Polyacid modified composite resins (PMCR) are designed to combine the aesthetics of composites-resins with the fluoride release of glass-ionomers. Objectives: to compare the relative biostability and fluoride release of PMCR (F2000 [3M]; Dyract eXtra [DENTSPLY]) and a composite-resin (Z250 [3M]). Standardized samples were incubated in either buffer or human saliva derived esterases (HSDE) for up to 14 days. High- performance-liquid-chromatography revealed higher amounts of degradation products for all HSDE incubated groups, as compared with the buffer. Z250 samples released higher amounts of bishydroxypropoxyphenylpropane (Bis-HPPP) and triethylene-glycol-dimethacrylate (TEGDMA) than both PMCR. Dyract eXtra and F2000 samples released unique degradation products, respectively di-ester of 2-hydroxyethyl di-methacrylate with butane tetracarboxylic acid (TCB) and glyceryl dimethacrylate (GDMA). F2000 samples released more fluoride for both incubation periods in the presence of HSDE as compared with Dyract eXtra samples. Scanning electron microscopy analysis confirmed the greater degradation of both PMCR, as compared with Z250.

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Els Processos Avançats d'Oxidació (PAOs) són tècniques de degradació química basades en la producció in situ del potent reactiu radical hidroxil. L'acoblament entre PAOs i sistemes biològics pel tractament d'aigua contaminada amb compostos biorecalcitrants és una alternativa útil als mètodes de gestió convencionals. El principal benefici d'aquests tractaments acoblats és la minimització del pretractament químic fins a generar intermedis més biodegradables. Subseqüentment, un tractament convencional d'aigües residuals, basat en la activitat de microorganismes, es pot utilitzar per eliminar completament la matèria orgànica del medi.Aquest tesi desenvolupa una estratègia d'acoblament entre sistemes químics i biològics per tractar herbicides específics com exemple de contaminants tòxics i no biodegradables produïts per l'home. / Advanced Oxidation Processes (AOPs) are chemical degradation techniques based on the in situ production of the powerful reactive hydroxyl radical. The coupling between AOPs and biological systems for the treatment of water polluted with biorecalcitrant compounds is a useful alternative to conventional management methods. The main benefit of these coupled treatments is the minimization of the chemical pretreatment to generate more biodegradable by-products. Subsequently, a conventional wastewater treatment, based on the activity of microorganisms, can be used to completely remove organic matter from solution. This thesis deals with the development of a chemical and biological coupling strategy to treat some specific herbicides as examples of toxic and non biodegradable anthropogenic pollutants.

Ethanol is used as fuel in neat form in some countries (Brazil and India) or blended with gasoline (Europe, Canada and the United States). The benefits of ethanol use include octane enhancement, a cleaner environment and a secure renewable energy supply. BTEX compounds (benzene, toluene, ethylbenzene, m-xylene, p-xylene and o-xylene) are aromatic hydrocarbons present in gasoline. The fate of these compounds in the environment is of great health concern due to their carcinogenic (benzene) and toxic properties, and due to their high solubility in water compared to the other gasoline hydrocarbons. Ethanol present in gasoline may affect BTEX degradation, in an event of a spill into the subsurface environment. To address the effects of ethanol on subsurface microorganisms, microbial activity and growth in the presence of ethanol (concentrations ranging 0 to 70% v/v) were assessed. Microcosms studies showed that ethanol at concentration ranging 0. 5 to3% (v/v) enhanced microbial activity and did not interfere inmicrobial growth at 10oC temperature, when another source of carbon was present (glucose). Ethanol at 0. 5% concentration enhanced microbial activity over water soluble gasoline components and R2A medium combined. Both microbialactivity and growth were not detected at ethanol concentrations equal and above 5%. Biodegradation study was conducted, in which subsurface material and ground water were exposed to BTEX and ethanol at 0. 5 and 1. 5% (v/v) concentration. The controls had BTEX alone and ethanol alone, sterile and nutrient-free. Total BTEX degradation was observed whenever ethanol was absent. Ethanol and BTEX were simultaneously degraded, however in microcosms containing 0. 5% ethanol, BTEX degradation was slowed, compared to microcosms without ethanol. Competition for inorganic nutrients was the major problem in slowed BTEX degradation in the presence of ethanol. In microcosms where 1. 5% ethanol was present, BTEX compounds and ethanol degradation were not observed.

