Thesis (MTech (Agriculture))--Cape Peninsula University of Technology, 2014. / In this study, laboratory and greenhouse experiments were conducted to evaluate the effects of utilization of land fill leachate for irrigation purposes on potted soil and Swiss chard, to provide more insight into effects of landfill leachates on the environment. Swiss chard was grown and irrigated with different concentrations of leachates in pot experiments. For several weeks, the experimental soil and Swiss chard leaves was analyzed to assess extent of change in different chemical compositions, post-irrigation. The leachate samples had a high electrical conductivity (mean = 383 mS cm-1) and high soluble salts content (mean values, Na = 714.5 mg/L, K= 56.8 mg/L, Ca = 133.7 mg/L, Mg = 68.8 mg/L, Cl = 983 mg/L); while the composition of heavy metals in these wastewater leachates were of low concentrations. The application of leachates in irrigation resulted in increased soil cation concentrations, particularly those of Na ions (increased sodicity). Similarly, an increase in electrical conductivity and pH were recorded in the soils after irrigation with leachates. The soil metal concentrations were low and there was no significant difference in soil heavy metal concentrations between the soils irrigated with leachate and those of the controls. The results also show significant (p <0.05) reduction (up to 50%) in Swiss chard growth with application of (100%, 50% and 25%) of leachate as source of irrigation water compared to the growth observed in leachate-free (control) irrigation systems. This reduction in growth was best attributed to the high cation content in plant tissue picked up from the soil which was high in cations as a result of leachate irrigation.

A dissertation submitted to the faculty of Science, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Master of Science. / Unable to load abstract.

A dissertation submitted to the Faculty of Science, University of Witwatersrand, in fulfilment of the requirements for the degree of Masters of Science Johannesburg, 2012. / Amplified loads of sulfate and nitrate have caused increased stress on soil systems in many areas of the world, as both are dominant components of acid rain. This is a critical environmental stress due to the damage caused to soil, water quality and ecosystem functioning. Issues concerning the rising emissions of these elements from local industries have begun to attract increasing attention in South Africa, as the rates of deposition in the Mpumalanga Highveld region alone is comparable to those experienced in First World countries. This study sought to investigate the use of natural stable isotopes of sulfur and nitrogen to identify the process transformations that these species undergo in environmental cycles. Total δ34S, δ15N and δ13C isotope signature of soils in the Mpumalanga region were combined with total elemental concentrations to determine the effect of deposition on the soil system. Soil samples from two soil depths (0 – 10 cm and 20 – 40 cm) were taken along a distance gradient from an identified pollution source, the Majuba power station. Long-term air quality data from the study area were also obtained from Eskom’s air quality monitoring stations, as well as sulfur and nitrogen deposition data from selected literature. Elemental concentrations decreased with soil depth as expected, while sites located approximately 25 km downwind of the power station were seen to contain higher concentrations of both soil sulfur and nitrogen. The mean per site soil sulfur concentration across all depths ranged from 0.009 % to 0.048 %, while the mean per site nitrogen concentration across all depths ranged from 0.056 % to 0.346 %. The mean soil carbon concentration in the top-soils ranged from 0.97 % to 7.93 %, and decreased in the sub-soils to 0.490 % to 3.270 %.The mean δ34S value for the top-soils was found to be 8.28 ‰ and increased to 10.78 ‰ in the sub-soils. Soil δ15N also increased with soil depth from 6.55 ‰ to 8.28 ‰. Soil δ13C values were seen to increase from -12.83 ‰ in the top-soils to -11.90 ‰ in the sub-soils. Lighter δ34S values at the surface may be due to anthropogenic deposition. The positive δ34S shift was attributed to a two-source mixing model (atmospheric deposition and bedrock) and isotopic fractionation processes that occur within the soil profile. The δ15N values of the top-soil were higher than what is expected if all nitrogen was derived from atmospheric nitrogen gas fixation. The increase in δ15N with depth suggested that isotope fractionation occurred during nitrogen export due to the faster reaction rate of 14N compared to 15N. The soil δ13C values indicated a typical C4 grassland system. New carbon at the top-soil depths was enriched in 13C due to the slower decay of 13C-depleted lignin; whereas in the sub-soils microbial recycling of carbon dominates and explained the higher 13C content of the older carbon. The conceptual framework presented for this project involves simultaneous processes of deposition and export in the soil system. This was particularly true for sulfur, where sites with lower isotope values had lower soil sulfur concentrations and vice versa. This indicates that high levels of deposition correspond to high net export. The sulfur and nitrogen isotopic signatures could not be used to as a direct means of source identification; however, the effectiveness of isotopes in elucidating transfer of these nutrients in the soil system was illustrated.

