Sedimento do reservatório hipereutrófico de Salto Grande, localizado na cidade de Americana, São Paulo, foi cultivado em condições anaeróbias em meio mineral adicionado de compostos orgânicos (ácidos voláteis e álcoois) com a finalidade de favorecer a metanogênese do sistema. Com a produção de 70% de metano o sedimento foi utilizado para o teste de degradação anaeróbica do TCE. Os testes foram realizados sob atmosfera de N2/CO2 (70:30%) em frascos reatores a 25ºC e agitação constante de 150 rpm. Os frascos reatores foram preparados com meio mineral, acrescido de fontes orgânicas (5 mM de ácidos acético, fórmico e butírico, mas 2,5 mM de ácido lático e 5 mM de etanol e metanol) e inoculado com 5 g de sólidos totais voláteis por litro. Foram preparados frascos com 12 e 6 mg de tricloroetileno por litro. Dois tipos de controles foram preparados, um sem tricoroetileno e outro sem inóculo. Análise da diversidade microbiana utilizando a metodologia do DGGE - Eletroforese em Gel com Gradiente Desnaturante - foram feitas com amostras dos frascos reatores no final do experimento. O DNA da comunidade foi extraído de acordo com o protocolo descrito por TSAI & OLSON (1991) e fragmentos do DNAr 16S foram amplificados com \"primers\" do Domínio Archaea e Bacteria. Os resultados dos testes de degradação do TCE demonstraram a remoção biótica de 68% e 66% nos reatores contendo 6 e 12 mg TCE/L, respectivamente, depois de 56 dias de incubação. No final do experimento morfologias similares aos gêneros Methanosarcina e Methanosaeta estavam presentes. A análise da diversidade microbiana não revelou uma significativa na comunidade após a adição do TCE, demonstrando que a microbiota enriquecida proveniente do reservatório de Salto Grande foi resistente à concentração do TCE estudada podendo ser responsável pelo processo de degradação sob metanogênese. / Sediments from the supereutrophic reservoir of Salto Grande, City of Americana, São Paulo State, Brazil, were cultivated under anaerobic conditions in a mineral medium added of organic compounds (volatile fatty acids and alcohols) in order to produce methane. Under 70% of methane production, sediment samples were used for tests of TCE anaerobic degradation. The tests were carried out under N2/CO2 (70:30%) atmosphere in reactor flasks, at 25°C, and constant shaking at 150 rpm. The reactor flasks were prepared with mineral medium, added with organic sources [5 mM of acetic, formic and butyric acids, plus 2.5 mM of lactic acid and 5 mM of ethanol and methanol each], and inoculated with 5 g of STV/L of the sediments. Amounts of 6 and 12 mg/L of TCE concentrations were evaluated. Two types of control reactors were prepared, without TCE and without sediments. Diversity analyses using the DGGE - Denaturing Gradient Gel Eletrophoresis - technique were done with samples from the reactor flasks at the end of the experiment. The community DNA was extracted as described by TSAl & OLSON (1991) and fragments of the 16SDNAr were magnified using the PCR methodology, with Bacteria and Archaea domain primers. The results showed degradation of 40% of TCE at concentrations of 6 mg/L and 12 mg/L after 13 days of incubation time, and complete organic acids removal with 40% of methane in the atmosphere. A second addition of 9 mM of the former organic acids indicated and 4.5 mM of lactic acid resulted in 90% of TCE removal, with 50% of methane, after 56 days of incubation time. Morphologies similar to the genera Methanosarcina, Methanosaeta and Methanospirillum were verified. The microbial diversity analysis did not reveal significant differences among Bacteria and Archaea domains under TCE additions. It was possible to assume that the enriched microbiota from the Salto Grande reservoir was resistant to the concentrations of TCE studied and can be responsible for the degradation processes under methanogenesis.

