Les minéraux nominalement anhydres du manteau terrestre (NAMs) contiennent de l’eau en faible quantité, dissoute sous forme de défauts ponctuels, et qui affecte de manière drastique les propriétés physico-chimiques du manteau supérieur terrestre. Afin de mieux comprendre cet effet, il est nécessaire d’estimer la capacité de stockage de l’eau des phases mantelliques et les mécanismes de solubilité. De nombreuses données expérimentales sur la solubilité de l’eau dans les NAMs tels que l’olivine, le pyroxène et le grenat, sont disponibles dans la littérature. Toutefois, la majorité de ces études ont été réalisées en système simple, et à des températures ou des pressions trop basses pour être représentatives du manteau supérieur terrestre. L’objectif de cette étude était de contraindre les effets combinés de la pression, de la température et de la composition sur la solubilité de l’eau dans l’olivine et le pyroxène dans les conditions du manteau supérieur terrestre. Les expériences ont été réalisées en condition de saturation en eau dans le système MSH enrichi en fer et en fer et aluminium, à 2,5 ; 5 ; 7,5 et 9 GPa, entre 1175 et 1400°C, à l’aide d’une presse multi-enclumes. Les teneurs en eau ont été mesurées par spectroscopie infrarouge en mode polarisé, à partir d’échantillons finement double polis, sur des cristaux orientés de manière aléatoire. Al est incorporé dans l’olivine et le pyroxène selon la réaction de type Tschermak, et diminue avec la pression dans les deux phases. L’ajout d’Al3+ dans le système favorise l’incorporation de H+ dans l’olivine et surtout dans le pyroxène, mais cet effet disparaît à mesure que la pression et la température augmentent. Dans ces conditions, la solubilité de l’eau dans les deux phases est contrôlée par l’activité de l’eau dans le liquide qui se charge de plus en plus en silicates. Le mécanisme majeur de l’incorporation de l’eau dans l’olivine se fait via le remplacement de sites métalliques par 2H+, impliquant que la solubilité de l’eau dans l’olivine est directement proportionnelle à la fugacité de l’eau dans le liquide. Le partage de l’eau entre pyroxène et olivine est toujours inférieur à 1, sauf à basse pression et basse température, quand Al aide à l’incorporation de l’eau dans le pyroxène par rapport à l’olivine. Dans les conditions du manteau convectif profond, l’eau va préférentiellement dans l’olivine. L’effet de la température sur le partage de l’eau entre les deux phases est négligeable. Ces données ont permis de construire un modèle de stockage de l’eau dans l’olivine à toutes pressions et toutes températures, dans le système MFASH. En combinant ce modèle au partage de l’eau entre pyroxène et olivine calculé dans notre étude, et aux données disponibles dans la littérature sur la solubilité de l’eau dans le clinopyroxène et le grenat, nous avons pu modéliser la capacité de stockage de l’eau dans le manteau supérieur terrestre. Ce modèle prédit que la couche de faible vitesse sismique, détectée à 350 km de profondeur par les observations sismiques, peut être expliquée par la fusion partielle de matériel hydraté provenant de la zone de transition et contenant initialement 750 ppm pds H2O. / Trace amounts of hydrogen dissolved as defects in nominally anhydrous minerals (NAMs) in the mantle are believed to play a key role in physical and chemical processes in the Earth’s upper mantle. Hence the estimation of water storage in mantle phases and solubility mechanisms are important in order to better understand the effect of water. Experimental data on water solubility in NAMs are available for upper mantle minerals such as olivine, pyroxenes and garnet. However, the majority of studies are based on single phases, and at temperatures or pressures that are too low for the Earth’s upper mantle. The aim of this study was to constrain the combined effects of pressure, temperature and composition on water solubility in olivine and pyroxene under upper mantle conditions. The solubility of water in coexisting pyroxene and olivine was investigated by simultaneously synthesising the two phases at high pressure and high temperature in a multi-anvil press. Experiments were performed under water-saturated conditions in the MSH systems with Fe and Al at 2.5, 5, 7.5 and 9 GPa and temperatures between 1175 and 1400°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on doubly-polished thin sections of randomly-oriented crystals. Al is incorporated in pyroxene and olivine via the Tschermak substitution and decreases rapidly as pressure increases in both phases. Addition of Al3+ into the system enhances water solubility notably in pyroxene and also in olivine. However, this effect tends to vanish as pressure and temperature increase. Under these conditions, water solubility in both phases is controlled by water activity in the fluid due to dissolution of silicate component. The main mechanism responsible for water incorporation in olivine is 2H+ substituting for metal sites, which indicates that water solubility in olivine is directly proportional to water fugacity. Water partitioning between pyroxene and olivine is always lower than unity except at low pressure and temperature, in which case Al favours water incorporation into pyroxene rather than into olivine. In the conditions of the deep convective mantle, water preferentially goes into olivine. The effect of temperature on water partitioning between the two phases is negligible. The newly collected data allowed the construction of a water storage capacity model in olivine at all pressures and temperatures in the MFASH system. Combining this model with the newly measured partitioning of water between olivine and pyroxene, as well as previous data on solubility in clinopyroxene and garnet, we are able to build a model of the water saturation curve in the upper mantle. This model predicts that the low velocity layer reported by seismic observations at a depth of 350 km depth can be explained by partial melting triggered by the rise of a hydrated mantle-transition-zone material containing 750 wt ppm H2O.

