O presente trabalho realizou simulações meteorológicas e de dispersão de poluentes com fontes de emissão da Região Metropolitana de São Paulo (RMSP) e de Cubatão, entre 23 a 26/08/2006. Neste período ocorreu um experimento de inverno realizado pelo IGC-USP, me- dindo e fazendo a análise elementar de Material Particulado Inalável (diâmetro aerodinâmico médio < 10m, M P 10 ) em Cubatão e em outros dois pontos de amostragem da RMSP (USP e Juquitiba). Empregou-se de modo articulado o modelo meteorológico de mesoescala BRAMS (Brazilian Regional Atmospheric Modelling System) e o modelo lagrangeano estocástico de dispersão de partículas SPRAY. Na área da RMSP considerou-se a dispersão das emissões de Monóxido de Carbono (CO) por veículos, enquanto em Cubatão tomou-se o MP proveniente das fábricas do Polo industrial de Cubatão. Os resultados da simulação de dispersão foram comparados com os valores medidos nas estações da CETESB (Companhia Ambiental do Estado de São Paulo), na estação meteorológica do IAG-USP e no experimento de inverno. O acoplamento BRAMS/SPRAY mostrou boa habilidade para simulação da meteorologia e das concentrações de poluentes. Foi possível discutir o transporte de poluentes entre a RMSP, Cubatão e arredores, durante este período, considerando inclusive um episódio particular ocorrido nos dias 25 e 26/08/2006. / This work performed meteorological and pollutants dispersion simulations using sources of the Metropolitan Area of São Paulo (MASP) and Cubatão city, between 23 and 26 August, 2006. During this period, a wintertime experiment was realized by IGC-USP (Institute of Geosciences - University of São Paulo) to measure and make the elemental analysis of the inhalable particulate matter from Cubatão, USP (In São Paulo, capital of São Paulo State, and MASPs major city) and Juquitiba (a MASPs border limits city). BRAMS/SPRAY (Brazilian Regional Atmospheric Modelling System, and the lagrangean stochastic dispersion Model SPRAY) were coupled to simulate meteorological variables and pollutant concentrations. The vehicular emissions of CO was the source used as input at MASP for SPRAY, and the imput used at Cubatão was the industrial emissions of PM at Cubatão industrial city. The results of the simulations were compared with meteorological data and the concentrations of pollutants measured in the CETESBs stations (CETESB - São Paulos Environmental Agency), at IAGs meteorological station (IAG - Institute for Astronomy, Geophisics and Atmospheric Sciences of University of São Paulo), and in the wintertime experiment stations. BRAMS/SPRAY coupled model showed good skill to simulate meteorological data and the concentrations of pollutants. They enabled the discussion of the pollutants transport between MASP, Cubatão and nearby areas, during studied period, specially a particular episode that took place in August 25 and 26, 2006

O presente trabalho realizou simulações meteorológicas e de dispersão de poluentes com fontes de emissão da Região Metropolitana de São Paulo (RMSP) e de Cubatão, entre 23 a 26/08/2006. Neste período ocorreu um experimento de inverno realizado pelo IGC-USP, me- dindo e fazendo a análise elementar de Material Particulado Inalável (diâmetro aerodinâmico médio < 10m, M P 10 ) em Cubatão e em outros dois pontos de amostragem da RMSP (USP e Juquitiba). Empregou-se de modo articulado o modelo meteorológico de mesoescala BRAMS (Brazilian Regional Atmospheric Modelling System) e o modelo lagrangeano estocástico de dispersão de partículas SPRAY. Na área da RMSP considerou-se a dispersão das emissões de Monóxido de Carbono (CO) por veículos, enquanto em Cubatão tomou-se o MP proveniente das fábricas do Polo industrial de Cubatão. Os resultados da simulação de dispersão foram comparados com os valores medidos nas estações da CETESB (Companhia Ambiental do Estado de São Paulo), na estação meteorológica do IAG-USP e no experimento de inverno. O acoplamento BRAMS/SPRAY mostrou boa habilidade para simulação da meteorologia e das concentrações de poluentes. Foi possível discutir o transporte de poluentes entre a RMSP, Cubatão e arredores, durante este período, considerando inclusive um episódio particular ocorrido nos dias 25 e 26/08/2006. / This work performed meteorological and pollutants dispersion simulations using sources of the Metropolitan Area of São Paulo (MASP) and Cubatão city, between 23 and 26 August, 2006. During this period, a wintertime experiment was realized by IGC-USP (Institute of Geosciences - University of São Paulo) to measure and make the elemental analysis of the inhalable particulate matter from Cubatão, USP (In São Paulo, capital of São Paulo State, and MASPs major city) and Juquitiba (a MASPs border limits city). BRAMS/SPRAY (Brazilian Regional Atmospheric Modelling System, and the lagrangean stochastic dispersion Model SPRAY) were coupled to simulate meteorological variables and pollutant concentrations. The vehicular emissions of CO was the source used as input at MASP for SPRAY, and the imput used at Cubatão was the industrial emissions of PM at Cubatão industrial city. The results of the simulations were compared with meteorological data and the concentrations of pollutants measured in the CETESBs stations (CETESB - São Paulos Environmental Agency), at IAGs meteorological station (IAG - Institute for Astronomy, Geophisics and Atmospheric Sciences of University of São Paulo), and in the wintertime experiment stations. BRAMS/SPRAY coupled model showed good skill to simulate meteorological data and the concentrations of pollutants. They enabled the discussion of the pollutants transport between MASP, Cubatão and nearby areas, during studied period, specially a particular episode that took place in August 25 and 26, 2006

