Nous avons procédé dans cette thèse, à l'étude de la phase supraconductrice du composé organique quasi unidimensionnel, (TMTSF)2ClO4, dans son état relaxé et dans son état faiblement désordonné en se servant de la vitesse de refroidissement comme paramètre modifiable au passage de la température de transition de la mise en ordre des anions à TAO=24K comme c'est montré par les mesures de rayons X. Des mesures de transport électronique linéaire (mesure de résistivité) et non linéaire (V-I) ont été effectuées en injectant un courant le long de l'axe c de plus faible conduction et sous champ magnétique appliqué perpendiculairement (H//c) et parallèlement (H//b) aux plans supraconducteurs. Dans l'état relaxé, nous avons déterminé, pour la première fois, le diagramme de phase de vortex à partir des mesures de résistivité interplans et sous champ H//c, en établissant les différentes lignes caractéristiques de ce diagramme de phase (ligne du champ critique, ligne de fusion, ). L'analyse des courants critiques et des fluctuations supraconductrice nous révèlent bien clairement l'existence de fluctuations dont le caractère est de nature tridimensionnelle (3D). L'extrapolation de Hc2(T) à T=0K nous donne Hc2(0)=0.19T. Dans l'état liquide de vortex, au dessus de la température de fusion, l'analyse des courbes de résistivité électrique nous révèle un comportement thermiquement activé dans le modèle de TAFF (thermally activated flux flow) décrit par la loi d'Arrhenius. Nous avons fini l'étude de l'état liquide de vortex par une analyse de l'énergie d'activation. Nous avons trouvé une dépendance en 1/H de l'énergie d'activation indiquant une caractéristique liée à la déformation plastique des lignes de flux tridimensionnelles à cause vraisemblablement des joints de grains apparaissant lors du refroidissement. Cette dépendance est en faveur de l'anisotropie modérée dans notre composé. Les mesures de résistivité en champ magnétique appliqué le long de l'axe b de conduction modérée(H//b) montre une survie de la supraconductivité à très fort champ magnétique Cette possible survie de la supraconductivité, peut être expliquée par le changement de la dimensionnalité effective du système 3D vers 2D, résultant de la réduction de la longueur de cohérence supraconductrice à très fort champ magnétique. Le changement de la dimensionnalité 3D vers 2D à partir d'un champ de découplage évalué à H*=1T, s'accompagne d'une transition métal- isolant. A ce champ correspond une température de découplage des plans qui est de 0.65K. L'augmentation du désordre introduit par la vitesse de refroidissement montre une augmentation du champ critique supérieur, une ligne de fusion qui se décale vers les plus basses températures et une diminution de la longueur de corrélation des lignes de flux selon la direction la plus faiblement conductrice.

Multipotent mesenchymal stem cells (MSCs), found in many adult tissues, may be useful for regenerative medicine applications. Their identification and purification have been difficult due to their low frequency and lack of unambiguous markers. Using a magnetic micro-beads negative selection technique to remove contaminating hematopoietic cells from mouse bone marrow stromal cells (BMSCs), our lab recently isolated a highly purified osteoprogenitor (HipOp) population that was also enriched for other mesenchymal precursors, including MSCs (Itoh and Aubin, 2009). To further enhance enrichment, we positively selected BMSCs and HipOps for CD73, a putative MSC marker, which resulted in no significant additional enrichment for osteoprogenitors when the population was tested in vitro. However, we also found that HipOps were enriched in vascular endothelial cells, and that removing these cells by further negative selection with CD31/PECAM resulted in a CD31(-) HipOp population with higher osteogenic capacity than HipOps in vitro and in vivo.