The interest in using sugarcane straw as a feedstock for bioenergy production has been increased considerably. However, indiscriminate straw removal may negatively affect soil functioning. Therefore, this work aimed to quantify and characterize soil solution translocating along the profile, under straw removal rates from the soil surface. Lysimeter systems were built with 1, 20, 50, and 100 cm soil columns, with a sandy clay loam texture, from a commercial sugarcane field in Piracicaba-SP, southeastern Brazil. The experiment was conducted in open area, where the lysimeters were subjected to rainfall and sun radiation. After the soil stabilization within the lysimeters, the treatments were added, consisting of four straw amounts (0, 3, 6, and 12 Mg ha-1), representing straw removal rates of 100 (bare soil), 75, 50, and 0%, respectively. After one year of the first straw addition, the same straw amounts were added again simulating the second harvest. Drained solution was collected and quantified by 17 months and soil moisture was determined over a period of two months using sensors. Dissolved organic carbon (DOC) concentration was measured in automatic analyzer. The soil solution and straw solution, made in water infusion, were characterized in High performance liquid chromatography (HPLC) to verify the presence of toxic compounds. After that, straw and soil solution were used in tests with soybean seed to evaluate the effects in plant germination and initial growth. At the end of the experiment, soil bulk density and soil organic carbon (SOC) analyses were performed. Remaining straw was weight before the new addition, and weight again at the end to determine the decomposition rates. The accumulated volume of solution drained was 30, 11 and 4% lower under 100, 75 and 50% removal rates compared to no removal. Bare soil stored less water, indicating susceptibility to lose water by evaporation. Simulation showed that 100% and 75% removal can induce longer periods of water restriction, which impair sugarcane growth. The DOC production on topsoil was higher in no straw removal; the retention was higher in 1 to 20 cm in no removal and higher in 20 to 50 cm in 50 and 75% removal rates. Bare soil released more DOC below 01 cm indicating a possible C loss. Below 100 cm DOC leachate was quite similar in all treatments, what shows a higher C retention and small C loss even in higher DOC production. Even with differences in DOC retention, increases in C stock below 5 cm were not noticed. We found many phenolic compounds in the straw solution, not found in the soil solution, indicating that in natural conditions straw does not release toxic compounds into soil solution. Plant growth was negatively affected by straw solution, but not by soil solution. Our findings suggest that the medium straw maintenance prevents variations and loss on soil water content. Higher straw amount increases DOC production, which likely alters its composition and subsequent retention in soil. Carbon stock did not increase in the soil subsurface, but probably will in the long-term. The higher straw removal, proportionally, the higher the C losses in the form of CO2 and DOC, consequently the lower soil C retention. More straw on soil surface release more C amounts to the soil, retained or translocated with soil water, may be stored in deeper soil layers. Higher water percolation in the soil profile does not mean higher C losses by leaching in deeper soil. This study has the practical objective of finding an amount of straw to be maintained in the field that ensures the C storage and the better soil functioning, and also supply feedstock for bioenergy production. / O interesse no uso da palha de cana-de-açúcar como matéria-prima para a produção de bioenergia vem crescendo consideravelmente. No entanto, a remoção excessiva da palha pode afetar negativamente o funcionamento do solo. Portanto, o objetivo deste trabalho foi quantificar e caracterizar a solução ao longo do perfil sob níveis de remoção de palha da superfície do solo. Para isso, foi construído um sistema de lisímetros com colunas de 1, 20, 50 e 100 cm de solo, de textura franco argilo arenosa, proveniente de área comercial de cana-de-açúcar em Piracicaba-SP, Brasil. O experimento foi conduzido em área aberta, sujeito a precipitação e luz natural. Depois da estabilização do solo dentro dos tubos, foram adicionados os seguintes tratamentos: 0, 3, 6 e 12 Mg ha-1 de massa seca, representando 100 (solo nu), 75, 50 e 0% de intensidade de remoção de palha, respectivamente, sendo adicionados novamente após um ano. A solução percolada foi coletada e quantificada por 17 meses, a umidade do solo foi determinada por dois meses usando sensores. A concentração de carbono orgânico dissolvido (COD) foi mensurada com analisador automático. A solução do solo e solução da palha, feita por infusão em água, foram caracterizadas em HPLC para verificar a presença de compostos tóxicos. Posteriormente, as soluções da palha e solo foram usadas em testes de sementes de soja para avaliar os efeitos na germinação e crescimento inicial. Ao final do experimento, foram realizadas análises de densidade do solo e carbono orgânica do solo (COS). A palha remanescente foi pesada após um ano, anterior a nova adição, e pesada novamente ao final do experimento, para determinar a taxa de decomposição. O volume de solução percolado foi 30, 11 e 4% menor em 100, 75 e 50% do que em 0% de remoção, respectivamente. O solo descoberto armazenou menos água, indicando susceptibilidade à perda de água por evaporação. A simulação mostrou que 100 e 75% de remoção induzem longos períodos de restrição hídrica, que pode prejudicar o crescimento da planta. A produção de COD na camada superficial foi maior no solo sem remoção; a retenção foi maior de 1 a 20 cm em solo sem remoção, e maior em 20 a 50 cm em 50 e 75% de remoção. O solo descoberto liberou mais COD em de 20 cm do que em superfície, indicando perda de C. Abaixo de 100 cm, o COD lixiviado foi similar nos tratamentos, indicando grande retenção de C e pequenas perdas por lixiviação, mesmo em alta produção de COD. Mesmo com diferenças na retenção de COD, não foi identificado aumento no estoque de C abaixo de 5 cm. Foram encontrados compostos fenólicos na solução da palha, não encontrados na solução do solo, indicando que em condições naturais a palha não libera quantidades significativas de compostos tóxicos na solução do solo. O crescimento de plantas foi negativamente afetado pela solução da palha, mas não pela solução do solo. Nossos resultados sugerem que a manutenção de quantidade média de palha previne perdas e variação no conteúdo de água do solo. Maior quantidade de palha aumenta a produção de COD, que provavelmente altera sua composição, alterando a retenção no solo. O estoque de C não aumentou consideravelmente em subsuperfície, mas muito provavelmente aumentará em escala de tempo maior. Quanto maior a remoção de palha, proporcionalmente maior as taxas de C liberadas na forma de CO2 e COD em subsuperfície, consequentemente, menor a retenção de C no solo. Maiores quantidades de palha na superfície liberam mais C para o solo, retido ou translocado com a água, podendo ser estocado em maiores profundidades do solo. Maior percolação de água no solo não significa maiores perdas de C por lixiviação em profundidade.