Sedimento do reservatório hipereutrófico de Salto Grande, localizado na cidade de Americana, São Paulo, foi cultivado em condições anaeróbias em meio mineral adicionado de compostos orgânicos (ácidos voláteis e álcoois) com a finalidade de favorecer a metanogênese do sistema. Com a produção de 70% de metano o sedimento foi utilizado para o teste de degradação anaeróbica do TCE. Os testes foram realizados sob atmosfera de N2/CO2 (70:30%) em frascos reatores a 25ºC e agitação constante de 150 rpm. Os frascos reatores foram preparados com meio mineral, acrescido de fontes orgânicas (5 mM de ácidos acético, fórmico e butírico, mas 2,5 mM de ácido lático e 5 mM de etanol e metanol) e inoculado com 5 g de sólidos totais voláteis por litro. Foram preparados frascos com 12 e 6 mg de tricloroetileno por litro. Dois tipos de controles foram preparados, um sem tricoroetileno e outro sem inóculo. Análise da diversidade microbiana utilizando a metodologia do DGGE - Eletroforese em Gel com Gradiente Desnaturante - foram feitas com amostras dos frascos reatores no final do experimento. O DNA da comunidade foi extraído de acordo com o protocolo descrito por TSAI & OLSON (1991) e fragmentos do DNAr 16S foram amplificados com \"primers\" do Domínio Archaea e Bacteria. Os resultados dos testes de degradação do TCE demonstraram a remoção biótica de 68% e 66% nos reatores contendo 6 e 12 mg TCE/L, respectivamente, depois de 56 dias de incubação. No final do experimento morfologias similares aos gêneros Methanosarcina e Methanosaeta estavam presentes. A análise da diversidade microbiana não revelou uma significativa na comunidade após a adição do TCE, demonstrando que a microbiota enriquecida proveniente do reservatório de Salto Grande foi resistente à concentração do TCE estudada podendo ser responsável pelo processo de degradação sob metanogênese. / Sediments from the supereutrophic reservoir of Salto Grande, City of Americana, São Paulo State, Brazil, were cultivated under anaerobic conditions in a mineral medium added of organic compounds (volatile fatty acids and alcohols) in order to produce methane. Under 70% of methane production, sediment samples were used for tests of TCE anaerobic degradation. The tests were carried out under N2/CO2 (70:30%) atmosphere in reactor flasks, at 25°C, and constant shaking at 150 rpm. The reactor flasks were prepared with mineral medium, added with organic sources [5 mM of acetic, formic and butyric acids, plus 2.5 mM of lactic acid and 5 mM of ethanol and methanol each], and inoculated with 5 g of STV/L of the sediments. Amounts of 6 and 12 mg/L of TCE concentrations were evaluated. Two types of control reactors were prepared, without TCE and without sediments. Diversity analyses using the DGGE - Denaturing Gradient Gel Eletrophoresis - technique were done with samples from the reactor flasks at the end of the experiment. The community DNA was extracted as described by TSAl & OLSON (1991) and fragments of the 16SDNAr were magnified using the PCR methodology, with Bacteria and Archaea domain primers. The results showed degradation of 40% of TCE at concentrations of 6 mg/L and 12 mg/L after 13 days of incubation time, and complete organic acids removal with 40% of methane in the atmosphere. A second addition of 9 mM of the former organic acids indicated and 4.5 mM of lactic acid resulted in 90% of TCE removal, with 50% of methane, after 56 days of incubation time. Morphologies similar to the genera Methanosarcina, Methanosaeta and Methanospirillum were verified. The microbial diversity analysis did not reveal significant differences among Bacteria and Archaea domains under TCE additions. It was possible to assume that the enriched microbiota from the Salto Grande reservoir was resistant to the concentrations of TCE studied and can be responsible for the degradation processes under methanogenesis.

Made available in DSpace on 2015-05-14T12:20:03Z (GMT). No. of bitstreams: 1 ArquivoTotalCarlos.pdf: 18836457 bytes, checksum: 7f91c4802d5cf87f50a5c63ef01320f4 (MD5) Previous issue date: 2013-06-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Na sociedade da informação, os órgãos julgadores, dentre os quais se inclui o Tribunal de Contas do Estado da Paraíba, são incansavelmente cobrados por métodos cada vez mais eficiente, célere e eficaz no desempenho de suas atribuições evitando transtornos e consequências prejudiciais aos que a eles recorrem para resolução de suas lides. Nessa perspectiva, a egrégio Corte de Contas Paraibana dentro de uma nova ordem processual, procedeu à mudança nos processos sobre a sua jurisdição de procedimentos do suporte em meio físico para o eletrônico, regulamentado pela Lei Complementar estadual n.º 91, de 29 de outubro de 2009. Nessa pesquisa, o caso analisado é um estudo objetivando apreciar se o procedimento eletrônico implantado pelo TCE/PB, contribui, com a diminuição do prazo para julgamento dos processos de prestação de contas, garantindo assim o cumprimento do Princípio da Celeridade Processual e Duração Razoável do Processo. Para concretização da pesquisa se realizou uma pesquisa do tipo exploratória, seguindo uma abordagem quantitativa baseado nos elementos da estatística descritiva, utilizando-se de um estudo de caso tendo como universo o próprio TCE/PB, de onde foram extraídos os dados da pesquisa através do sistema eletrônico de tramitação-TRAMITA. Quanto aos Sujeitos apreciou-se a média de dias para julgamento das prestações de contas anuais das camaras municipais, Prefeituras, órgão integrantes da administração pública Indireta, assembleia legislativa, governo do Estado e Tribunal de Justiça, durante os exercícios de 2008 a 2011. Com isso, foi possível demonstrar, que a implementação do procedimento eletrônico pelo Tribunal de Contas do Estado da Paraíba,tem logrado êxito no cumprimento do Princípio da Celeridade Processual e Duração Razoável do Processo .