O Estado do Rio Grande do Sul é responsável por 90% da produção nacional de uvas, sobretudo para a elaboração de vinhos finos. O município de Encruzilhada do Sul apresenta potencial edafoclimático ideal para a produção de uvas que abastecem grandes vinícolas da Serra Gaúcha. Entretanto o uso indiscriminado do solo pode resultar em uma degradação do solo. Este trabalho foi dividido em três estudos, que tiveram como objetivo Identificar as classes de solos ocorrentes no vinhedo, de acordo com a descrição morfológica e análise dos atributos químicos e físicos dos horizontes superficiais e subsuperficiais; Avaliar o efeito do manejo na qualidade química do solo de um vinhedo comercial, em áreas com 4, 9 e 16 anos de manejo após o plantio de videira da variedade Vitis vinifera L. cv. Pinot Noir para a elaboração de espumantes; Avaliar o efeito do tráfego de máquinas agrícolas na qualidade física do solo de um vinhedo comercial com diferentes anos de condução após o plantio das mudas. Foram realizados análises de perfis de 8 trincheiras em campo e com análises laboratoriais. Foi realizado o estudo dos atributos químicos e físicos do solo utilizados como indicadores de qualidade do solo, para avaliar o efeito do manejo do vinhedo com 4, 9 e 16 anos de condução após o plantio das mudas. Para análise da qualidade química do solo foram coletadas amostras indeformadas do solo nas profundidades de 0-10, 10-20, 20-30, 30-40, 40-50 e 50-60 cm, em três repetições. Os atributos físicos do solo foram analisados nas mesmas áreas e profundidades, que foram coletadas no local de trafego do rodado (R), entre rodados (ER) e linha de plantio (LP). 80% da propriedade é constituída por Argissolos diversificados, além de Cambissolos, estes ideais para a cultura da videira. Além desses solos, foi identificado na propriedade a presença de Gleissolo, que não são recomendados para o cultivo devido ao seu caráter hidromórfico. Pode-se observar uma redução na acidez do solo e incremento da fertilidade devido ao histórico de cultivo do vinhedo. Para a análise dos indicadores de qualidade física do solo, foram coletadas amostras do solo nas mesmas profundidades, em três locais na entrelinha: entre rodados, rodados e linha de plantio. A área com 16 anos de condução após o plantio apresentou maior efeito do uso de máquinas no vinhedo, sobretudo na posição de tráfego dos rodados do trator, afetando seriamente a qualidade física devido à compactação e baixa infiltração de água no solo. / The State of Rio Grande do Sul is responsible for 90% of the national production of grapes, mainly for the elaboration of fine wines. The municipality of Encruzilhada do Sul presents ideal edafoclimatic potential for the production of grapes that supply large wineries in the Serra Gaúcha. However the indiscriminate use of the soil can result in a degradation of the soil. This work was divided into three studies, which aimed to identify the soil classes occurring in the vineyard, according to the morphological description and analysis of the chemical and physical attributes of the superficial and subsurface horizons; To evaluate the effect of the management on the chemical quality of the soil of a commercial vineyard in areas with 4, 9 and 16 years of management after planting Vitis vinifera L. cv. Pinot Noir for the preparation of sparkling wines; To evaluate the effect of the traffic of agricultural machines on the physical quality of the soil of a commercial vineyard with different years of driving after planting the seedlings. Analyzes of profiles of 8 trenches were carried out in the field and with laboratory analyzes. The study of soil chemical and physical attributes used as soil quality indicators was carried out to evaluate the effect of vineyard management at 4, 9 and 16 years of age after planting the seedlings. For the analysis of soil chemical quality, undisturbed soil samples were collected at depths of 0-10, 10-20, 20-30, 30-40, 40-50 and 50-60 cm in three replicates. The physical attributes of the soil were analyzed in the same areas and depths, which were collected in the traffic site of the wheel tracks of the tractor (WT), between the wheel tracks (BWT), and in the area under the line projection of the canopy (CLP). 80% of the property consists of diversified Argissolos, in addition to Cambisols, these are ideal for vine growing. In addition to these soils, the presence of Gleissolo was identified in the property, which are not recommended for cultivation due to its hydromorphic character. A reduction in soil acidity and an increase in fertility can be observed due to the vineyard's cultivation history. For the analysis of soil physical quality indicators, soil samples were collected at the same depths, at three sites in the interline: between rounds, rounds and planting line. The area with 16 years of driving after planting showed a greater effect of the use of machines in the vineyard, especially in the traffic position of tractor wheels, seriously affecting the physical quality due to compaction and low infiltration of water in the soil.