Multipotent mesenchymal stem cells (MSCs), found in many adult tissues, may be useful for regenerative medicine applications. Their identification and purification have been difficult due to their low frequency and lack of unambiguous markers. Using a magnetic micro-beads negative selection technique to remove contaminating hematopoietic cells from mouse bone marrow stromal cells (BMSCs), our lab recently isolated a highly purified osteoprogenitor (HipOp) population that was also enriched for other mesenchymal precursors, including MSCs (Itoh and Aubin, 2009). To further enhance enrichment, we positively selected BMSCs and HipOps for CD73, a putative MSC marker, which resulted in no significant additional enrichment for osteoprogenitors when the population was tested in vitro. However, we also found that HipOps were enriched in vascular endothelial cells, and that removing these cells by further negative selection with CD31/PECAM resulted in a CD31(-) HipOp population with higher osteogenic capacity than HipOps in vitro and in vivo.

From the Proceedings of the 1971 Meetings of the Arizona Section - American Water Resources Assn. and the Hydrology Section - Arizona Academy of Science - April 22-23, 1971, Tempe, Arizona / Recharge wells may be used in various problems relating to chemical water quality because of the phenomenon of in-aquifer mixing. This paper reviews specific recharge well-mixing techniques of possible utility in underground mixing operations for nitrate control. Illustrative data from field studies at a recharge site near Tucson, Arizona are presented. Both single- and 2-well types of mixing were investigated. In single-well operations, effluent recharge and pumping of the subsequent mixture occur at the same well. Differences in chlorine ion levels were used to distinguish between recharge effluent and native groundwater. Undiluted effluent was discharged in single-well operations until a pumped volume ratio of about 0.4 was attained. Dilution increased steadily with increased pumping and the relative concentration versus pumped volume curve was s-shaped. Seven-day pauses after effluent recharge resulted in immediate pumping of almost completely diluted water, probably because groundwater movement swept the effluent beyond the pumping unit during the pause. With 2-well pumping, the chlorine breakthrough curve reached a constant level at about 13 days and was close to that of the pause-type, single-well regime.

Le mercure est un contaminant présent dans l'ensemble des compartiments de l'environnement et l'homme y est directement exposé via l'alimentation. Actuellement, les organismes gouvernementaux évaluent la sécurité des produits alimentaires en se basant essentiellement sur la concentration totale de cet élément. Cependant, la toxicité du mercure dépend, entre autre, de l'espèce absorbée (dont le méthylmercure, sa forme la plus toxique). Par conséquent, l'analyse de spéciation, c'est à dire la détection et quantification des différentes formes chimiques de cet élément, présente un intérêt croissant. Le principal objectif de ce projet a donc été de développer et de valider, sous assurance qualité, une méthode sensible et d'une grande exactitude, basée sur l'utilisation de la dilution isotopique. Elle sera par la suite appliquée comme méthode de référence par l'agence pour l'analyse en spéciation du mercure dans les produits de la pêche afin de permettre une meilleure évaluation des risques encourus par le consommateur. La première partie de ce travail a porté sur l'étude du cycle biogéochimique du mercure et de l'état de l'art des diverses méthodes de préparation de l'échantillon, de séparation et de quantification du Hg dans les matrices biologiques, afin d'émettre des choix analytiques. Ainsi, les principaux composés mercuriels susceptibles d'être retrouvés dans les produits de la pêche (le méthylmercure et le mercure inorganique) ont été déterminés par couplage GC-ICP-MS et une quantification par dilution isotopique. La seconde partie des travaux a été consacrée à l'optimisation de la méthode de préparation des échantillons et de la technique de quantification. Ces travaux sur différents matériaux de référence certifiés ont montré que des modifications de la distribution naturelle de l'échantillon pouvaient survenir dès l'étape d'extraction, préconisant un marquage isotopique avant extraction solide-liquide par digiPREP des espèces mercurielles et dérivation par propylation par le tétrapropylborate de sodium et agitation rotative. Les résultats expérimentaux ont été traités par dilution isotopique simple et multiple. Les teneurs obtenues ont été similaires, pour l'ensemble des matrices analysées, montrant que peu ou pas de transformation inter-espèces surviennent au cours de la procédure analytique. Une quantification par double marquage isotopique et dilution isotopique simple a donc été conservée. L'évaluation des critères analytique a démontré que la méthode est validée pour la spéciation du mercure dans les produits de la pêche, selon les normes françaises AFNOR NF V03-110 de 1998 et de 2010. La dernière partie des travaux a porté sur l'application de la méthode validée à la spéciation du mercure dans des échantillons biologiques réels, ainsi qu'à la participation à plusieurs essais interlaboratoires d'aptitudes organisés par le CSL-FAPAS sur un échantillon de thon en conserve et par l'IRMM sur le matériau IMEP-109 de homard.