Trichloroethylene (TCE) is one of the most common groundwater pollutants in the United States. The EPA estimated that between 9% and 34% of the drinking water sources in the United States may contain TCE. The United States Environmental Protection Agency set a maximum contaminant level at 5 µg/L of trichloroethylene for drinking water. This study investigated the feasibility of removing TCE from water by sorption to ZSM-5 and advanced oxidation to destroy the TCE on the zeolite. Aqueous oxidation of TCE with Fenton's reagent was shown to be efficient for the destruction of TCE. The quantified by-products were cis-DCE and trans-DCE. ZSM-5 rapidly removed TCE from water. A Freundlich isotherm was created for the uptake of TCE by ZSM-5. Once TCE was sorbed to ZSM-5, preliminary experiments showed that the oxidation was able to destroy the TCE while producing the same by-products.

abstract: Trichloroethene (TCE) is a ubiquitous soil and groundwater contaminant. The most common bioremediation approach for TCE relies on the process of reductive dechlorination by Dehalococcoides mccartyi. D. mccartyi use TCE, dichloroethene, and vinyl chloride as electron acceptors and hydrogen as an electron donor. At contaminated sites, reductive dechlorination is typically promoted by adding a fermentable substrate, which is broken down to short chain fatty acids, simple alcohols, and hydrogen. This study explored microbial chain elongation (MCE), instead of fermentation, to promote TCE reductive dechlorination. In MCE, microbes use simple substrates (e.g., acetate, ethanol) to build medium chain fatty acids and also produce hydrogen during this process. Soil microcosm using TCE and acetate and ethanol as MCE substrates were established under anaerobic conditions. In soil microcosms with synthetic groundwater and natural groundwater, ethene was the main product from TCE reductive dechlorination and butyrate and hydrogen were the main products from MCE. Transfer microcosms using TCE and either acetate and ethanol, ethanol, or acetate were also established. The transfers with TCE and ethanol showed the faster rates of reductive dechlorination and produced more elongated products (i.e., hexanoate). The microbial groups enriched in the soil microcosms likely responsible for chain elongation were most similar to Clostridium genus. These investigations showed the potential for synergistic microbial chain elongation and reductive dechlorination of chlorinated ethenes. / Dissertation/Thesis / Masters Thesis Civil, Environmental and Sustainable Engineering 2019

The purpose of this work was to investigate the use of nanoscale Fe3O4 as a catalytst for destruction of trichloroethylene (TCE) and 1,2-dichloroethane (1,2-DCA) by persulfate in spiked water and soil. First, nanoscale Fe3O4 was prepared by chemical coprecipitation. X-ray powder diffraction (XRD) was used to confirm the crystal structure; And size identification was performed using the scanning electron microscopy (SEM). The effectiveness of using 3 wt% soluble starch (SS) to stabilize nanoscale Fe3O4 was also studied. It was found that SS could effectively disperse the nanoparticles for more than one month. Therefore, SS was chosen to prepare the nanoscale Fe3O4 slurry. The efficiency of nanoscale Fe3O4 as an activator for persulfate remediation of TCE and 1,2-DCA in aqueous solutions (DI water, simulated groundwater, and actual groundwater) was then investigated. The results showed that all test removal efficiency of TCE and 1,2-DCA was more than 95%. Use of the persulfate for destruction of TCE and 1,2-DCA produced some by-products. The primary reaction products were cis-1,2-Dichloroethylene (cis-1,2-DCE) and trans-1,2-Dichloroethylene (trans-1,2-DCE)¡F The secondary daughter prodnct was vinyl chloride (VC). The VC produced is gradually degraded to safer substances (ethene, ethane, and methane). The nanoscale Fe3O4 slurry and the persulfate injection coupled with the electrokinetic (EK) process was tested for remediation of TCE and 1,2-DCA in saturated soil. The results showed that injection of persulfate into the EK reservoir could decrease the electrode polarization, and increase the electroosmotic flow and current density. When persulfate was injected into the cathode reservoir, the derived sulfate radicals would transfer into the soil compartment by ion migration. The injection of persulfate into the cathode reservoir was more efficient than injection of persulfate into the anode reservoir. The removal efficiency for TCE and 1,2-DCA was more than 96% in all tests. The remediation system was assessed for potential application in-situ. Soil was spiked with high TCE and 1,2-DCA and aged for a week. The injection of persulfate and nanoscale Fe3O4 slurry coupled with the EK process was tested for remediation of the aged contaminated soil. The results showed that the target contaminants (TCE and 1,2-DCA) met the Taiwan¡¦s EPA¡¦s control standard. After 30 d of remediation, the by-products (cis-1,2-DCE, trans-1,2-DCE, and VC) had also been removed to below the action limit. A cost analysis was performed in order to demonstrate the economic feasibility of the remediation method in this study. Operating costs (chemicals + electricity bill) of all tests were assessed. The results showed that the costs were 8000-17000 NT$/m3, which is economically reasonable.