Os fertilizantes fosfatados (FF) mais utilizados na agricultura são solúveis em água, e requerem enxofre elementar e concentrados apatíticos de elevada qualidade para produção, conduzindo à subutilização dos depósitos de fosfato (perdas elevadas de P no beneficiamento). Conseqüentemente, é necessário estudar as fontes alternativas de P. Neste trabalho foram estudadas quanto à: (i) revisão de literatura que tenta mostrar a situação atual no Brasil e no mundo; (ii) produção alternativa de fonte de P que integra matéria orgânica e RF (Humifert); e (iii) utilização de software para predizer a eficiência agronômica (EA) de RF, relativamente às fontes de P solúveis em água. Na revisão da literatura foram enfatizados: tratamento térmico, acidulação parcial, compactação ou mistura com FF solúveis em água, tratamentos com resíduos orgânicos e/ou microrganismos. Outros aspectos apontaram: (i) condições gerais para utilizar fontes de P de elevada solubilidade em água e alternativas; (ii) manejo de solos prevendo solubilização de formas de P nativo e aumento na EA de fontes de P através de cultivos precedentes ou microrganismos; (iii) calcinação de RFs do tipo Ca-Al-P (crandallita); e (iv) necessidade de pesquisas com fontes alternativas de P em condições de casa-de-vegetação e campo. Quanto ao processo Humifert, um reator foi construído para trabalhar em escala de bancada. Os objetivos foram gerar informações sobre produção dos fertilizantes &#34;Humifert&#34; e testar a EA dos mesmos. Diversos testes foram conduzidos quanto às condições de operação do equipamento, como tempo de reação e solubilidade dos materiais produzidos. Dois experimentos agronômicos foram conduzidos em casa-de-vegetação, relacionando os resultados dos produtos obtidos no equipamento com fonte padrão de P. Esse processo conduz a desempenho agronômico superior da RF quando comparada a mesma sem submissão às reações. Embora algumas vantagens em aumento de produção devido ao Humifert, a solubilidade e os resultados agronômicos indicam necessidade de mais pesquisas para adequar as reações, para obter fontes de P de melhor qualidade. O software para predizer a eficiência das RFs denomina-se &#34;Phosphate Rock Decision Support System&#34; (PRDSS) e foi desenvolvido com colaboração entre &#34;IFDC&#34; e &#34;IAEA&#34;. O objetivo final é predizer a EA de RF específica relativamente a fontes de P de elevada solubilidade em água, considerando solo, características da RF, manejo do solo e clima na localidade. O experimento foi conduzido em Rondonópolis, em um LV com pH em água de 5,2, teor muito baixo de P e capacidade média de adsorção de P. As fontes de P utilizadas foram superfosfato simples, RF de Araxá e de Gafsa, aplicadas a lanço e incorporadas em 15 cm de solo, nas doses 60, 120 e 240 kg ha-1 de P2O5 total. Um controle foi adicionado para cada fonte de P. Os resultados de EAR para soja no campo foram de 100%, 51% e 97% para o SSP, RF Araxá e Gafsa, respectivamente. Os valores de EAR preditos pelo PRDSS foram de 33% e 100% para a RF Araxá e Gafsa, respectivamente, sendo consideradas boas estimativas da EAR real em condições brasileiras, inicialmente comprovando a aplicabilidade deste software para uso futuro. / The most utilized phosphate fertilizers (PF) in agriculture are the water-soluble sources, that require elemental sulfur and high quality apatite concentrates for the production, leading to the subutilization of phosphate deposits (high losses of P during the beneficiation). Consequently, it is necessary to study the alternative sources of P. In this work they were studied as related to: (i) literature review trying to show the present situation in Brazil and worldwide, (ii) alternative production of a P source combining organic matter and PR (Humifert), and (iii) utilization of software to predict the agronomic effectiveness (AE) of PR, related to water-soluble P sources. For the literature review were emphasized: thermal treatment, partial acidulation, compaction with high water-soluble PF, organic residues and/or microrganisms treatments. Other aspects targeted: (i) general conditions to utilize high water-soluble P sources and alternatives, (ii) management of soils foreseeing the solubilization of forms of native P and increase in AE of P sources through previous crops or microrganisms, (iii) calcination of PRs of the type Ca-Al-P (crandallite), and (iv) requirement for research with different sources of P in greenhouse and field conditions. As related to the Humifert process a reactor was built to work in bench scale. The objectives were to generate information relative to the production of the &#34;Humifert&#34; fertilizers and test the AE of them. Several tests were applied as related to the operating conditions of the equipament, as reaction time and solubility. Two agronomic experiments were conducted in a greenhouse, relating the results of the products obtained in the equipament with a standard source of P. The process lead to higher agronomic performance of the PR, when comparing it without submission to the reactions. Although some advantages in increase of production due to the Humifert, the solubility and agronomic results indicate that more research is necessary to adequate the reaction to obtain better quality P sources. The software to predict PR effectiveness is called &#34;Phosphate Rock Decision Support System (PRDSS)&#34; and was developed in collaboration between &#34;IFDC&#34; and &#34;IAEA&#34;. The final objective is to predict the RAE of a specific PR, as related to WSP sources, taking into consideration soil, PR characteristics, soil management and clima at locality. Our experiment was conducted in Rondonopolis, in an Oxisol with pH 5.2 in water, very low content of P and medium P adsorption capacity. The P sources utilized were the single superphosphate, the Araxa PR and Gafsa, all applied broadcasted to the soil into the 15 cm soil layer, in rates 60, 120 and 240 kg ha-1 of total P2O5. A control was added for each P source. The results for RAE for soybean at field condition were 100%, 51% and 97% for the SSP, Araxa PR and Gafsa, respectively. The RAE predicted by the PRDSS were of 33% and 100% for Araxa PR and Gafsa, respectively, which can be considered good estimates of the real RAE at Brazilian conditions, initially attesting the feasibility of this software for future use.