La caractérisation géochimique et isotopique des eaux souterraines de la " zone minéralisée de l'Entre-Deux-Mers " indique une origine commune de la minéralisation, directement liée à la minéralogie des formations captées par les forages.La géochimie montre que les interactions eau-roche sont majoritairement influencées par la présence d'évaporites, mais que d'autres interactions mettant en jeu des carbonates, des silicates et des argiles existent. Un modèle géochimique d'acquisition de la minéralisation reconstitue parfaitement la chimie des eaux souterraines à l'échelle de la zone d'étude. Ce modèle, construit en se basant sur la géochimie des eaux et sur la minéralogie des formations tertiaires du nord du Bassin aquitain, met à l'équilibre des eaux avec des formations carbonatées et évaporitiques. Afin de mieux comprendre la distribution latérale et verticale des formations tertiaires et leur minéralogie, une approche paléogéographique et sédimentologique a permis de localiser les différents horizons riches en sulfates et/ou en fluorures, mais aussi de comprendre leur origine de dépôt. En se basant sur l'hydrogéologie, la paléogéographie, la minéralogie et la géochimie, des hypothèses de répartition de la minéralisation à l'échelle du forage ont pu être testées. Les résultats de la modélisation couplée hydrodynamique-transport reconstituent la chimie des eaux prélevées par les forages de la " zone minéralisée de l'Entre-Deux-Mers ". Au vu de ces résultats, un modèle avec obturation des horizons riches en sulfates et en fluorures a été testé et les résultats obtenus ouvrent des perspectives pour des futures recherches. Ce travail a donc permis de comprendre l'origine de la minéralisation des eaux de " la zone minéralisée de l'Entre-Deux-Mers ", mais aussi de proposer des améliorations et des perspectives pour une meilleure gestion d'une des principales ressources en eau potable de la Gironde.

Une voie agroécologique pour améliorer la fourniture des services écosystémiques dans les agroécosystèmes est d'associer plusieurs espèces végétales au sein d'une même parcelle. Dans ce contexte, les agroforêts tropicales, caractérisées par une forte diversité végétale, sont un modèle d'étude d'intérêt croissant. Dans ce travail qui porte sur le service de régulation des bioagresseurs, notre hypothèse est que la structure des agroforêts influence la régulation naturelle des bioagresseurs de la culture principale. La composition en plante hôte de l'agroforêt est susceptible d'influencer les bioagresseurs via les variations de la ressource. La structure spatiale de la végétation est susceptible d'influencer les bioagresseurs via les variations des conditions microclimatiques. Enfin, les variations de la ressource et du microclimat ne sont pas des mécanismes indépendants puisqu'un microclimat favorable à la croissance de la plante hôte du bioagresseur peut augmenter la quantité des tissus sensibles et donc la ressource pour ce bioagresseur. Pourtant, l'importance relative de l'effet de la composition et de la structure spatiale de la végétation des agroforêts sur l'intensité l'attaque des bioagresseurs a rarement été étudiée. Les objectifs de ce travail de thèse sont (1) de caractériser la composition et la structure spatiale des peuplements végétaux d'agroforêts à cacaoyers et (2) de quantifier leurs interactions avec l'intensité d'attaque de biogresseurs du cacaoyer. Ce travail est appliqué à trois bioagresseurs du cacaoyer : au Costa Rica, la moniliose sur un réseau de parcelles installé dans la région de Talamanca ; au Cameroun, la pourriture brune des cabosses et les mirides sur un réseau de parcelles installé dans la région Centre. Premièrement, nous avons caractérisé la composition et la structure spatiale de la végétation des agroforêts à cacaoyers du Costa Rica et du Cameroun. Au Costa Rica, nous avons identifié une diversité de structure spatiale des arbres forestiers entre parcelles, allant de l'agrégation à la régularité ce qui semble indiquer un gradient croissant de gestion entre ces parcelles. Au Cameroun, nous avons également observé une diversité de structure spatiale entre peuplement d'une même parcelle. En effet, les arbres forestiers sont aléatoirement distribués ou agrégés alors que les arbres fruitiers sont aléatoirement ou régulièrement distribués à l'échelle de la parcelle ce qui semble indiquer une différence d'intensité de gestion entre ces deux peuplements. Deuxièmement, nous avons hiérarchisé les caractéristiques de composition en hôte, de quantité de tissus sensibles et de structure