The behaviour of hydrocarbon fuels in contaminated groundwater systems is studied using a multicomponent reactive transport model. The simulated processes include residual NAPL dissolution, aerobic and anaerobic biodegradation with daughter-product transport, and transport of a reactive carrier with mixed equilibrium/kinetic sorption. The solution algorithm is based on a three-dimensional Galerkin finite element scheme with deformable brick elements and capacity for a free watertable search. Nonlinearities are handled through Picard iteration. Convergence is rapid for most applications and mass balance errors for all phases are minimal. The model is first applied to simulate a pilot scale diesel fuel dissolution experiment in which humic acid is used as a natural organic carrier to enhance dissolution and to promote biodegradation of the aqueous components. The pilot scale experiment is described by Lesage et al. (1995) and Van Stempvoort et al. (2000). The conceptual model includes 8 unique components dissolving from 500 mL of residual diesel fuel within a 3D saturated domain. Oxygen-limiting competitive aerobic biodegradation with a dynamic microbial population is also included. A mixed 2-site equilibrium/kinetic model for describing sorption of the carrier to the aquifer solids was adopted to reproduce the observed breakthrough of the humic acid and organic components. Most model parameters were obtained independently with minimal calibration. Batch sorption data were found to fit well at the pilot scale, however biodegradation and dissolution rates were not well known and had to be fitted. Simulations confirmed the observed 10-fold increase in effective solubility of trimethylnaphthalene, and increases on the order of 2-5 for methyl- and dimethylnaphthalene. The simulated plumes showed almost complete attenuation after 5 years, in excellent agreement with observed data. A sensitivity analysis showed the importance of carrier concentrations, binding coefficients, dissolution and biodegradation rates. Compared to a dissolution scenario assuming no carrier, the humic acid-enhanced dissolution case decreased the remediation time by a factor of about 5. The second application of the model involves simulating the effect of ethanol on the persistence of benzene in gasoline-impacted groundwater systems. The conceptual model includes a 4-component residual gasoline source which is dissolving at the watertable into a 3D aquifer. Comparisons are made between dissolved plumes from a gasoline spill and those from an otherwise equivalent gasohol spill. Simulations have shown that under some conditions, a 10% ethanol component in gasoline can extend the travel distance of a benzene plume by at least 150% relative to that from an equivalent ethanol-free gasoline spill. The increase is due to preferred consumption of oxygen by ethanol and a corresponding reduction in the biodegradation rate of benzene while the two plumes overlap. Because of differences in retardation however, the ethanol and benzene plumes gradually separate. The impact therefore becomes limited because oxygen rapidly disperses behind the ethanol plume and benzene degradation eventually resumes. A sensitivity analysis for two common spill scenarios showed that background oxygen concentrations, and benzene retardation had the most significant influence on benzene persistence. A continuous gasohol spill over 10 years was found to increase the benzene travel distance by over 120% and a pure ethanol spill into an existing gasoline plume increased benzene travel distance by 150% after 40 years. The results are highly relevant in light of the forthcoming ban of MTBE in California and its likely replacement by ethanol by the end of 2002.