Apesar da preocupação atual com a contaminação do ambiente, pelo uso agrícola de resíduos industriais e urbanos, metais pesados podem ser incorporados ao solo por práticas agrícolas tradicionais como uso de fertilizantes e defensivos. Objetivando avaliar o comportamento do cobre aplicado ao solo através de calda bordalesa foram conduzidos ensaios nos quais o fungicida foi aplicado ao solo acondicionado em colunas, bem como consideradas amostras de solo sob cultura de frutíferas. A mobilização do Cu foi estudada em experimento com colunas de lixiviação, feitas de tubos de cloreto de polivinil (PVC), utilizando dois tipos de solos: Latossolo Vermelho eutroférrico (LVef) e Latossolo Vermelho Amarelo distrófico típico (LVAd). O cobre aplicado por um material alcalino como a calda bordalesa é relativamente imóvel no solo, mas pressupõe-se que poderá ser mobilizado pela ação de compostos orgânicos que atuam como complexantes. Desta forma, foram aplicados como compostos orgânicos: dois materiais de uso generalizado na agricultura (esterco de galinha e torta de filtro); um material sintético de elevado poder complexante (NaH2EDTA) e citrato de amônio para representar os agentes quelantes de ocorrência natural no ambiente. Em adição ao experimento em colunas, para determinar as frações de cobre presente no solo, foram coletadas amostras de solo na profundidade de 0-20 cm, no município de Louveira, Estado de São Paulo, em pomares de frutíferas onde se usa rotineiramente calda bordalesa como fungicida. Nesses locais, o teor de Cu do solo extraído por DTPA variou entre 6,5-34,3 mg Cu kg-1, enquanto que o teor de Cu total variou entre 40,8-108,8 mg kg-1. Para avaliar a disponibilidade do Cu nos solos de Louveira e nos solos do experimento em colunas foi escolhido o método de Neubauer, pela vantagem de ser um método biológico de determinação da quantidade disponível de elementos no solo. A lixiviação na coluna do solo LVAd, onde foi aplicado o EDTA, conseguiu mobilizar 436,5 µg de Cu, massa que representa uma fração muito pequena do cobre total aplicado ao solo por meio da calda bordalesa. Trata-se, entretanto, de um valor bastante significativo frente ao que foi removido nos demais tratamentos. Embora quase não tenha sido mobilizado cobre para fora das colunas, os resultados da análise química do solo indicaram a movimentação do cobre dos segmentos superiores para os inferiores, sob a ação dos tratamentos, na faixa de 5,0-48,2 mg Cu. Quanto à absorção de cobre pelas plantas no experimento de Neubauer, observou-se que a aplicação do EDTA favoreceu a absorção do cobre pelas plantas de arroz em ambos os solos estudados, entretanto não influenciou na massa seca das plantas. Já nas amostras dos solos de Louveira a absorção de cobre diminuiu a massa seca das plantas, tanto quando se considerou a concentração de cobre no tecido vegetal como a massa total de cobre absorvido. O Cu absorvido pelas plantas também se correlacionou com teores de cobre trocável, cobre ligado a carbonato e cobre ligado a óxidos de Fe e Mn, obtidos no estudo de fracionamento. O extrator DTPA mostrou ainda ser um bom indicador da disponibilidade de cobre aplicado pela calda bordalesa. / Despite the current concerns regarding the environment contamination by the agricultural use of industrial and urban wastes, heavy metals can be incorporated to the soil through traditional fertilizers and defensives. Aiming to evaluate the behavior of copper applied to the soil through the Bordeaux mixture, trials were carried out in which the fungicide was applied to the soil packed in columns, as well as samples of soil under fruit cultures were considered. The mobilization of Cu was studied in experiments with leaching columns, which consisted of polyvinyl chloride tubes (PVC), using two types of soil: Latossolo Vermelho eutroférrico (LVef) e Latossolo Vermelho Amarelo distrófico típico (LVAd). Copper applied through an alkaline material such as the Bordeaux mixture is relatively immobile in the soil but it is expected to be mobilized by the action of organic complexing compounds. This way they were applied as organic compounds, two materials generally used in agriculture: poultry manure and filter cake; a synthetic material with high affinity for metals (NaH2EDTA) and ammonium citrate in order to represent the ligants of wide spread occurrence in the environment. In addition to the experiment in columns and to determine the fractions of copper present in the soil, 0-20 cm samples of soil were collected in grape and fig orchard located in the city of Louveira , SP, where the Bourdeaux mixture is commonly used as a fungicide. Is these places the total copper content of the soil extracted by DTPA varied between 40,8-108,8 mg kg-1. To evaluate the availability of copper in the soil of Louveira, and in the soils of the column experiment, the Neubauer method was chosen due to the advantage of being a biological method of determination of the available amount of elements in the soil. The leaching in the LVAd soil column, where EDTA was applied was able to mobilize 436,5 µg of cu, mass that represents a very small fraction of the total copper applied to the soil through the Bordeaux mixture. It refers to, subconsequently to a very significant amount when compared to the quantity obtained through other methods. Although almost no copper was removed out of the columns, the results of the chemical analysis indicated the movement of copper from the upper segments to the lower segments, under the action of treatments, the range of 5-48,2 mg of copper. Regarding the absorption of copper by plants in the Neubauer experiment it was observed that the application of EDTA favored the absorption of copper by the rice plants, in both studied soil, however it didn’t influence the dry mass of plants. In the soil samples from Louvreira, the copper absorption diminished the total dry mass of the plants, when considered the copper concentration in the vegetal tissue, as well as the total content of copper absorbed. The copper absorbed by the plants was correlated to exchangeable copper content as well as copper linked to carbonate and copper linked to oxides of Fe and Mn, obtained through the fractioning study. The DTPA extractor proved to be a good indicator of the availability to plants of copper applied through the Bordeaux mixture.