spatiale de la végétation des agroforêts qui influencent l'intensité (i) de la moniliose (ii) de la pourriture brune et (iii) des mirides. L'intensité de la moniliose et la densité en mirides diminuent lorsque les quantités de tis- sus sensibles diminuent et lorsque les arbres forestiers sont aléatoirement ou régulièrement distribués plutôt qu'agrégés ou en faible densité à l'échelle de la parcelle. D'autre part, l'intensité de la moniliose diminue lorsque la densité en cacaoyers augmente et l'intensité de la pourriture brune diminue lorsque l'abondance en cacaoyers augmente, ces résultats étant contraires aux hypothèses de diminution et de dilution de la ressource. Globalement, nos résultats indiquent donc que les variations de la ressource liées aux variations de la composition en hôte ne sont pas le principal effet qui explique la présence des bioagresseurs dans les agroforêts complexes. La structure spatiale des arbres d'ombrage, encore jamais décrite à notre niveau de précision, joue un rôle déterminant et son optimisation pourrait être un moyen de lutte agroécologique contre la moniliose et les mirides du cacaoyer. Dans le cadre de l'agroécologie, ce travail nous a permis d'améliorer notre compréhension des mécanismes écologiques impliqués dans la régulation des bioagresseurs du cacaoyer à l'échelle de la parcelle et ouvre des perspectives pour leur gestion agroécologique.

There is an increase in the prevalence of obesity among people with schizophrenia thought to be due in part to the weight enhancing side-effects of medications commonly used to treat the symptoms of schizophrenia. Despite the deleterious health effects associated with obesity and its impact on quality of life and medication compliance, little is known about body composition and energy expenditure in this clinical group. The primary purpose of this thesis was to enhance understanding of body composition and energy expenditure, particularly resting energy expenditure in men with schizophrenia who take atypical antipsychotic medications. Unique to this investigation is the evaluation of clinical tools used to predict body composition and energy expenditure against reference methodologies in men with schizophrenia. Further, given the known links between obesity and physical activity, an additional but less comprehensive component of the thesis was a consideration of total and activity energy expenditure in addition to the interaction between psychiatric symptoms, side-effects of antipsychotic medications and physical activity also occurred as part of this thesis. Collectively, the goals of this thesis were addressed through a series of studies – the first two studies were related to the measurement and characteristics of body composition in men with schizophrenia, while the third and fourth studies were related to the measurement and characteristics of resting energy expenditure in men with schizophrenia. The fifth and sixth studies the utilised doubly labelled water technique to quantify activity and total energy expenditure in a small group of men with schizophrenia and explored the use of accelerometry in this cohort. The final study briefly considered the impact of psychiatric symptoms and self-reported medication side-effects on objectively measured physical activity. In the first study, thirty-one male adults previously diagnosed with schizophrenia and sixteen healthy male controls were recruited. Estimates of body composition derived from an anthropometry-based equation and from bioelectric impedance analysis (BIA) using deuterium dilution as the reference methodology to determine total body water were compared. The study also determined the validity of equations commonly used to predict body composition from BIA in the men with schizophrenia. A further aim was to determine the superiority of either BIA or body mass index (BMI) as an indicator of obesity in this cohort. The inclusion of the control group, closely matched for age, body size and body composition demonstrated that there was no difference in the ability of body composition prediction methods to distinguish between fat and fat-free mass (FFM) in controls and men with schizophrenia when both groups had similar body composition. However this study indicated that an anthropometry-based equation previously used in people with schizophrenia was a poor predictor of body composition in this cohort, as evidenced by wide limits of agreement (25%) and systematic variation of the bias. In comparison, the best predictor of percentage body fat (%BF) in this group was