Made available in DSpace on 2014-06-11T19:26:46Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-02-27Bitstream added on 2014-06-13T20:15:41Z : No. of bitstreams: 1 moraes_dac_me_botfca.pdf: 849456 bytes, checksum: c3e1db334cc08afff00ab382d3952add (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Universidade Estadual Paulista (UNESP) / O uso inadequado de defensivos agrícolas pode levar a impactos ambientais relevantes, como a contaminação de diversos compartimentos ambientais, sendo os mais vulneráveis, os compartimentos aquáticos. Nesse contexto, a espacialização das estimativas de concentração de defensivos agrícolas na água subterrânea fornece importantes subsídios para a tomada de decisão no gerenciamento e monitoramento do uso de defensivos agrícolas. Assim, este trabalho teve por objetivo espacializar as estimativas de contaminação de águas subterrâneas por defensivos agrícolas, considerando diferentes lâminas de irrigação na Bacia do Rio Pardo, Pardinho-SP. As simulações realizadas com o sistema computacional ARAquá foram realizadas considerando quatro defensivos agrícolas e cinco lâminas de irrigação. Técnicas geoestatísticas foram utilizadas em conjunto com as simulações para obter a espacialização dessas estimativas. Foram obtidos os mapas das estimativas de concentração de defensivos agrícolas na água subterrânea pelo método de interpolação por krigagem, sendo que estes indicaram as áreas com maior potencial de contaminação da água subterrânea. Considerando todas as simulações pode-se concluir que não houve risco de contaminação da água subterrânea por defensivos agrícolas e que as maiores concentrações foram obtidas considerando uma lâmina de irrigação anual de 400 mm. As simulações estimaram que as áreas com maior potencial de contaminação da água subterrânea foram as mais próximas da rede drenagem da Bacia do Rio Pardo. As técnicas de geoestatística contribuíram fortemente para a espacialização das estimativas de concentração de defensivos agrícolas na água subterrânea, por meio da análise dos variogramas e dos mapas gerados pela interpolação por krigagem / Improper use of pesticides can lead to significant environmental impacts such as contamination of environmental compartments, the most vulnerable, the aquatic compartments. In this context, the spatialization of the estimating concentrations of pesticides in groundwater provides important insights for decision making in managing and monitoring of the use of pesticides. Thus, this study aimed to spatialize the estimating of groundwater contamination by pesticides, with different irrigation blades in the Rio Pardo basin, Pardinho-SP. The simulations were performed with the computer system ARAquá considering four pesticides and five irrigation blades. Geostatistical techniques were used in conjunction with the simulations to obtain the spatial distribution of the estimating. The maps of the estimating concentration of pesticides in groundwater were obtained by Kriging interpolation method, and these indicate the areas with greatest potential for groundwater contamination. Considering all the simulations can be concluded that there was no risk of groundwater contamination by pesticides and that the highest concentrations were obtained considering an anual irrigation blade of 400 mm. The simulations have estimated that the areas with greatest potential for groundwater contamination were the closest to the drainage network of the Rio Pardo basin. Geostatistical techniques have contributed greatly to the estimates of spatial concentration of pesticides in ground water, through the analysis of variograms and maps generated by Kriging interpolation

Orientador: Célia Regina Lopes Zimback / Coorientador: Claudio Aparecido Spadotto / Banca: Antonio Evaldo Klar / Banca:Osmar Delmanto Júnior / Resumo: O uso inadequado de defensivos agrícolas pode levar a impactos ambientais relevantes, como a contaminação de diversos compartimentos ambientais, sendo os mais vulneráveis, os compartimentos aquáticos. Nesse contexto, a espacialização das estimativas de concentração de defensivos agrícolas na água subterrânea fornece importantes subsídios para a tomada de decisão no gerenciamento e monitoramento do uso de defensivos agrícolas. Assim, este trabalho teve por objetivo espacializar as estimativas de contaminação de águas subterrâneas por defensivos agrícolas, considerando diferentes lâminas de irrigação na Bacia do Rio Pardo, Pardinho-SP. As simulações realizadas com o sistema computacional ARAquá foram realizadas considerando quatro defensivos agrícolas e cinco lâminas de irrigação. Técnicas geoestatísticas foram utilizadas em conjunto com as simulações para obter a espacialização dessas estimativas. Foram obtidos os mapas das estimativas de concentração de defensivos agrícolas na água subterrânea pelo método de interpolação por krigagem, sendo que estes indicaram as áreas com maior potencial de contaminação da água subterrânea. Considerando todas as simulações pode-se concluir que não houve risco de contaminação da água subterrânea por defensivos agrícolas e que as maiores concentrações foram obtidas considerando uma lâmina de irrigação anual de 400 mm. As simulações