O presente trabalho teve como objetivo principal avaliar as relações entre a composição mineralógica de solos representativos do Estado de São Paulo e alguns de seus atributos eletroquímicos como o ponto de efeito salino nulo (PESN) e a capacidade de troca aniônica (CTA). Especial atenção foi dada também à quantificação de cargas negativas de caráter permanente e à contrastação dos resultados com a composição mineralógica da fração argila, a qual foi avaliada de forma qualitativa e semiquantitativa. Além dos atributos eletroquímicos supracitados, a adsorção e a dessorção de sulfato, principal forma inorgânica de enxofre presente nos solos sob condições aeróbicas, foram estudadas visando-se à determinação de índices representativos desses fenômenos e à associação dos mesmos com atributos mineralógicos, químicos e eletroquímicos dos solos. Em uma primeira etapa, amostras coletadas em camadas subsuperficiais de quinze solos localizados em diferentes regiões do Estado de São Paulo foram submetidas à uma intensa caracterização mineralógica, química e eletroquímica. Além dessas avaliações, as amostras foram utilizadas como adsorvedores em estudos de adsorção e dessorção de sulfato. Em um momento posterior e por meio do tratamento estatístico dos dados, procurou-se analisar as relações individuais dos diversos atributos avaliados com o ponto de efeito salino nulo, capacidade de troca aniônica, adsorção e dessorção de sulfato. Os resultados experimentais obtidos durante a avaliação do ponto de efeito salino nulo das amostras permitiram o desenvolvimento de um programa computacional para o tratamento matemático dos referidos dados visando-se à determinação analítica do valor desse atributo eletroquímico. Testes realizados com dados obtidos por outros autores demonstraram a adequação do programa para a determinação rápida e não-subjetiva do PESN. Em relação às cargas elétricas negativas de superfície, pôde-se verificar uma significativa presença de cargas de caráter permanente, fato que apresentou razoável concordância com a composição mineralógica das amostras. Contudo, faz-se necessária a contrastação de resultados obtidos com o método da adsorção de césio com quantidades de cargas permanentes determinadas por meio do uso de outros procedimentos metodológicos. Ao avaliar-se a capacidade de troca catiônica (CTC) das amostras, utilizando-se diferentes métodos, pôde-se observar que os solos com caráter ácrico estiveram dentre aqueles em que as maiores discrepâncias foram verificadas, fato que sugere a necessidade da reavaliação dos métodos empregados para a determinação da CTC efetiva nesses solos. Os procedimentos adotados permitiram verificar que os óxidos de alumínio mal cristalizados, pres entes na fração argila, são os componentes mais diretamente associados ao ponto de efeito salino nulo e à capacidade de troca aniônica das amostras estudadas. Em relação à adsorção de sulfato, novamente observou-se acentuada relação direta entre o teor dos óxidos de alumínio mal cristalizados e a capacidade adsortiva das amostras bem como com a afinidade apresentada pela fase sólida em relação ao referido ânion. A gibbsita e os óxidos de alumínio mal cristalizados são os constituintes inorgânicos da fase sólida mais diretamente associados à restrição à dessorção de sulfato nas amostras avaliadas, ao passo que a liberação do sulfato retido apresentou relação direta com o teor de caulinita. Esses dados indicam que as aplicações de gesso agrícola devem ser feitas com maior cautela em solos cauliníticos. Em relação aos atributos de fácil e rápida determinação, o pH das amostras medido em solução de fluoreto de sódio (pH NaF) apresentou estreita relação com a presença de óxidos de alumínio nas amostras estudadas e, por essa razão, mostrou-se como um índice bastante promissor para a avaliação indireta da capacidade de retenção aniônica de amostras de camadas subsuperficiais de solos das regiões tropicais. Finalmente, um grande número de correlações não significativas obsevadas entre os teores de óxidos de ferro cristalinos (hematita e goethita) tanto para com atributos eletroquímicos quanto para com a adsorção e dessorção de sulfato parece indicar a existência de acentuada variabilidade comportamental para esses minerais nas amostras estudadas. Desse modo, novos estudos devem ser realizados com os referidos óxidos de ferro visando-se analisar a influência da morfologia, tamanho de cristais e grau de cristalinidade sobre os atributos eletroquímicos e propriedades adsortivas desses minerais. Igualmente, o desenvolvimento de trabalhos de pesquisa de natureza similar envolvendo a gibbsita são também necessários, haja vista a completa ausência de informações relacionadas à variabilidade comportamental desse óxido de alumínio. / The present research aimed at studying the relationships