gained when impedance values were used to predict percentage body fat via the equation published by Lukaski et al (1986). Although percentage body fat was underpredicted using the Lukaski et al. (1986) equation, the mean magnitude was relatively small (1.3%), with the limits of agreement approximately 13%. Linear regression analysis revealed that %BF predicted using the Lukaski et al. (1986) equation explained 25% more of the variance in percentage body fat than BMI. Further, this study also indicated that BIA was more sensitive than BMI in distinguishing between overweight and obesity in this cohort of men with schizophrenia. Because of the almost exclusive use of BMI as an indicator of obesity in people with schizophrenia, the level of excess body fat may be in excess of that previously indicated. The second study extended the examination of body composition in men with schizophrenia. In this study, the thirty-one participants with schizophrenia (age, 34.2 ± 5.7 years; BMI, 30.2 ± 5.7 kg/m2) were individually matched with sedentary controls by age, weight and BMI. Deuterium dilution was used to distinguish between FFM and fat mass. The previous study had indicated that while BIA was a suitable group measure for obesity, on an individual level the technique lacked the precision required for investigating body composition in men with schizophrenia. Waist circumference was used as an indicator of body fat distribution. The findings of this study indicated that in comparison with healthy sedentary controls of similar body size and age, men with schizophrenia had higher levels of body fat which was more centrally distributed. Percentage body fat was on average 4% higher and waist circumference, on average 5 cm greater in men with schizophrenia than the sedentary controls of the same age and BMI. Further, this study indicates that the use of BMI to predict body fat in men with schizophrenia will result in greater bias than when it is used to predict body fat in other sedentary men. Commonly used regression equations to predict energy requirements at rest are based on the relationships between weight and resting energy expenditure (REE) and in such equations, weight acts as a surrogate measure of FFM. The objectives of study three were to measure REE in a small group of men with schizophrenia who were taking the antipsychotic medication clozapine and to determine whether REE can be predicted with sufficient accuracy to substitute for the measurement of REE in the clinical and/or research settings. Body composition was determined using deuterium dilution and REE was measured using a Deltatrac Metabolic Cart via a ventilated hood. The male participants, (aged 28.0 ± 6.7 yrs, BMI 29.8 ± 6.8 kg/m2) were weight stable at the time of the study and had been taking clozapine for 20.5 ± 12.8 months, with doses of 450 ± 140 mg/day. Of the six prediction equations evaluated, the equation of Mifflin et al. (1990) with no systematic bias, the lowest bias and the lowest limits of agreement proved to be the most suitable equation to predict REE in this cohort. The overestimation of REE can be corrected for by deducting 160 kcal/day from the predicted REE value when using the Mifflin et al. (1990) equations. However, the magnitude of the error associated with the prediction of REE for an individual is 370 kcal/day. The findings of this study indicate that REE cannot be predicted with sufficient individual accuracy in men with schizophrenia, therefore it was necessary to measure rather than predict REE in subsequent studies. In the fourth study, indirect calorimetry (Deltatrac Metabolic Cart via ventilated hood) and deuterium dilution were used to accurately determine REE, respiratory quotient (RQ) and FFM in 31 men with schizophrenia and healthy sedentary controls individually matched for age and BMI. Data from this study indicated that gross REE was lower in men with schizophrenia than in healthy sedentary controls of a similar age and body size. However, there was no difference between the groups in REE when REE was adjusted for FFM using the mathematically correct method (analysis of covariance with FFM as the covariate). There was however a statistically and clinically significant difference in resting, fasted RQ between men with schizophrenia and controls, suggesting that RQ rather than REE may be an important correlate worthy of further investigation in men with schizophrenia who take antipsychotic medications. Studies five and six involved the application of the doubly labelled water (DLW) technique to accurately