estimaram que as áreas com maior potencial de contaminação da água subterrânea foram as mais próximas da rede drenagem da Bacia do Rio Pardo. As técnicas de geoestatística contribuíram fortemente para a espacialização das estimativas de concentração de defensivos agrícolas na água subterrânea, por meio da análise dos variogramas e dos mapas gerados pela interpolação por krigagem / Abstract: Improper use of pesticides can lead to significant environmental impacts such as contamination of environmental compartments, the most vulnerable, the aquatic compartments. In this context, the spatialization of the estimating concentrations of pesticides in groundwater provides important insights for decision making in managing and monitoring of the use of pesticides. Thus, this study aimed to spatialize the estimating of groundwater contamination by pesticides, with different irrigation blades in the Rio Pardo basin, Pardinho-SP. The simulations were performed with the computer system ARAquá considering four pesticides and five irrigation blades. Geostatistical techniques were used in conjunction with the simulations to obtain the spatial distribution of the estimating. The maps of the estimating concentration of pesticides in groundwater were obtained by Kriging interpolation method, and these indicate the areas with greatest potential for groundwater contamination. Considering all the simulations can be concluded that there was no risk of groundwater contamination by pesticides and that the highest concentrations were obtained considering an anual irrigation blade of 400 mm. The simulations have estimated that the areas with greatest potential for groundwater contamination were the closest to the drainage network of the Rio Pardo basin. Geostatistical techniques have contributed greatly to the estimates of spatial concentration of pesticides in ground water, through the analysis of variograms and maps generated by Kriging interpolation / Mestre

Contaminated land is a widespread, global issue affecting millions of people. Atrazine is a commonly used herbicide which often contaminates groundwater and drinking water supplies and is associated with adverse health outcomes. Biochar is the solid product of pyrolysis and is associated with several environmental benefits. It may be an effective remediation tool when used as a soil amendment. This thesis investigates the mechanisms through which biochar can immobilise atrazine, and the implications of the mechanisms for remediating contaminated land. Nine biochar samples were obtained from the United Kingdom Biochar Research Centre , which were produced from softwood pellets (SWP), wheat straw pellets (WSP), miscanthus straw pellets (MSP), rice husk (RH) and oil seed rape (OSR) each at pyrolysis temperatures of 550°C and 700°C (excluding OSR at 700°C). The sorption mechanisms controlling atrazine sorption to these biochars were determined through various characterisation methods and batch sorption experiments. The sorption tests showed that sorption to each of the standard biochars occurs via multiple simultaneously occurring mechanisms, which are each promoted under certain conditions. Studies investigating sorption kinetics, isotherms and interactions with humic acids showed that for all biochars in this study, pore filling was a significant process through which atrazine is transported to adsorption sites, although poor intraparticle diffusion for softwood and oil seed rape biochars can prevent efficient transport. Wheat straw and rice husk biochars showed effective pore diffusion, resulting in high sorption capacities. Partitioning was associated with poor remediation outcomes and was significant to softwood biochars, although adsorption dominated overall sorption for all other biochars. pH was shown to significantly influence the occurrence of various sorption mechanisms. At low pH values, most biochars showed evidence of electrostatic repulsion between positive atrazine species and the positively charged biochar surface. At intermediate pH values, all biochars showed strong hydrogen bonding between H+ groups on the surface of the biochar and atrazine. A meta-analysis of previous relevant studies provided further evidence for hydrogen bonding of atrazine to biochar and showed that hydrophobic effects likely play little role in adsorption after accounting for the effects of surface area. Varying contributions of π-π EDA interactions, hydrogen bonding involving biochar O- groups, and interactions with ash minerals resulted in different sorption profiles for each biochar at high pH values. In order to further determine the mechanisms controlling sorption at high pH, surface compositions of SWP550, RH700 and OSR550 biochars were modified using hydrofluoric acid. Modification with hydrofluoric acid successfully removed the ash contents of rice husk and oil seed rape biochars and reduced atrazine removal at high pH values. This suggested that the ash fraction increases atrazine removal at high pH through complexation or catalytic hydrolysis. The roles of the various mechanisms are related to remediation outcomes in a novel manner allowing for the improved design of biochar for environmental remediation.