between the mineralogical composition of representative soils from São Paulo State and some of their electrochemical properties, particularly the point of zero salt effect (PZSE) and the anion exchange capacity (AEC). Additionally, it was given special attention to the presence of permanent negative charges in those soils, whose magnitudes were also associated with the mineralogical composition of their clay fractions, which was evaluated by using qualitative and semiquantitative approaches. Besides the above mentioned electrochemical properties, the adsorption and desorption of sulfate, the main inorganic form of sulfur found in soils under aerobic conditions, were studied in order to associate the representative indexes of these phenomena with mineralogical, chemical and electrochemical soil properties. Initially, samples collected in subsurface layers of fifteen soils situated in different regions of São Paulo State were highly characterized as for their mineralogical, chemical and electrochemical properties Besides these evaluations, the soil samples were used as adsorbents in studies of sulfate adsorption and desorption reactions. After this, and through the statistical analyses of data, it was aimed at verifying the individual relationships of the evaluated properties with the PZSE, AEC, sulfate adsorption and desorption indexes. The experimental results obtained during the evaluation of the PZSE values of samples, gave us the possibility of the development of one software for mathematical manipulation of them in order to allow the analytical determination of the above mentioned electrochemical property. The software was evaluated through the analyses of potentiometric titration data from experiments of other authors. The results showed very good agreement between PZSE values calculated by the software and those determined by the authors. By this reason, this approach can be considered very useful for this determination. In relation to surface charges, it was possible to verify reasonable amounts of permanent negative charges in evaluated soil samples and good correspondence of them with soil mineralogical properties. However, more studies are necessary in order to compare the results of cesium adsorption method, employed for this determination in the present research, with ones from other methodologies. The determination of cation exchange capacity (CEC) values through different approaches have shown that the soil samples with acric character were among the ones that present the biggest discrepancies. These results suggest the necessity of reevaluation for the usual methods employed to measurements of CEC values in soils with acric character. The methods used in this research allowed us to verify that the contents of amorphous aluminum oxides in the clay fraction present direct associations with PZSE and AEC values determined in soil samples. In relation to sulfate adsorption, it was also observed the positive effect of amorphous aluminum oxides on the sulfate adsorptive capacities of the studied soils. In the same way, the content of above mentioned oxides present significative and direct correlation with the affinity of surfaces by sulfate ions. The gibbsite and amorphous aluminum oxides are the clay fraction constituents associated with the restriction to sulfate desorption in evaluated soil samples; on the other hand, the transference of sulfate ions from solid surfaces to soil solutions was favored by the high kaolinite contents. These data suggest that the use of gypsum in kaolinitic soils with low contents of oxides must be done with more criteria.Considering the soil properties whose determinations are not time consuming, the pH values evaluated in suspensions of soil-NaF 1 mol L -1 solution (pH NaF) presented very good associations with the aluminum oxides contents of soil samples and, by this reason, it showed also significative correlations with soil sulfate adsorption capacity. These founds indicate that the pH NaF is a very promising index for the indirect evaluation of the anion retention capacity of samples from subsurface layers of tropical soils. Finally, the great number of non-significative correlations verified in this research between crystalline iron oxides (hematite and goethite) contents and electrochemical properties or sulfate adsorption/desorption indexes suggest the existence of non-systematic variations in their intrinsic properties. So, it is very important the establishment of new researches with the objective of acquiring more information about the influence of morphology and crystals size and crystallinity of these adsorbents on their electrochemical properties and adsorptive capacities. These considerations are also applied to gibbsite, since there is no information about this topic associated to this mineral.