In order to preserve groundwater resources from contamination by volatile organic compounds and to clean up sites contaminated with the compounds, we should understand fate and transport of contaminants in the subsurface systems and physicochemical processes involving remediation technologies. To enhance our understanding, numerical studies were performed on the following topics: (i) multiphase flow and contaminant transport in subsurface environments; (ii) biological transformations of contaminants; (iii) in-situ air sparging (IAS); and, thermal-enhanced venting (TEV). Among VOCs, trichloroethylene (TCE) is one of the most-frequently-detected chemicals in the contaminated groundwater. TCE and its daughter products (cis-1,2-dichloroethylene (cDCE) and vinyl chloride (VC)) are chosen as target contaminants. Density-driven advection of gas phase is generated by the increase in gas density due to vaporization of high-molecular weight contaminants such as TCE in the unsaturated zone. The effect of the density-driven advection on fate and transport of TCE was investigated under several environmental conditions involving infiltration and permeability. Biological transformations of contaminants can generate byproducts, which may become new toxic contaminants in subsurface systems. Sequential biotransformations of TCE, cDCE, and VC are considered herein. Under different reaction rates for two bioreaction kinetics, temporal and spatial concentration profiles of the contaminants were examined to evaluate the effect of biotransformations on multispecies transport. IAS injects clean air into the subsurface below the groundwater table to remediate contaminated groundwater. The movement of gas and the groundwater as a multiphase flow in the saturated zone and the removal of TCE by IAS application were analyzed. Each fluid flow under IAS was examined in terms of saturation levels and fluid velocity profiles in a three-dimensional domain. Several scenarios for IAS systems were simulated to evaluate remedial performance of the systems. TEV was simulated to investigate its efficiency on the removal of a nonaqueous phase liquid in the unsaturated zone under different operational conditions. For numerical studies herein, the governing equations for multiphase flow, multispecies transport, and heat energy in porous media were developed and solved using Galerkin finite element method. A three-dimensional numerical model, called TechFlowMP model, has been developed.