O conhecimento do armazenamento de água pelo solo (ARM) é importante por tratarse de uma cultura de grande interesse agronômico. Os tensiômetros de polímero são novos dispositivos capazes de verificar a tensão de água no solo em situações de solo bem seco e realizam medidas do potencial matricial do solo que podem ser utlizadas para o cálculo de ARM. O presente trabalho tem por objetivos: (i) estimar o armazenamento de água no solo através dos métodos de estimativa de balanço hídrico de Thornthwaite e Mather (M), Rijtema e Aboukhaled (R) e Cossenoidal (C), combinados com a evapotranspiração de cultura estimada pelos métodos de Thornthwaite, Penamn e Penman-Monteith, a fim de compara-los com valores de ARM medidos com tensiômetros de polímeros; (ii) estimar a produtividade deplecionada por água e comparar com os dados observados em um experimento de campo com uma cultura da soja. O experimento foi conduzido no município de Piracicaba, SP, com tensiômetros instalados a 0,05, 0,15 e 0,30 m de profundidade, representando as camadas de 0-0,1, 0,1-0,2 e 0,2-0,4 m, respectivamente. De acordo com os resultados obtidos, conclui-se que: (i) o método M subestima a evapotranspiração atual ( ). Consequentemente, superestima o déficit hídrico e subestima S pois assume que (a) só é igual à evapotranspiração potencial quando ARM é igual à capacidade de armazenamento do solo (CAD); (b) M assume aumento linear entre nulo até a ; (ii) os métodos R e C apresentam estimativas de equivalentes; consequentemente, também apresentam estimativas equivalentes de e déficit hídrico. Porém, enquanto o método R assume aumento linear de na faixa de nulo até crítico, o método C assume variação sigmoidal (o que condiz mais com a realidade); (iii) o método de estimativa de evapotranspiração que melhor ajustou-se aos dados reais foi o de Penman e Monteith. Porém, quando apenas houver dados de temperatura disponíveis, recomenda-se a utilização do método de Thornthwaite; (iv) a capacidade de campo pode ser determinada experimentalmente com base no valor médio do potencial matricial ou umidade durante o período chuvoso; (v) para efeito de realização de balanço hídrico, a pode ser determinada com base na determinação prévia do ponto de murcha permanente (teor de água correspondente ao potencial matricial de -15 atm), profundidade efetiva do sistema radicular (profundidade do solo que contribui com 95% da evapotranspiração), com o coeficiente angular da reta igual a um; e (vi) a produtividade deplecionada por água da soja foi de 4279,7 kg ha-1, com uma quebra de 55% em relação à produtividade potencial. / The knowledge about soil water storage (ARM) is essential in agriculture mainly for crops of great agronomic importance. Polymer tensiometers are new instruments capable of measuring soil water tension in very dry soil conditions and perform measurements of soil matrix potential that can be use to calculate ARM. The aims of this study were: (i) to estimate ARM by the water balance estimation methods of Thornthwaite and Mather (M), Rijtema and Aboukhaled (R), and Cossenoidal (C), combined with crop evapotranspiration estimated by Thornthwaite, Penman and Penman-Monteith, in order to compare them with ARM values calculated from polymer tensiometer data; (ii) to estimate the water-depleted productivity of the soybean and compare it with observed data in a field experiment with a soybean crop. The experiment was conducted in Piracicaba, São Paulo State, Brazil, with tensiometers installed at 0.05; 0.15 and 0.3 m depths, representing 0-0.1; 0.1-0.2 and 0.2-0.4 m soil layers. The results show that: (i) the M method underestimates the actual evapotranspiration (ETa). Consequently, it overestimates the hydric deficit and underestimates ARM because it assumes that (a) ETa is only equal to the potential evapotranspiration when ARM is equal to the available soil water storage capacity (AWC); (b) M assumes a linear increase from null ARM until ; (ii) the R and C methods provide equivalent estimates of Eta; consequently, they also present equivalent estimates of ARM and hydric deficit. However, while R assumes a linear increase of Eta from null ARM until a critic ARM, C assumes a sigmoidal variation (which agrees more with reality); (iii) the best method of evapotranspiration estimative was M. However, when only temperature data is available, it is recommended to use the Thornthwaite method; (iv) the field capacity can be determined experimentally based on the average matric potential and moisture during the rainy season; (v) for calculating water balances, AWC can be determined based on the previous determination of the permanent wilting point (water content corresponding to the matric potential of -15 atm), effective depth of the root system (soil depth whichs contributes with 95% of the evapotranspiration), with the slope equal to one; and (iii) the water-depleted productivity of the soybeans was 4279.7 kg ha-1, 55% less than the potential productivity.

Este estudo teve como objetivo analisar o efeito da contaminação por saliva humana na resistência de união (RU) da interface adesiva em dentina por microtração, nas características morfológicas da camada híbrida (CH) em microscopia confocal e no grau de conversão (GC) de 2 sistemas adesivos: Adper Single bond 2 (SB) e Single Bond® Universal (SU). Cento e oitenta dentes terceiros humanos hígidos foram divididos em 12 grupos (n=10), de acordo com o sistema adesivo utilizado, a presença de saliva e o tempo de armazenagem. Após o procedimento adesivo e aplicação da resina composta Filtek Z250, os dentes foram mantidos em água destilada em estufa a 37°C por 48 horas, 6 meses ou 12 meses antes de serem seccionados em palitos (0,8mm x 0,8mm, aproximadamente) para serem levados à máquina de ensaios universal Instron para os testes de microtração. Para à análise da interface adesiva em microscopia confocal de varredura a laser para verificação e mensuração de alterações internas na interface foram utilizados 60 dentes divididos em 6 grupos (n=10) de acordo com os tempos de 48 horas, 6 meses, e 12 meses respectivamente, empregando os sistemas adesivos (SB) e (SU). O efeito da presença de saliva também foi avaliado pelo grau de conversão dos adesivos, empregando-se espectroscopia de infravermelho transformada de Fourier empregando os sistema adesivos (SB) e (SU) com incorporação de saliva humana na sua