The goal of this study was to use molecular biology techniques to access and monitor the efficacy of bioremediation on a trichloroethene (TCE) polluted site. We added emulsified hydrogen releasing materials to stimulate onsite microbial growth and the biodegradation of TCE. This process was known as enhanced bioremediation. In this study, there were two bioremediation sites had been treated anaerobically. Groundwater samples were taken periodically for microbial analysis. Denaturing gradient gel electrophoresis (DGGE) was used to evaluate the variations in microbial community structures during the in situ groundwater remediation. The DGGE DNA bandings were sequenced to determine the 16S rRNA gene sequences and identify the dominate bacterial species. In addition, we used Dehalococcoides spp. 16S rRNA genes as the targets to do real-time PCR. Results show that the emulsified hydrogen releasing materials could enhance anaerobic reductive dechlorination. After addition of emulsified hydrogen releasing materials, we found that the volatile organic compounds concentrations (i.e., TCE, 1, 1-DCE and VC) were decreased. In microbial analysis, the diversities of the microbial community were increased after nutrient supplement. According to the DNA sequencing results, there were 31 bacterial species had been found that related to TCE degradation (i.e., Acidovorax sp., Burkholderiales, Pseudomonas sp., £]-proteobacterium, Comamonadaceae, Iron-reducing bacterium, Hydrogenophilaceae, Clostridium sp., Geobacter sp., Rhodoferax ferrireducens, Dehalospirillum multivorans and Dehalococcoides spp.). Dehalococcoides spp. can be used as a biomarker to evaluate the efficacy of anaerobic bioremediation on a TCE contaminated site. Therefore, we quantified Dehalococcoides populations to explain the capacity of bioremediation after addition of emulsified hydrogen releasing materials to groundwater. Results reveal that Dehalococcoides cell numbers of site A were 4.47¡Ñ103-8.26¡Ñ104 CFU/liter, site B were 4.60¡Ñ102-9.31¡Ñ107 CFU/liter. This data indicated that the addition of emulsified substrate would increase the growth of total Dehalococcoides population under anaerobic conditions. Overall, results from this study demonstrated that the microbial analysis and quantities of Dehalococcoides at different time points can provide useful information to proceed with bioremediation methods.

Abstract The industrial solvents tetrachloroethylene (PCE) and trichloroethylene (TCE) are among the most ubiquitous chlorinated compounds found in groundwater contamination. One potential method for managing PCE/TCE contaminated sites is the intrinsic bioremediation. Recent regulations adopted by U.S. Environmental Protection Agency allow intrinsic bioremediation to be considered as an alternative during development of corrective action plans. In some remediation cases, enhanced bioremediation are performed to accelerate the contaminant biodegradation rate. The main objective of this study was to evaluate the potential of using intrinsic and enhanced bioremediation technologies to clean up PCE/TCE contaminated aquifers. PCE/TCE bioavailability was evaluated by laboratory microcosms under four reduction/oxidation (redox) conditions including aerobic cometabolism, methanogenesis, iron reduction, and reductive dechlorination. Acclimated bacteria, activated sludge, and aquifer sediments from a pentachlorophenol contaminated site were used as the inocula in this study. Methane, toluene, phenol, sludge cake, and cane molasses were used as the primary substrates (carbon sources) in the cometabolism and reductive dechlorination microcosms. Results from this study show that PCE and TCE can be significantly biodegraded under reductive dechlorination and aerobic cometabolism conditions, respectively. All five carbon sources evaluated in this study can be applied as the primary substrates by microbial consortia to enhance the aerobic cometabolism of TCE. The highest TCE degradation rate [Up to 100% of TCE removal (with an initial concentration of 3.6µM)] was observed in the microcosms with toluene enrichment bacteria as the microbial inocula and toluene as the primary substrate. Under reductive dechlorination conditions, both sludge cake and cane molasses could be used as the primary substrates by microbial consortia (from activated sludge and aquifer sediments) and enhanced the biodegradation of PCE. The highest PCE degradation rate [Up to 100% of PCE removal (with an initial concentration of 17µM)] was observed in the microcosms with anaerobic activated sludge as the microbial inocula and sludge cake as the primary substrate. Except for reductive dechlorination microcosms, no significant PCE removal was observed in the microcosms prepared under iron reduction conditions. Results from this feasibility study would be useful in designing a scale-up in situ (e.g., in situ biobarrier system) or on-site bioremediation system (e.g., bioslurry reactor) for field application. Moreover, the application of non-toxic organic waste to enhance PCE/TCE biodegradation has the potential to become an environmentally and economically acceptable technology for the bioremediation of chlorinated-solvent contaminated groundwater.