determine total energy expenditure (TEE) and activity energy expenditure (AEE) in a small group of men with schizophrenia who had been taking the atypical antipsychotic medication clozapine. The participants were those who took part in study three. The purpose of these studies was to assess the validity of a commercially available tri-axial accelerometer (RT3) for predicting free-living AEE and to investigate TEE and AEE in men with schizophrenia. There was poor agreement between AEE measured using DLW and AEE predicted using the RT3. However, using the RT3 to measure inactivity explained over two-thirds of the variance in AEE. This study found that the relationship between current AEE per kilogram of body weight and change from baseline weight in men taking clozapine was strong although not significant. The sedentary nature of the group of participants in this study was reflected in physical activity levels, (PAL, 1.39 ± 0.27), AEE (435 ±352 kcal/day) and TEE (2511 ± 606 kcal/day) that fell well short of values recommended by WHO (2000) for optimal health and to prevent weight gain. Given the increasing recognition of the importance of sedentary behaviour to weight gain in the general community, further examination of the unique contributing factors such as medication side effects and symptoms of mental illness to activity levels in this clinical group is warranted. The final study used accelerometry (RT3) to objectively measure activity in a group of 31 men with schizophrenia who had been taking atypical antipsychotic medications for more than four months. The purpose of this study was to explore the relationships between psychiatric symptomatology, side-effects of medication and physical activity. Accelerometry output was analysed to provide a measure of inactivity and moderate intensity activity (MIA). The well-validated and reliable standardised clinical interview, the Positive and Negative Syndrome Scale (PANSS) was used as a measure of psychiatric symptoms. Perceived side-effects of medication were assessed using the Liverpool University Neuroleptic Rating Side-Effects Scale (LUNSER). Surprisingly, there was no relationship reported between any measures of negative symptoms and physical inactivity. However, self-reported measures of medication side-effects relating to fatigue, sleepiness during the day and extrapyramidal symptoms explained 40% of the variance in inactivity. This study found significant relationships between some negative symptoms and moderate intensity activity. Despite the expectation that as symptoms of mental illness reduce, inactivity may diminish and moderate intensity activity will increase, it may not be surprising that in practice this is an overly simplistic view. It may be that measures of social functioning and possibly therefore cognition may be better predictors of physical activity than psychiatric symptomatology per se.

An injection technique, in which undisturbed soil cores are labelled with ³²P to study dissolution of phosphate fertilisers in the soil, was evaluated in field and glasshouse trials. When ³²P was injected between 0-150 mm depths of the undisturbed soil columns and fertilisers applied at the surface, the amounts of fertiliser P dissolved, as measured by the increases in the exchangeable P pools, were overestimated. Three possible reasons were suggested: (i) the interaction between surface-applied fertiliser, ³²P injected through the whole soil column, and the vertical decline in root density, (ii) the decline of specific activity in the exchangeable P pool due to losses of ³²P to nonexchangeable P pools and continuous addition of P from fertiliser dissolution, and (iii) non-uniform distribution of ³²P vis-a-vis ³¹P phosphate. The injection technique may be employed to assess the effectiveness of phosphate fertilisers by introducing a concept, the fertiliser equivalent (FE). The FE is a measure of the amounts of soil exchangeable P that the fertilisers are equivalent to in supplying P to plants, when applied at the specific location. Soluble single superphosphate (SSP) applied at the surface of undisturbed grassland soil cores (Tekapo fine sandy loam), was much more effective than surface-applied unground North Carolina phosphate rock (NCPR) and 30% acidulated NCPR with phosphoric acid (NCPAPR) within the 56 day period of plant growth. An isotopic dilution method, based on tracer kinetic theory, was developed to study the rates of dissolution (F in) and retention (F out) of phosphate fertilisers in the soil in growth chamber experiments. The