composição (n=5) com concentrações 10%, 25% e 50% em vol. Para a comparação das variáveis: RU, (GC), espessura da CH, na presença de saliva e tempo de armazenamento foram utilizados os testes de Análise de Variância a três critérios e de comparações múltiplas de Tukey (p<0,05). Os valores de RU (MPa±dp: 48horas/6meses/1ano) foram: SB (43,53 ±6,0; 40,10±3,4; 38,59±5,4); SalSB (43,09±6,2; 39,86±6,6; 37,255,8); SU (42,98±4,3; 39,30±3,6; 40,44±5,7); Sal SU (44,39±4,2; 42,26±2,5; 38,26±5,7). Os Valores médios da CH (MPa±dp: 48horas/6meses/1ano) foram: SalSB (3,59±0,8; 3,59±1,0; 2,08±1,5). SalSU (1,26±0,5; 1,73±0,8; 1,07±0,3). Os valores de GC (MPa±dp: 10%/25%/50%vol) foram: SB (85,59±3,4; 49,68±12,8; 38,56±11,8); SU (85,52±3,3; 86,27±3,5; 57,82±11,1).Conclui-se, portanto, que a contaminação por saliva humana não interferiu na RU da interface dentina/resina composta após 48 horas, 6 meses e 12 meses. A morfologia da camada hibrida foi alterada pela presença da saliva nos períodos 6 e 12 meses,. O GC dos sistemas adesivos foi afetado pela presença de saliva após a polimerização imediata. Entretanto o fator tempo foi determinante para a deformação da interface dentina/resina para ambos os sistemas adesivos. / The objective of this study was to analyze the effect of human saliva contamination on bond strength of the dentin/adhesive interface, morphology of the hybrid layer by confocal microscopy and SEM analysis and degree of conversion of 2 adhesive systems: Adper Single bond 2 (SB) and Single Bond® Universal ( SU). One hundred and eighty healthy human third teeth were divided into 12 groups (n = 10), according to the adhesive system used, the presence of saliva and the storage time. After the adhesive procedure and placement of resin composite (Filtek Z250), the teeth were stored in distilled waterat 37 ° C for 48 hours, 6 months or 12 months before being cut into sticks (0.8mm x 0.8mm, approximately) to the microtensile strength tests. For the analysis of the adhesive interface in confocal microscopy of laser scanning for verification and measurement of internal interface changes, 60 teeth were used divided into 6 groups (n = 10) according to the storage time: 48 hours, 6 months, and 12 monthsand (SB) and (SU). The effect of the presence of saliva was also evaluated by the degree of conversion of the adhesives using Fourier transform infrared spectroscopy employing adhesive (SB) and (SU) systems incorporating human saliva in its composition (n = 5) with 10%, 25% and 50% vol. For the comparison of the variables: bond strength, degree of conversion, and hybrid layer thickness in the presence of saliva and storage time, the three criteria Variance Analysis and Tukey multiple comparisons tests (p <0.05) were used. The values of bond strength (MPa ± dp: 48hours / 6meses / year) were: SB (43.53 ± 6.0, 40.10 ± 3.4, 38.59 ± 5.4); SalSB (43.09 ± 6.2, 39.86 ± 6.6, 37.255.8); SU (42.98 ± 4.3, 39.30 ± 3.6, 40.44 ± 5.7); SU salt (44.39 ± 4.2, 42.26 ± 2.5, 38.26 ± 5.7). The mean values of hybrid layer thickness (MPa ± dp: 48hours / 6meses / year) were: SalSB (3.59 ± 0.8, 3.59 ± 1.0, 2.08 ± 1.5). SalSU (1.26 ± 0.5, 1.73 ± 0.8, 1.07 ± 0.3). The values of degree of conversion (MPa ± dp: 10% / 25% / 50% vol) were: SB (85.59 ± 3.4, 49.68 ± 12.8, 38.56 ± 11.8); (85.52 ± 3.3, 86.27 ± 3.5, 57.82 ± 11.1). It was therefore concluded that human saliva contamination did not interfere on bond strength of the dentin/adhesive interface after 48 hours, 6 months and 12 months. The morphology of the hybrid layer was altered by the presence of saliva after 6 and 12 months. The degree of conversion of adhesive systems was affected by the presence of saliva immediately after polymerization. However, the time factor was determinant for the dentine/resin interface deformation for both adhesive systems.

Legionella pneumophila, the causative agent of Legionnaires' disease, is a water born pathogenic bacteria commonly found in natural and manmade water systems such as rivers, lakes, wet soil, hot and cold water storage systems (being able to survive at temperatures between 6-63 °C, and proliferating between 20-45 °C), showerheads, cooling towers and spa pools. The main pathway of exposure to Legionella is by inhaling the aerosols containing the microorganism. Legionnaires' disease can be fatal if not diagnosed and treated at the right time. Practical Legionella control starts with a risk assessment of the water system and followed by the regular monitoring and water sampling. UK Health and Safety Executive (HSE) have implemented strict legislations to protect the public from Legionnaires' disease. This research highlights and addresses three major data gaps identified in Legionella control and management strategy employed in the UK and worldwide; namely, (i) the underestimation of microbiological threat in current cold water storage sampling strategy, (ii) the inability of current qPCR diagnostic methods to detect live Legionella in water samples, and (iii) the lack of predictive 'risk management system' for Legionella control in domestic water systems. During my PhD, 15 relevant cold water storage tanks (selected from more than 6000 tanks surveyed at different sites located in different London Boroughs) were used to investigate the risk factors that contribute towards Legionella proliferation, and revealed serious shortcomings in the appropriateness of the water sample taken for regulatory testing. Secondly, molecular biology research was carried out to develop an accurate, reliable and rapid testing method for the detection and quantification of live Legionella using qPCR techniques. This was successfully achieved by extracting RNA from a Legionella lenticule, converting the RNA into cDNA and amplifying the cDNA using qPCR techniques. Finally, regular monitoring data from 120 London buildings (60 known to be Legionella positive and 60 known to be Legionella negative) was used to identify the possible risk factors contributing towards Legionella outbreaks. Data for these factors was then used to develop a predictive risk model for Legionella contamination using Principal Component Analysis (PCA). The model was validated with 66 new London buildings and 9 out of London buildings. The model showed 100% accuracy in predicting the risk of Legionella by distinguishing infected and non-infected sites in London as well as for the sites in out of London.

