT) of 60 to 24 h in the first reactor and 13,6 to 5,4 h in the second reactor. The mean CODtotal removal efficiency varied from 69 to 88% in ABR and from 34 to 58% in UASB reactor, resulting in average values ranging from 87 to 95% for the two stage anaerobic treatment system (ABR+UASB) under organic volumetric load (OVL) of 11.51 to 21.12 g CODtotal (L d)-1 in ABR and 4.21 to 13.29 g CODtotal (L d)-1 in UASB reactor. The TSS and VSS removal efficiency varied from 86 to 96% and 88 to 97% in anaerobic treatment system (ABR+UASB). The maximum volumetric methane production of 0.455 m3 CH4 (m3 reactor d)-1 occurred in ABR reactor with OVL of 13.42 g CODtotal (L d)-1 and HDT of 48 h. The average mean removal efficiencies of 62 to 95% for Cu, Fe, Mn and Zn and of 30 to 71% for NTK and P-total. There was removal efficiency of total and fecal coliforms of 91,935 to 99,667% however, a number of fecal coliforms above 1,5 x 105 NMP/100 mL was observed on the effluents, which restricts its use for crop irrigation ...(Complete abstract, click electronic access below) / Mestre