O objetivo desse trabalho foi estudar o comportamento do herbicida glifosato em solos sob diferentes aspectos e o deslocamento miscível da atrazina, empregando a modelagem matemática na determinação de parâmetros de sorção e transporte. Para tal, foram conduzidos vários experimentos com o glifosato, no Laboratório de Ecotoxicologia do Centro de Energia Nuclear na Agricultura (CENA/USP), sendo os ensaios referentes a atrazina conduzidos no Forchungszentrum Jülich, Jülich, Alemanha. No primeiro capítulo foi avaliada a influência da matéria orgânica na sorção e dessorção do glifosato em três solos brasileiros com diferentes atributos mineralógicos. A base deste estudo foi o estudo de isotermas de sorção, pela técnica "batch", em amostras de solo com e sem oxidação da matéria orgânica. No segundo capítulo, foi verificada a extensão do efeito de níveis crescentes de fósforo no solo na sorção e dessorção do glifosato. No capítulo terceiro foi estudado o comportamento do glifosato num caso especial: um solo mantido há 23 anos sob plantio direto ou plantio convencional. Para tanto, foram conduzidos 4 experimentos, nos quais foram verificados a mineralização e a formação de resíduo- ligado, a cinética de sorção e dessorção, a sorção/dessorção e a fitodisponibilidade do glifosato, através de um teste biológico. No último capítulo estudou-se o deslocamento miscível da atrazina em colunas deformadas de solo, empregando-se estudo de traçador (Br - ) e modelagem matemática para a determinação de parâmetros de sorção e de transporte do herbicida. Aos resultados de deslocamento do traçador foi aplicado o modelo de transporte baseado na equação de convecção-dispersão, considerando o equilíbrio de sorção. Para o deslocamento da atrazina foi utilizado o modelo matemático "two-site", também baseado na equação de convecção-dispersão, entretanto, considerando o não-equilíbrio químico de sorção. Neste capítulo também foi avaliada a sorção/dessorção da atrazina pela técnica "batch". Optou-se por utilizar a atrazina no estudo de deslocamento miscível e não o glifosato, pelo fato do segundo não apresentar potencial de mobilidade vertical no solo. Concluiu-se que a sorção do glifosato é instantânea, extremamente elevada e está relacionada, principalmente, a fração mineral do solo, sendo que a matéria orgânica desempenha papel secundário no caso de solos oxídicos. O glifosato compete com os fosfatos inorgânicos pelos sítios de sorção no solo, entretanto, esta competição somente passa a ser importante para níveis de P extremamente elevados, os quais não são atingidos em condições reais de campo. O glifosato não pode ser extraído do solo em condições normais de solos agricultáveis, permanecendo na forma de resíduo- ligado. O sistema de plantio direto pode contribuir com a aceleração da mineralização do glifosato no solo, todavia, sua meia-vida é baixa e está relacionada à formação de resíduo-ligado, não tendo apresentado problemas de fitotoxidez nos testes realizados. Com relação ao deslocamento da atrazina, concluiu-se que a molécula apresenta potencial de lixiviação no solo, sendo que este potencial é dependente da sorção nos sítios em equilíbrio e em não-equilíbrio com a solução do solo. No entanto, a sorção irreversível foi mais importante que a sorção "reversível" em ambos os sítios em equilíbrio e não-equilíbrio. Os modelos de transporte foram ajustados com sucesso aos dados de deslocamento miscível do traçador e da atrazina. Todavia, o modelo "two-site" superestimou a sorção irreversível (formação de resíduo-ligado), para a concentração residente na coluna. O modelo de transporte "two-site", ajustado aos dados de deslocamento miscível da atrazina, previu coeficientes de sorção linear semelhantes aos gerados pelo método "batch", o que não foi verdade para a dessorção. / The aim of this research was to evaluate the glyphosate behavior in soils under different aspects, as well as the miscible displacement of atrazine, using mathematical modeling to determine sorption and transport parameters. The experiments about glyphosate were carried out at Laboratory of Ecotoxicology of the Centro de Energia Nuclear na Agricultura (CENA/USP), Piracicaba, SP (Brazil), and the studies about atrazine at Forchungszentrum Jülich, Jülich, Germany. In the first chapter we evaluated the effects of soil organic matter on the sorption and desorption of glyphosate in three soils with different mineralogical attributes. This was an isotherm batch experiment in soil samples with or without organic matter. In the second chapter we evaluated the effects of the increasing rates of phosphorus on the sorption and desorption of glyphosate. In the third chapter we studied the glyphosate behavior as an especial situation: An Brazilian Oxisol collected from both a no-till and a conventional management soil systems. Both agricultural systems had been in production for 23 years. Glyphosate mineralization, its bound-residue forms, sorption and desorption batch kinetics, sorption/desorption batch isotherms experiments, and glyphosate phythoavailability (to Panicum maximum) were determined. In the last chapter, the miscible displacement and the sorption/desorption of atrazine. In order to fit the atrazine breakthrough curves, to evaluate the contribution of sorption on the atrazine leaching (equilibrium vs nonequilibrium sorption; reversible vs irreversible sorption), we employed a tracer study (Br - ) and used mathematical modeling. We fitted the Br - displacement with an equilibrium convective dispersive transport model, and atrazine displacement with two-site chemical nonequilibrium dispersive convective transport model. The atrazine was employed in this study, instead glyphosate, because the second one does not present leaching potential. We concluded the glyphosate sorption is instantaneous, extremely high and presents relationship, mainly, with the mineral soil fraction. Soil organic matter only plays a secondary role for oxidic soils. Glyphosate competes with inorganic phosphates for specific sorption sites, but this competition becomes important when phosphorus is at rates higher than the normally seen in real field conditions. The glyphosate can not be extracted from the soil, under normal conditions of agricultural soils, remaining as bound-residues. The no-till system may contribute to the enhancement of glyphosate mineralization in the soil. However, its half-life is low and is related with the bound-residue formation. Glyphosate did not present phytotoxicity in the specific studied. About atrazine displacement, we concluded the atrazine presented a potential leaching. This potential was dependent of equilibrium and nonequilibrium sorption sites. However, irreversible sorption was more important than "reversible" sorption in equilibrium and nonequilibrium sites. Both equilibrium and nonequilibrium models successfully fitted the Br - and atrazine breakthrough curves, respectively, for both management systems. However, the two-site nonequilibrium model overestimated the irreversible sorption (bound-residue formation) for resident concentration of atrazine within soil column. The two-site nonequilibrium transport model predicted partition coefficients for sorption very similar to these measured in the sorption batch experiment. This was not true for desorption data.