O conhecimento do armazenamento de água pelo solo (ARM) é importante por tratarse de uma cultura de grande interesse agronômico. Os tensiômetros de polímero são novos dispositivos capazes de verificar a tensão de água no solo em situações de solo bem seco e realizam medidas do potencial matricial do solo que podem ser utlizadas para o cálculo de ARM. O presente trabalho tem por objetivos: (i) estimar o armazenamento de água no solo através dos métodos de estimativa de balanço hídrico de Thornthwaite e Mather (M), Rijtema e Aboukhaled (R) e Cossenoidal (C), combinados com a evapotranspiração de cultura estimada pelos métodos de Thornthwaite, Penamn e Penman-Monteith, a fim de compara-los com valores de ARM medidos com tensiômetros de polímeros; (ii) estimar a produtividade deplecionada por água e comparar com os dados observados em um experimento de campo com uma cultura da soja. O experimento foi conduzido no município de Piracicaba, SP, com tensiômetros instalados a 0,05, 0,15 e 0,30 m de profundidade, representando as camadas de 0-0,1, 0,1-0,2 e 0,2-0,4 m, respectivamente. De acordo com os resultados obtidos, conclui-se que: (i) o método M subestima a evapotranspiração atual ( ). Consequentemente, superestima o déficit hídrico e subestima S pois assume que (a) só é igual à evapotranspiração potencial quando ARM é igual à capacidade de armazenamento do solo (CAD); (b) M assume aumento linear entre nulo até a ; (ii) os métodos R e C apresentam estimativas de equivalentes; consequentemente, também apresentam estimativas equivalentes de e déficit hídrico. Porém, enquanto o método R assume aumento linear de na faixa de nulo até crítico, o método C assume variação sigmoidal (o que condiz mais com a realidade); (iii) o método de estimativa de evapotranspiração que melhor ajustou-se aos dados reais foi o de Penman e Monteith. Porém, quando apenas houver dados de temperatura disponíveis, recomenda-se a utilização do método de Thornthwaite; (iv) a capacidade de campo pode ser determinada experimentalmente com base no valor médio do potencial matricial ou umidade durante o período chuvoso; (v) para efeito de realização de balanço hídrico, a pode ser determinada com base na determinação prévia do ponto de murcha permanente (teor de água correspondente ao potencial matricial de -15 atm), profundidade efetiva do sistema radicular (profundidade do solo que contribui com 95% da evapotranspiração), com o coeficiente angular da reta igual a um; e (vi) a produtividade deplecionada por água da soja foi de 4279,7 kg ha-1, com uma quebra de 55% em relação à produtividade potencial. / The knowledge about soil water storage (ARM) is essential in agriculture mainly for crops of great agronomic importance. Polymer tensiometers are new instruments capable of measuring soil water tension in very dry soil conditions and perform measurements of soil matrix potential that can be use to calculate ARM. The aims of this study were: (i) to estimate ARM by the water balance estimation methods of Thornthwaite and Mather (M), Rijtema and Aboukhaled (R), and Cossenoidal (C), combined with crop evapotranspiration estimated by Thornthwaite, Penman and Penman-Monteith, in order to compare them with ARM values calculated from polymer tensiometer data; (ii) to estimate the water-depleted productivity of the soybean and compare it with observed data in a field experiment with a soybean crop. The experiment was conducted in Piracicaba, São Paulo State, Brazil, with tensiometers installed at 0.05; 0.15 and 0.3 m depths, representing 0-0.1; 0.1-0.2 and 0.2-0.4 m soil layers. The results show that: (i) the M method underestimates the actual evapotranspiration (ETa). Consequently, it overestimates the hydric deficit and underestimates ARM because it assumes that (a) ETa is only equal to the potential evapotranspiration when ARM is equal to the available soil water storage capacity (AWC); (b) M assumes a linear increase from null ARM until ; (ii) the R and C methods provide equivalent estimates of Eta; consequently, they also present equivalent estimates of ARM and hydric deficit. However, while R assumes a linear increase of Eta from null ARM until a critic ARM, C assumes a sigmoidal variation (which agrees more with reality); (iii) the best method of evapotranspiration estimative was M. However, when only temperature data is available, it is recommended to use the Thornthwaite method; (iv) the field capacity can be determined experimentally based on the average matric potential and moisture during the rainy season; (v) for calculating water balances, AWC can be determined based on the previous determination of the permanent wilting point (water content corresponding to the matric potential of -15 atm), effective depth of the root system (soil depth whichs contributes with 95% of the evapotranspiration), with the slope equal to one; and (iii) the water-depleted productivity of the soybeans was 4279.7 kg ha-1, 55% less than the potential productivity.

The interest in using sugarcane straw as a feedstock for bioenergy production has been increased considerably. However, indiscriminate straw removal may negatively affect soil functioning. Therefore, this work aimed to quantify and characterize soil solution translocating along the profile, under straw removal rates from the soil surface. Lysimeter systems were built with 1, 20, 50, and 100 cm soil columns, with a sandy clay loam texture, from a commercial sugarcane field in Piracicaba-SP, southeastern Brazil. The experiment was conducted in open area, where the lysimeters were subjected to rainfall and sun radiation. After the soil stabilization within the lysimeters, the treatments were added, consisting of four straw amounts (0, 3, 6, and 12 Mg ha-1), representing straw removal rates of 100 (bare soil), 75, 50, and 0%, respectively. After one year of the first straw addition, the same straw amounts were added again simulating the second harvest. Drained solution was collected and quantified by 17 months and soil moisture was determined over a period of two months using sensors. Dissolved organic carbon (DOC) concentration was measured in automatic analyzer. The soil solution and straw solution, made in water infusion, were characterized in High performance liquid chromatography (HPLC) to verify the presence of toxic compounds. After that, straw and soil solution were used in tests with soybean seed to evaluate the effects in plant germination and initial growth. At the end of the experiment, soil bulk density and soil organic carbon (SOC) analyses were performed. Remaining straw was weight before the new addition, and weight again at the end to determine the decomposition rates. The accumulated volume of solution drained was 30, 11 and 4% lower under 100, 75 and 50% removal rates compared to no removal. Bare soil stored less water, indicating susceptibility to lose water by evaporation. Simulation showed that 100% and 75% removal can induce longer periods of water restriction, which impair sugarcane growth. The DOC production on topsoil was higher in no straw removal; the retention was higher in 1 to 20 cm in no removal and higher in 20 to 50 cm in 50 and 75% removal rates. Bare soil released more DOC below 01 cm indicating a possible C loss. Below 100 cm DOC leachate was quite similar in all treatments, what shows a higher C retention and