Ethanol can affect the biodegradation of gasoline hydrocarbons in groundwater. High concentrations of ethanol can be toxic to subsurface microorganisms that are otherwise capable of degrading hydrocarbons, such as benzene, toluene, ethylbenzene and xylenes (BTEX). At lower concentrations, ethanol may hinder BTEX degradation through substrate competition and the depletion of inorganic nutrients (e.g., nitrogen and phosphorus), oxygen and other electron acceptors needed for BTEX degradation. A series of laboratory experiments were designed to study the effect of ethanol on aquifer microorganisms and on aerobic BTEX biodegradation. A microcosm experiment was conducted to investigate the effect of ethanol on the biodegradation of BTEX. Microcosms were set up with Borden aquifer material and groundwater in which oxygen and nutrients were not limited. These microcosms contained BTEX in combination with a range of ethanol concentrations. Under these favourable conditions, the presence of ethanol up to concentrations of 1.9% (v/v) (equivalent to 15000 mg/L) caused little inhibition of BTEX degradation. Further experiments were conducted to study the antimicrobial effects of higher concentrations of ethanol. Following exposure to ethanol concentrations of 25% (v/v) or higher, microbial activity and survival was significantly diminished. Results suggest that a high concentration ethanol slug will have a major impact on the microbial community but that there would likely be potential for recovery. The recovery potential was examined further in laboratory column experiments designed to simulate a dynamic field situation where a high ethanol pulse is followed by a BTEX plume. These column experiments were conducted with Borden aquifer material and groundwater under aerobic conditions. The concentration of the ethanol pulse was 25% (v/v), which was expected to significantly alter the microbial population without destroying it. Following the ethanol exposure, groundwater and BTEX were allowed to flow through one column to simulate the reinoculation of microorganisms from upgradient groundwater advecting into the contaminated zone. The other column was fed with sterile groundwater and BTEX to evaluate the regeneration of within-column microorganisms that survived the ethanol exposure. Recovery in both columns was rapid. Unfortunately, during the recovery phase, sterility of the influent groundwater could not be maintained. As a result, recovery by regeneration could not be evaluated. Nonetheless, it is evident that recovery in terms of aerobic BTEX biodegradation was significant under the conditions of the column experiment. Ethanol did not appear to pose a long-term impact on BTEX biodegradation when oxygen and nutrients were in excess. In field situations, nutrients and electron acceptors may be limited; however, ethanol toxicity is not likely to cause a prolonged inhibition of BTEX biodegradation.

Ethanol is used as fuel in neat form in some countries (Brazil and India) or blended with gasoline (Europe, Canada and the United States). The benefits of ethanol use include octane enhancement, a cleaner environment and a secure renewable energy supply. BTEX compounds (benzene, toluene, ethylbenzene, m-xylene, p-xylene and o-xylene) are aromatic hydrocarbons present in gasoline. The fate of these compounds in the environment is of great health concern due to their carcinogenic (benzene) and toxic properties, and due to their high solubility in water compared to the other gasoline hydrocarbons. Ethanol present in gasoline may affect BTEX degradation, in an event of a spill into the subsurface environment. To address the effects of ethanol on subsurface microorganisms, microbial activity and growth in the presence of ethanol (concentrations ranging 0 to 70% v/v) were assessed. Microcosms studies showed that ethanol at concentration ranging 0. 5 to3% (v/v) enhanced microbial activity and did not interfere inmicrobial growth at 10oC temperature, when another source of carbon was present (glucose). Ethanol at 0. 5% concentration enhanced microbial activity over water soluble gasoline components and R2A medium combined. Both microbialactivity and growth were not detected at ethanol concentrations equal and above 5%. Biodegradation study was conducted, in which subsurface material and ground water were exposed to BTEX and ethanol at 0. 5 and 1. 5% (v/v) concentration. The controls had BTEX alone and ethanol alone, sterile and nutrient-free. Total BTEX degradation was observed whenever ethanol was absent. Ethanol and BTEX were simultaneously degraded, however in microcosms containing 0. 5% ethanol, BTEX degradation was slowed, compared to microcosms without ethanol. Competition for inorganic nutrients was the major problem in slowed BTEX degradation in the presence of ethanol. In microcosms where 1. 5% ethanol was present, BTEX compounds and ethanol degradation were not observed.