estimation of F in and F out required labelling of the soils with carrier-free ³²P and determination of the corresponding values of the specific activities of the exchangeable P pools, SA₁ and SA₂, and the sizes of the exchangeable P pools, Q₁ and Q₂, at times t₁ and t₂. Most of the phosphate in the monocalcium phosphate (MCP) solution entered the exchangeable P pool immediately after addition to the soils (Tekapo fine sandy loam and Craigieburn silt loam), and there was little further phosphate input. With increasing periods of incubation, the phosphate was quickly transformed to less rapidly exchangeable forms. In the soils treated with ground North Carolina phosphate rock (<150 µm, NCPR) or partially acidulated (30%) NCPR with phosphoric acid (NCPAPR), the initial exchangeable P pools were not as large as those in the soils treated with MCP, but were maintained at relatively stable concentrations for extended periods, due to the continuous dissolution of PR materials and to lower rates of pretention. An increase in P-retention caused a slight rise in the rate of PR dissolution, but also a rise in the rate of P-retention by the soil. The rate of dissolution was higher at a lower application rate in relative terms, but smaller in absolute terms. The trends in the changes of plant-available P in the soils, measured by the water extractable P, Bray I P and Olsen P, correspond to those predicted by the F in and F out values. The average rates of dissolution between 1-50 and 50-111 days estimated by the F in, however, were higher than those estimated by extractions with 0.5 M NaOH followed by 1 M HCl, and with 0.5 M BaCl₂/TEA. This is partly because the Fin values reflect a plant growth effect on PR dissolution. The relative agronomic effectiveness of NCPR and NCPAPR with respect to MCP was higher after 50 and 111 days of incubation than after 1 day. The F in values were included in all the two-variable models constructed by stepwise regression to describe the relationship between plant P uptake and soil measurements. The amounts of variation in plant P uptake accounted for by the regression model was significantly improved by including F in in the model. This indicates the importance of fertiliser dissolution rates in affecting soil P supply, when phosphate fertilisers differing in solubility are applied.

The work presented in this thesis investigates transitions between quantum states in superconducting double dots (SDDs), a nanoscale device consisting of two aluminium superconducting islands coupled together by a Josephson junction, with each dot connected to a normal state lead. The energy landscape consists of a two level manifold of even charge parity Cooper pair states, and continuous bands corresponding to charge states with single quasiparticles in one or both islands. These devices are fabricated using shadow mask evaporation, and are measured at sub Kelvin temperatures using a dilution refrigerator. We use radio frequency reflectometry to measure quantum capacitance, which is dependent on the quantum state of the device. We measure the quantum capacitance as a function of gate voltage, and observe capacitance maxima corresponding to the Josephson coupling between even parity states. We also perform charge sensing and detect odd parity states. These measurements support the theoretical model of the energy landscape of the SDD. By measuring the quantum capacitance in the time domain, we observe random switching of capacitance between two levels. We determine this to be the stochastic breaking and recombination of single Cooper pairs. By carrying out spectroscopy of the bath responsible for the pair breaking we attribute it to black-body radiation in the cryogenic environment. We also drive the breaking process with a continuous microwave signal, and find that the rate is linearly proportional to incident power. This suggests that a single photon process is responsible, and demonstrates the potential of the SDD as a single photon microwave detector. We investigate this mechanism further, and design an experiment in which the breaking rate is enhanced when the SDD is in the antisymmetric state rather than the symmetric state. We also measure the quantum capacitance of a charge isolated double dot. We observe 2e periodicity, indicating the tunnelling of Cooper pairs and the lack of occupation of quasiparticle states. This work is relevant to the range of experiments investigating the effect of non-equilibrium quasiparticles on the operation of superconducting qubits and other superconducting devices.