small C loss even in higher DOC production. Even with differences in DOC retention, increases in C stock below 5 cm were not noticed. We found many phenolic compounds in the straw solution, not found in the soil solution, indicating that in natural conditions straw does not release toxic compounds into soil solution. Plant growth was negatively affected by straw solution, but not by soil solution. Our findings suggest that the medium straw maintenance prevents variations and loss on soil water content. Higher straw amount increases DOC production, which likely alters its composition and subsequent retention in soil. Carbon stock did not increase in the soil subsurface, but probably will in the long-term. The higher straw removal, proportionally, the higher the C losses in the form of CO2 and DOC, consequently the lower soil C retention. More straw on soil surface release more C amounts to the soil, retained or translocated with soil water, may be stored in deeper soil layers. Higher water percolation in the soil profile does not mean higher C losses by leaching in deeper soil. This study has the practical objective of finding an amount of straw to be maintained in the field that ensures the C storage and the better soil functioning, and also supply feedstock for bioenergy production. / O interesse no uso da palha de cana-de-açúcar como matéria-prima para a produção de bioenergia vem crescendo consideravelmente. No entanto, a remoção excessiva da palha pode afetar negativamente o funcionamento do solo. Portanto, o objetivo deste trabalho foi quantificar e caracterizar a solução ao longo do perfil sob níveis de remoção de palha da superfície do solo. Para isso, foi construído um sistema de lisímetros com colunas de 1, 20, 50 e 100 cm de solo, de textura franco argilo arenosa, proveniente de área comercial de cana-de-açúcar em Piracicaba-SP, Brasil. O experimento foi conduzido em área aberta, sujeito a precipitação e luz natural. Depois da estabilização do solo dentro dos tubos, foram adicionados os seguintes tratamentos: 0, 3, 6 e 12 Mg ha-1 de massa seca, representando 100 (solo nu), 75, 50 e 0% de intensidade de remoção de palha, respectivamente, sendo adicionados novamente após um ano. A solução percolada foi coletada e quantificada por 17 meses, a umidade do solo foi determinada por dois meses usando sensores. A concentração de carbono orgânico dissolvido (COD) foi mensurada com analisador automático. A solução do solo e solução da palha, feita por infusão em água, foram caracterizadas em HPLC para verificar a presença de compostos tóxicos. Posteriormente, as soluções da palha e solo foram usadas em testes de sementes de soja para avaliar os efeitos na germinação e crescimento inicial. Ao final do experimento, foram realizadas análises de densidade do solo e carbono orgânica do solo (COS). A palha remanescente foi pesada após um ano, anterior a nova adição, e pesada novamente ao final do experimento, para determinar a taxa de decomposição. O volume de solução percolado foi 30, 11 e 4% menor em 100, 75 e 50% do que em 0% de remoção, respectivamente. O solo descoberto armazenou menos água, indicando susceptibilidade à perda de água por evaporação. A simulação mostrou que 100 e 75% de remoção induzem longos períodos de restrição hídrica, que pode prejudicar o crescimento da planta. A produção de COD na camada superficial foi maior no solo sem remoção; a retenção foi maior de 1 a 20 cm em solo sem remoção, e maior em 20 a 50 cm em 50 e 75% de remoção. O solo descoberto liberou mais COD em de 20 cm do que em superfície, indicando perda de C. Abaixo de 100 cm, o COD lixiviado foi similar nos tratamentos, indicando grande retenção de C e pequenas perdas por lixiviação, mesmo em alta produção de COD. Mesmo com diferenças na retenção de COD, não foi identificado aumento no estoque de C abaixo de 5 cm. Foram encontrados compostos fenólicos na solução da palha, não encontrados na solução do solo, indicando que em condições naturais a palha não libera quantidades significativas de compostos tóxicos na solução do solo. O crescimento de plantas foi negativamente afetado pela solução da palha, mas não pela solução do solo. Nossos resultados sugerem que a manutenção de quantidade média de palha previne perdas e variação no conteúdo de água do solo. Maior quantidade de palha aumenta a produção de COD, que provavelmente altera sua composição, alterando a retenção no solo. O estoque de C não aumentou consideravelmente em subsuperfície, mas muito provavelmente aumentará em escala de tempo maior. Quanto maior a remoção de palha, proporcionalmente maior as taxas de C liberadas na forma de CO2 e COD em subsuperfície, consequentemente, menor a retenção de C no solo. Maiores quantidades de palha na superfície liberam mais C para o solo, retido ou translocado com a água, podendo ser estocado em maiores profundidades do solo. Maior percolação de água no solo não significa maiores perdas de C por lixiviação em profundidade.

Temporal gravimeter observations, used in geodesy and geophysics to study variation of the Earth’s gravity field, are influenced by local water storage changes (WSC) and – from this perspective – add noise to the gravimeter signal records. At the same time, the part of the gravity signal caused by WSC may provide substantial information for hydrologists. Water storages are the fundamental state variable of hydrological systems, but comprehensive data on total WSC are practically inaccessible and their quantification is associated with a high level of uncertainty at the field scale. This study investigates the relationship between temporal gravity measurements and WSC in order to reduce the hydrological interfering signal from temporal gravity measurements and to explore the value of temporal gravity measurements for hydrology for the superconducting gravimeter (SG) of the Geodetic Observatory Wettzell, Germany. A 4D forward model with a spatially nested discretization domain was developed to simulate and calculate the local hydrological effect on the temporal gravity observations. An intensive measurement system was installed at the Geodetic Observatory Wettzell and WSC were measured in all relevant storage components, namely groundwater, saprolite, soil, top soil and snow storage. The monitoring system comprised also a suction-controlled, weighable, monolith-filled lysimeter, allowing an all time first comparison of a lysimeter and a gravimeter. Lysimeter data were used to estimate WSC at the field scale in combination with complementary observations and a hydrological 1D model. Total local WSC were derived, uncertainties were assessed and the hydrological gravity response was calculated from the WSC. A simple conceptual hydrological model was calibrated and evaluated against records of a superconducting gravimeter, soil moisture and groundwater time series. The model was evaluated by a split sample test and validated against independently estimated WSC from the lysimeter-based approach. A simulation of the hydrological gravity effect showed that WSC of one meter height along the topography caused a gravity response of 52 µGal, whereas, generally in geodesy, on flat terrain, the same water mass variation causes a gravity change of only 42 µGal (Bouguer approximation). The radius of influence of local water storage variations can be limited to 1000 