A cylindrical electrochemical reactor with a 3 in diameter copper or nickel metal foam cathode and a concentric carbon cloth anode was used to destroy aqueous phase carbon tetrachloride (CT). The results show that a high CT conversion can be achieved in regions of the cathode near the anode, but a low CT conversion is obtained in the region around the center of the cathode. This CT conversion distribution in the radial current-conducting direction suggests that a portion of the cathode worked inefficiently even though the overall CT conversion is still adequate. Further research by changing the solution pH and conductivity suggests that the radial conversion distribution is due to radial variations in cathode surface availability. The inherent difficulties that these results imply with regards to reactor scale up suggested a new approach to the design. An annular reactor, consisting of a thin (3.2 mm) nickel foam cathode wrapped around an inert Plexiglas core and separated for an external concentric anode by a semi-permeable membrane was adopted. Under compatible operating conditions, the annular reactor showed a high overall effluent CT conversion. However, experiments at low pH (2.25) yielded higher conversions than under neutral pH conditions. This result suggests that CT conversion is favored by a relatively high proton concentration. This reactor can be simulated by a one dimensional model. The annular reactor was used to destroy PCE and TCE successfully, which suggests that this technique can be employed to treat groundwater contaminated with complex mixtures of chlorinated hydrocarbons.A multi-layer reactor based on the principle of the annular reactor was developed as an option for the scale up of the system. This reactor exhibited high and uniform radial CT conversion.

The current treatment of water contaminated with organic compounds includes adsorption, air stripping, and advanced oxidation processes. These methods large quantities of water and require excessive energy and time. A novel treatment process of concentrating and then electrochemically oxidizing compound would be a more feasible practice. This research investigated the oxidative destruction of perfluorooctane sulfonate (PFOS), perfluorobutane sulfonate (PFBS) and trichloroethene (TCE) at boron-doped diamond film electrodes and the adsorption of PFOS and PFBS on granular activated carbon and ion exchange resins.Experiments measuring oxidation rates of PFOS and PFBS were performed over a range in current densities and temperatures using a rotating disk electrode (RDE) reactor and a parallel plate flow-through reactor. Oxidation of PFOS was rapid and yielded sulfate, fluoride, carbon dioxide and trace levels of trifluoroacetic acid. Oxidation of PFBS was slower than that of PFOS. A comparison of the experimentally measured apparent activation energy with those calculated using Density Functional Theory (DFT) studies indicated that the most likely rate-limiting step for PFOS and PFBS oxidation was direct electron transfer. The costs for treating PFOS and PFBS solutions were compared and showed that PFOS is cheaper to degrade than PFBS.Screening studies were performed to find a viable adsorbent or ion exchange resin for concentrating PFOS or PFBS. Granular activated carbon F400 (GAC-F400) and an ion exchange resin, Amberlite IRA-458, were the best methods for adsorbing PFOS. Ionic strength experiments showed that the solubility of the compounds affected the adsorption onto solid phases. Regeneration experiments were carried out to determine the best method of recovering these compounds from the adsorbents; however, the compounds could not be effectively removed from the adsorbents using standard techniques.The electrochemical oxidation of trichloroethene (TCE) at boron-doped diamond film electrodes was studied to determine if this would be a viable degradation method for chlorinated solvents. Flow-through experiments were performed and showed TCE oxidation to be very rapid. Comparing the data from the DFT studies and the experimentally calculated apparent activation energies the mechanism for TCE oxidation was determined to be controlled by both direct electron transfer and oxidation via hydroxyl radicals.