The behaviour of hydrocarbon fuels in contaminated groundwater systems is studied using a multicomponent reactive transport model. The simulated processes include residual NAPL dissolution, aerobic and anaerobic biodegradation with daughter-product transport, and transport of a reactive carrier with mixed equilibrium/kinetic sorption. The solution algorithm is based on a three-dimensional Galerkin finite element scheme with deformable brick elements and capacity for a free watertable search. Nonlinearities are handled through Picard iteration. Convergence is rapid for most applications and mass balance errors for all phases are minimal. The model is first applied to simulate a pilot scale diesel fuel dissolution experiment in which humic acid is used as a natural organic carrier to enhance dissolution and to promote biodegradation of the aqueous components. The pilot scale experiment is described by Lesage et al. (1995) and Van Stempvoort et al. (2000). The conceptual model includes 8 unique components dissolving from 500 mL of residual diesel fuel within a 3D saturated domain. Oxygen-limiting competitive aerobic biodegradation with a dynamic microbial population is also included. A mixed 2-site equilibrium/kinetic model for describing sorption of the carrier to the aquifer solids was adopted to reproduce the observed breakthrough of the humic acid and organic components. Most model parameters were obtained independently with minimal calibration. Batch sorption data were found to fit well at the pilot scale, however biodegradation and dissolution rates were not well known and had to be fitted. Simulations confirmed the observed 10-fold increase in effective solubility of trimethylnaphthalene, and increases on the order of 2-5 for methyl- and dimethylnaphthalene. The simulated plumes showed almost complete attenuation after 5 years, in excellent agreement with observed data. A sensitivity analysis showed the importance of carrier concentrations, binding coefficients, dissolution and biodegradation rates. Compared to a dissolution scenario assuming no carrier, the humic acid-enhanced dissolution case decreased the remediation time by a factor of about 5. The second application of the model involves simulating the effect of ethanol on the persistence of benzene in gasoline-impacted groundwater systems. The conceptual model includes a 4-component residual gasoline source which is dissolving at the watertable into a 3D aquifer. Comparisons are made between dissolved plumes from a gasoline spill and those from an otherwise equivalent gasohol spill. Simulations have shown that under some conditions, a 10% ethanol component in gasoline can extend the travel distance of a benzene plume by at least 150% relative to that from an equivalent ethanol-free gasoline spill. The increase is due to preferred consumption of oxygen by ethanol and a corresponding reduction in the biodegradation rate of benzene while the two plumes overlap. Because of differences in retardation however, the ethanol and benzene plumes gradually separate. The impact therefore becomes limited because oxygen rapidly disperses behind the ethanol plume and benzene degradation eventually resumes. A sensitivity analysis for two common spill scenarios showed that background oxygen concentrations, and benzene retardation had the most significant influence on benzene persistence. A continuous gasohol spill over 10 years was found to increase the benzene travel distance by over 120% and a pure ethanol spill into an existing gasoline plume increased benzene travel distance by 150% after 40 years. The results are highly relevant in light of the forthcoming ban of MTBE in California and its likely replacement by ethanol by the end of 2002.