m and 50 % to 80 % of the local hydro¬logical gravity signal is generated within a radius of 50 m around the gravimeter. At the Geodetic Observatory Wettzell, WSC in the snow pack, top soil, unsaturated saprolite and fractured aquifer are all important terms of the local water budget. With the exception of snow, all storage components have gravity responses of the same order of magnitude and are therefore relevant for gravity observations. The comparison of the total hydrological gravity response to the gravity residuals obtained from the SG, showed similarities in both short-term and seasonal dynamics. However, the results demonstrated the limitations of estimating total local WSC using hydrological point measurements. The results of the lysimeter-based approach showed that gravity residuals are caused to a larger extent by local WSC than previously estimated. A comparison of the results with other methods used in the past to correct temporal gravity observations for the local hydrological influence showed that the lysimeter measurements improved the independent estimation of WSC significantly and thus provided a better way of estimating the local hydrological gravity effect. In the context of hydrological noise reduction, at sites where temporal gravity observations are used for geophysical studies beyond local hydrology, the installation of a lysimeter in combination with complementary hydrological measurements is recommended. From the hydrological view point, using gravimeter data as a calibration constraint improved the model results in comparison to hydrological point measurements. Thanks to their capacity to integrate over different storage components and a larger area, gravimeters provide generalized information on total WSC at the field scale. Due to their integrative nature, gravity data must be interpreted with great care in hydrological studies. However, gravimeters can serve as a novel measurement instrument for hydrology and the application of gravimeters especially designed to study open research questions in hydrology is recommended. / Zeitabhängigen Gravimetermessungen, die in der Geodäsie und der Geophysik eingesetzt werden, um Variationen des Erdschwerefelds zu messen, werden durch lokale Wasserspeicheränderungen beeinflusst und verursachen – aus dieser Perspektive – ein hydrologisches Störsignal in den Gravimetermessungen. Gleichzeitig bietet der Teil des Gravimetersignals, der durch Wasserspeicheränderungen hervorgerufen wird, das Potential wichtige Informationen über hydrologische Speicher zu gewinnen, da zwar Wasserspeicher eine grundlegende Zustandsgröße hydrologischer Systeme darstellt, jedoch ihre Quantifizierung mit einem hohen Maß an Unsicherheiten auf der Feldskala behaftet ist. Diese Studie untersucht die Beziehung zwischen zeitabhängigen Gravimetermessungen und Wasserspeicheränderungen, um die Gravimetermessungen von dem hydrologischen Störsignal zu bereinigen und um den Nutzen der Gravimetermessungen für die Hydrologie zu erkunden. Dies geschieht am Beispiel des Supraleitgravimeters (SG) des Geodätischen Observatoriums Wettzell in Deutschland. Ein 4D Vorwärtsmodel mit einer räumlich genesteten Diskretisierungsdomäne wurde entwickelt, um die lokalen hydrologischen Masseneffekte auf Gravimetermessungen zu simulieren. Des Weiteren wurde ein intensives Messsystem am Geodätischen Observatorium Wettzell installiert, um die Wasserspeicheränderungen in allen relevanten Speicherkomponenten, also im dem Grundwasser, in der ungesättigten Zone und im Schneespeicher zu messen. Das Monitoringsystem beinhaltete auch einen wägbaren, monolithischen Lysimeter mit Matrixpotentialübertragung, der es uns ermöglichte, zum ersten Mal einen Lysimeter direkt mit einem Gravimeter zu vergleichen. Die Lysimetermessungen wurden in Kombination mit komplementären hydrologischen Beobachtungen und einem 1D-Modell verwendet, um die Wasserspeicheränderungen auf der Feldskala zu bestimmen. Die Gesamtwasserspeicheränderungen wurden bestimmt, Unsicherheiten abgeschätzt und der hydrologische Masseneffekt auf Gravimetermessungen berechnet. Schlussendlich wurde ein einfaches, konzeptionelles, hydrologisches Modell mittels der Zeitreihen von dem SG, Bodenfeuchte- und Grundwassermessungen kalibriert und evaluiert. Das Modell wurde durch einen “Split-Sample-Test” evaluiert und basierend auf unabhängig bestimmten Wasserspeicheränderungen bestimmt auf Grundlage der Lysimetermessungen validiert. Die Simulation des hydrologischen Masseneffektes auf Gravimetermessungen zeigte, dass Wasserspeicheränderungen von einem Meter Höhe entlang der Topographie, einen Erdschwereeffekt von 52 µGal hervorriefen, während in der Geodäsie im Allgemeinen die gleiche Wassermassenvariation in flachem Terrain eine Erdschwereeffekt von nur 42 µGal (Bouguer-Platte) hervorruft. Der Einflussradius der lokalen Wasserspeicheränderungen kann auf 1000 m begrenzt werden, und 50 % bis 80 % des lokalen hydrologischen Erdschweresignals wird in einem Radius von 50 m um den Gravimeter generiert. Wasserspeichervariationen in der Schneedecke, im Oberboden, dem ungesättigten Saprolith und im gelüfteten Aquifer, sind allesamt wichtige Größen der lokalen Wasserbilanz. Mit der Ausnahme von Schnee beeinflussen alle Speicheränderungen die Gravimetermessungen in derselben Größenordnung und sind daher für die Gravimetermessungen von Bedeutung. Ein Vergleich des lokalen hydrologischen Gravitationseffektes mit den SG Residuen zeigte sowohl ereignisbezogene als auch saisonalen Übereinstimmungen. Weiterhin zeigten die Ergebnisse jedoch auch die Grenzen bei der Bestimmung der gesamten lokalen Wasserspeichervariationen mithilfe hydrologischer Punktmessungen auf. Die Ergebnisse des Lysimeter-basierten Ansatzes zeigten, dass SG Residuen mehr noch, als bisher aufgezeigt, durch lokale Wasserspeicheränderungen hervorgerufen werden. Ein Vergleich der Resultate mit anderen Methoden, die in der Vergangenheit zur Korrektur zeitabhängiger Erdschwerebeobachtungen durch Bestimmung des lokalen hydrologischen Masseneffekte verwendet wurden, zeigte, dass die unabhängige Berechnung von Wasserspeicheränderungen durch Lysimetermessungen erheblich verbessert werden kann und dass diese somit eine verbesserte Methode zur Bestimmung des lokalen hydrologischen Erdschwereeffekts darstellt. Die Installation eines Lysimeters ist somit im Zusammenhang mit einer Reduzierung des hydrologischen Störsignals und an Standorten, wo zeitabhängige Erdschwerebeobachtungen für geophysikalische Studien, die über die lokale Hydrologie hinausgehen verwendet werden, zu empfehlen. Aus hydrologischer Sicht zeigte diese Studie, dass die Verwendung von zeitabhängigen Gravimetermessungen als Kalibrierungsdaten die Modellergebnisse im Vergleich zu hydrologischen Punktmessungen verbesserten. Auf Grund ihrer Fähigkeit, über verschiedene Speicherkomponenten und ein größeres Gebiet zu integrieren, bieten Gravimeter verallgemeinerte Informationen über die Gesamtwasserspeicherveränderungen auf der Feldskala. Diese integrative Eigenschaft macht es notwendig, Erdschweredaten in hydrologischen Studien mit großer Vorsicht zu interpretieren. Dennoch können Gravimeter der Hydrologie als neuartiges Messinstrument dienen und die Nutzung von Gravimetern, die speziell für die Beantwortung noch offener Forschungsfragen der Hydrologie entwickelt wurden wird hier empfohlen.