The understanding of the spatial distribution of lead (Pb) in soil is important in the assessment of potential risks and development of remediation strategies for Pb contaminated land. In situ heterogeneity of Pb was measured at two heavily contaminated sites in the United Kingdom using the Portable X-ray Fluorescence Spectrometer (P-XRF) over a range of spatial scales (0.02 to 50 m). The pattern of the distribution of Pb was very variable, and when expressed as heterogeneity factor (HF), it ranged from 1.2 to 3.2 (highly heterogeneous). The effect of such Pb heterogeneity on plant uptake was investigated in greenhouse pot trials. Two earlier pot trials, which assessed the effect of Pb in a fixed concentration (1000 mg/kg) and in a range of concentration (100 to 10000 mg/kg) found a significant effect of the Pb added treatments, when compared to a control treatment (0 mg/kg Pb added). Biomass and uptake varied by 20 to 100% within and between 16 species/varieties. Results enhanced the selection of two species (Brassica napus and Brassica juncea) for further pot trials. A third pot experiment with Brassica napus and Brassica juncea in simplistic binary model of heterogeneity found 20 to 60% lower uptake in the binary treatment, than homogeneous the treatment. Biomass was higher by 10 to 50% in Brassica juncea and 20 to 40% lower for B. napus in the bianary treatment, when compared to the homogeneous and control treatments. The effect of a more realistic in situ heterogeneity on plant uptake was investigated in a further pot trial, which simulated low (LH), medium) (MH) and high (HH) heterogeneity treatments, compared to a homogeneous (HO) treatment. It detected a significant (P < 0.05) impact of heterogeneity on biomass and uptake between treatments and species. Four to five fold lower biomass were recorded in HH treatment, when compared to the HO treatment. Shoot and root uptake in (mg/kg) concentration increased with increasing heterogeneity with peak uptake (twice as high as HO treatment) in LH for B. napus and in HH and MH treatments for B. juncea respectively. Shoot and root Pb masses in (μg) were maximum in HO and MH treatments respectively with 50 to 70% lower Pb mass in the HH treatment. Results showed that response to heterogeneity is species specific. A sub-experiment explored the behaviour of plant roots in HH treatment and found 20 to 80% variation in root biomass between concentric patches with same nominal soil Pb concentrations. This provided insights into varied responses of these species to realistic Pb heterogeneity. The research demonstrated that the presence and extent of in situ heterogeneity of Pb in soil plays an important role in Pb uptake by plants. It also showed that the homogeneous and simplistic binary model of heterogeneity do not give reliable estimates of plant growth and Pb uptake in realistic field conditions. This work has implications for improving the efficiency of phytoremediation of Pb contaminated land, phytomining, reliability of risk assessment and models of human exposure to Pb.

Heterogeneity of contaminants in soils can vary spatially over a range of scales, causing uncertainty in environmental measurements of contaminant concentrations. Sampling designs may aim to reduce the impact of on-site heterogeneity, by using composite sampling, increased sample mass and off-site homogenisation, yet they could overlook the small scale heterogeneity that can have significant implications for plant uptake of contaminants. Moreover, composite sampling and homogenisation may not be relevant to target receptor behaviour, e.g. plants, and studies, using simplistic models of heterogeneity have shown that it can significantly impact plant uptake of contaminants. The alternative approach, to accept and quantify heterogeneity, requires further exploration as contaminant heterogeneity is inevitable within soils and its quantification should enable improved reliability in risk assessment and understanding variability in plant contaminant uptake. This thesis reports the development of a new sampling design, to characterise and quantify contaminant heterogeneity at scales, from 0.02m to 20m, using in situ measurement techniques, and 0.005m to 0.0005m, using ex situ techniques. The design was implemented at two contaminated land sites, with contrasting heterogeneity based upon historic anthropogenic activity and showed heterogeneity varying between contaminants and at different spatial scales, for Pb, Cu and Zn. Secondly, this research demonstrates how contaminant heterogeneity measured in situ can be recreated in a pot experiment, at a scale specific to the plant under study. Results, from 4 different plant species, demonstrated that existing simplistic models of heterogeneity are an inadequate proxy for plant performance and contaminant uptake under field conditions, and significant differences were found in plant contaminant concentrations between simplistic models and those based upon actual site measurements of heterogeneity. Implications of heterogeneity on plant roots were explored in the final experiment showing significant differences in root biomass between patches of differing contaminant concentrations.