Ethanol can affect the biodegradation of gasoline hydrocarbons in groundwater. High concentrations of ethanol can be toxic to subsurface microorganisms that are otherwise capable of degrading hydrocarbons, such as benzene, toluene, ethylbenzene and xylenes (BTEX). At lower concentrations, ethanol may hinder BTEX degradation through substrate competition and the depletion of inorganic nutrients (e.g., nitrogen and phosphorus), oxygen and other electron acceptors needed for BTEX degradation. A series of laboratory experiments were designed to study the effect of ethanol on aquifer microorganisms and on aerobic BTEX biodegradation. A microcosm experiment was conducted to investigate the effect of ethanol on the biodegradation of BTEX. Microcosms were set up with Borden aquifer material and groundwater in which oxygen and nutrients were not limited. These microcosms contained BTEX in combination with a range of ethanol concentrations. Under these favourable conditions, the presence of ethanol up to concentrations of 1.9% (v/v) (equivalent to 15000 mg/L) caused little inhibition of BTEX degradation. Further experiments were conducted to study the antimicrobial effects of higher concentrations of ethanol. Following exposure to ethanol concentrations of 25% (v/v) or higher, microbial activity and survival was significantly diminished. Results suggest that a high concentration ethanol slug will have a major impact on the microbial community but that there would likely be potential for recovery. The recovery potential was examined further in laboratory column experiments designed to simulate a dynamic field situation where a high ethanol pulse is followed by a BTEX plume. These column experiments were conducted with Borden aquifer material and groundwater under aerobic conditions. The concentration of the ethanol pulse was 25% (v/v), which was expected to significantly alter the microbial population without destroying it. Following the ethanol exposure, groundwater and BTEX were allowed to flow through one column to simulate the reinoculation of microorganisms from upgradient groundwater advecting into the contaminated zone. The other column was fed with sterile groundwater and BTEX to evaluate the regeneration of within-column microorganisms that survived the ethanol exposure. Recovery in both columns was rapid. Unfortunately, during the recovery phase, sterility of the influent groundwater could not be maintained. As a result, recovery by regeneration could not be evaluated. Nonetheless, it is evident that recovery in terms of aerobic BTEX biodegradation was significant under the conditions of the column experiment. Ethanol did not appear to pose a long-term impact on BTEX biodegradation when oxygen and nutrients were in excess. In field situations, nutrients and electron acceptors may be limited; however, ethanol toxicity is not likely to cause a prolonged inhibition of BTEX biodegradation.

A gas-fluidized bed bioreactor was developed in this research as a new method for treating polluted air. The fluidization characteristics of selected packing materials were investigated. Then, bioremediation was tested using two types of packing in a fluidized bioreactor, as well as in a comparable packed bed. Microorganisms on the particles biodegrade contaminants in the polluted air, which flows up through the bed. At high flowrates, the polluted air fluidizes the particles, while at low velocities the operation is in packed bed mode.<p>Initially, sawdust was selected for use as a packing material. Due to the poor fluidization properties of sawdust, glass spheres were added. A mixture of sawdust and glass spheres remained well mixed during fluidization. In the mixture, interparticle forces increased with increasing moisture in the sawdust, eventually causing defluidization of the bed. In the absence of bioremediation, mass transfer was studied between ethanol-contaminated air and sawdust/glass sphere packing, and found to be higher in the fluidized versus packed mode. In bioremediation experiments, ethanol removal efficiencies were as high as 95% in both operating modes. The maximum elimination capacities (EC) of ethanol were 75 and 225 g m^-3 sawdust h^-1 in the fluidized and packed beds respectively.<p>The packing of the fluidized bed bioreactor was optimized in order to boost bioremediation rates. Experiments showed that peat granules fluidized well in a bubbling regime, likely due to their relatively high density and sphericity. In peat bioremediation trials, the fluidized mode outperformed the packed bed; the maximum ECs were 1520 and 530 g m^-3 peat h^-1, respectively. Removal efficiency in the fluidized mode decreased with velocity, because the size and amount of large bubbles increased.<p>A steady-state model of the fluidized bioreactor was developed. By taking account of bubble properties during fluidization, the model helps to explain how bubble size, microbial properties and bioreactor residence time affect removal efficiency and elimination capacity of the bioreactor.<p>A peat gas-fluidized bioreactor shows promise as an efficient, low-cost technology for air treatment. Particle mixing in the fluidized bed may prevent operating problems associated with the packed bed bioreactor. Fluidized bioreactors are ideal for the treatment of high volume, low concentration air emissions.