Natural coarse textured soils comprise a significant portion (approximately 20%) of the area to be mined at Suncor, Syncrude (aurora mine), Albian/Shell, and CNRL mines in the Alberta’s oil sands (Macyk, 2006). Although similar in soil textural classifications, the undisturbed areas support a range of ecosite types which exhibit different moisture regimes, suggesting that there are natural mechanisms controlling the plant available water sufficient for forest development. The global objective of this study was to evaluate the potential for textural variability to enhance water storage in coarse textured soil. The observations of the infiltration and drainage behaviour of natural and reclaimed coarse-texture soils in this study have demonstrated that this potential exists and can be applied in reclamation design to achieve the ranges of soil water storage needed to establish different ecosites. Field based infiltration and drainage testing, pit excavation and sampling have been completed on 14 sites (7 natural and 7 reclaimed). Bulk saturated hydraulic conductivity and field capacity were estimated for each of the 14 sites based on the field test results. The observed transient water dynamics give an indication of the effect of layering on these material properties. Laboratory analysis of water content (650 samples), particle size (650 samples), water retention (35 samples), organic carbon (100 samples) as well as calibration of field instrumentation were completed on a large number of samples (approximate values shown in brackets above) across all sites. The laboratory analysis was used to characterize textural variability (mean and standard deviation of the particle diameter) for the layered sites and estimate the soil water retention curve (SWRC) relationships for the range of soil textures encountered at the study sites. Pedotransfer functions (PTFs) were used to investigate if there were significant differences in the residual sum of squares between estimated and measured SWRCs. The measured organic carbon was used to aid in estimating permanent wilting point (WP) used in the calculation of the available water holding capacity (AWHC) of all profiles. An investigation into the calibration of the moisture capacitance probe (MCP) was undertaken as part of a comparison of the measured and simulated volumetric water content (VWC) profiles. Water storage at the cessation of drainage was related to the soil texture and textural variability as measured in the laboratory. Sites with more textural variability generally stored more water for plant use. There appeared to be a limit to what can be considered ‘useful’ textural variability. If adjacent soil layers had too extreme a contrast in texture and therefore hydraulic conductivity, unstable/preferential flow (i.e. bypassing of some of the water and nutrients from plant roots) occurred. The total porosity calculated from field samples was often higher than the maximum measured VWC in each layer which may be indicative of one or more factors that resulted in less than full saturation being attained within the targeted 1 m depth of saturation during the test. Some of these factors include: errors in sampling leading to an overestimate of total porosity; lateral flow along textural interfaces; air entrapment within the rapidly advancing wetting front; unstable/preferential flow as a result of the high contrast in hydraulic conductivity (fine over coarse) between adjacent layers (i.e. Ks Ratio >20) or where tests were conducted on slopes (i.e. funnel flow). This latter case was common at the reclaimed sites. A modelling study of one uniform (SV10) and one layered (NLFH1) natural site was conducted. The models were built by incorporating soil properties of the layers in the various soil profiles as estimated from field and/or laboratory testing. This study offers a comparison between various PTFs and their ability to capture the soil-water storage/dynamics during infiltration and drainage testing. The Arya PTF gave a better estimation of the laboratory measured SWRCs. However, when modeling the measured infiltration and drainage testing for the relatively uniform site SV10, the Arya PTF and Modified Kovacs (MK) PTF performed similarly. The Arya PTF performing slightly better for the infiltration phase and the MK PTF performing slightly better for the drainage phase. Both PTFs gave a reasonable estimation of water storage but the MK PTF gave a better estimation of the water storage with time as compared to the Arya PTF. For the highly layered site NLFH1, neither model performed well. The Arya PTF gave a substantially better estimation of the infiltration phase and gave the better estimation of the magnitude of water storage with time, the MK PTF performed marginally better for the drainage phase and gave a better estimation of the shape of the water storage with time. Generally, the study showed that the replication of the profile water storage requirements for the layered natural ecosites (‘b’ and ‘d’ ecosites) has been achieved and can be achieved by layering (or even mixing) available coarse textured reclamation materials. This study has indicated that replicating the highly uniform ecosites (‘a’ ecosites) is where the bigger challenge lies in reclamation. Reclaiming with a diversity of target ecosites is essential to achieving the pre-disturbance land capability standard that the mine operators are bound by. The temptation may exist to simply condone reclamation that has met or exceeded the pre-exisiting land capability. However, problems with ground water recharge and regional water distribution are likely to arise if large areas of lower functioning ecosites are replaced with higher functioning ecosites.

Freshwater is a vital resource that circulates between the atmosphere, the land and the sea. Understanding and quantifying changes to the partitioning of precipitation into evapotranspiration, runoff and water storage change in the landscape are required for assessing changes to freshwater availability. However, the partitioning processes and their changes are complex due to multiple change drivers and effects. This thesis investigates and aims to identify and separate the effects of atmospheric climate change and various landscape drivers on long-term freshwater change. This is done based on hydroclimatic, land-use and water-use data from the beginning of the twentieth century up to present times and across different regions and scales, from catchment to global. The analyzed landscape drivers include historic developments of irrigated and non-irrigated agriculture and flow regulation. The thesis uses and develops further a data-motivated approach to interpret available hydroclimatic and landscape data for identification of water change drivers and effects, expanding the approach application from local to continental and global scales. Based on this approach development, the thesis identifies hydroclimatic change signals of landscape drivers against the background of multiple coexisting drivers influencing worldwide freshwater change, within and among hydrological basins. Globally, landscape drivers are needed to explain more than 70% of the historic hydroclimatic changes, of which a considerable proportion may be directly human-driven. These landscape- and human-driven water changes need to be considered and accounted for also in modeling and projection of changes to the freshwater system on land. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Submitted.</p> / VR, project 2009-3221