Land application of biosolids has become common practice in the United States as an alternative to industrial fertilizers. Although nutrient rich, biosolids have been found to contain high concentrations of emerging contaminants (e.g. pharmaceuticals, personal care products) while containing a significant fraction of inorganic nano-scale colloidal materials such as oxides of iron, titanium, and aluminum. Given their reactivity and small size, there are many questions concerning the potential migration of these nano-sized colloidal materials through the soil column and into our surface and groundwater bodies. Transport of emerging pollutants of concern through the soil column, at minimum, is impacted by colloidal properties (e.g. chemical composition, shape, aggregation kinetics), solution chemistry (e.g. pH, ionic strength, natural organic matter), and water flow velocity. The purpose of this current research was to characterize the long-term transport behavior of aluminum oxide nanoparticles (Al2O3) through a natural porous media with changes in pH, aqueous-phase concentration, pore-water velocity and electrolyte valence. Additionally, deposition rates during the initial stages of deposition were compared to several models developed based on colloid filtration theory and DLVO stability theory. Benchtop column laboratory experiments showed that, under environmentally relevant groundwater conditions, Al2O3 nanoparticles are mobile through saturated porous media. Mobility increased under conditions in which the nanoparticles and porous media were of like charge (pH 9). Changes in linear pore water velocity, under these same high pH conditions, showed similar transport behavior with little mass retained in the system. Deposition is believed to be kinetically controlled at pH 9, as evidenced by the slightly earlier breakthrough as flow rate increased and was further supported by observed concentration effects on the arrival wave following several stop flows. While lower aqueous-phase concentrations resulted in significantly longer breakthrough times, the total mass retained in the system was found to be independent of concentration. Additionally, experimental deposition rate coefficients (kd), used to describe deposition kinetics under "clean bed" conditions, were similar across the aqueous-phase concentrations studied. The use of calcium chloride electrolyte solution in transport studies resulted in enhanced mobility relative to potassium chloride suggesting that changes in groundwater solution chemistry could impact mobility of contaminants associated with biosolids. Predicted deposition rate coefficients, using three different models, were found to under- or over-predict values relative to those experimentally determined values depending on the model. This current research has shown that nanocolloids associated with biosolids, specifically Al2O3, are mobile through saturated porous media. Given the ubiquity of nanocolloidal materials, particularly engineered nanomaterials, coupled with the expected increase in land-application of biosolids, a clear understanding of their transport and fate is prudent to understanding the potential impact these emerging pollutants may have on our surface and groundwater bodies.

The deteriorating air quality in Cape Town (CT) is a threat to the social and economic development of the city. Although previous studies have shown that most of the pollutants are emitted in the city, it is not clear how the transport of pollutants from neighbouring cities may contribute to the pollution. This thesis studies the transport of atmospheric nitrogen oxides (NOx) and nitric acid (HNO3) pollutants over South Africa and examines the role of pollutant transport from the Mpumalanga Highveld on pollution in CT. The study analysed observation data (2001 - 2008) from the CT air quality network and from regional climate model simulation (2001 - 2004) over South Africa. The model simulations account for the influences of complex topography, atmospheric conditions, and atmospheric chemistry on transport of the pollutants over South Africa. Flux budget analysis was used to examine whether the city is a net source or sink for NOx and HNO3. The results show that north-easterly flow transports pollutants (NOx and HNO3) at low level (i.e., surface to 850 hPa) from the Mpumalanga Highveld towards CT. In April, a tongue of high concentration of HNO3 extends from the Mpumalanga Highveld to CT, along the southern coast. The flux budget analysis shows that CT can be a net sink for NOx and HNO3 during extreme pollution events. The study infers that, apart from the local emission of the pollutants in CT, the accumulation of pollutants transported from other areas may contribute to pollution in the city. / Environmental Sciences / M. Sc. (Environmental Science)

The deteriorating air quality in Cape Town (CT) is a threat to the social and economic development of the city. Although previous studies have shown that most of the pollutants are emitted in the city, it is not clear how the transport of pollutants from neighbouring cities may contribute to the pollution. This thesis studies the transport of atmospheric nitrogen oxides (NOx) and nitric acid (HNO3) pollutants over South Africa and examines the role of pollutant transport from the Mpumalanga Highveld on pollution in CT. The study analysed observation data (2001 - 2008) from the CT air quality network and from regional climate model simulation (2001 - 2004) over South Africa. The model simulations account for the influences of complex topography, atmospheric conditions, and atmospheric chemistry on transport of the pollutants over South Africa. Flux budget analysis was used to examine whether the city is a net source or sink for NOx and HNO3. The results show that north-easterly flow transports pollutants (NOx and HNO3) at low level (i.e., surface to 850 hPa) from the Mpumalanga Highveld towards CT. In April, a tongue of high concentration of HNO3 extends from the Mpumalanga Highveld to CT, along the southern coast. The flux budget analysis shows that CT can be a net sink for NOx and HNO3 during extreme pollution events. The study infers that, apart from the local emission of the pollutants in CT, the accumulation of pollutants transported from other areas may contribute to pollution in the city. / Environmental Sciences / M. Sc. (Environmental Science)