The intra-continental movement of waterborne contaminants is governed by the distribution of solute load in the landscape along with the characteristics and distribution of the hydrological pathways that transport the solutes. An understanding of the processes affecting the transport and fate of the contaminants is crucial for assessments of solute concentrations and their environmental effect on downstream recipients. Elevated concentration of nutrients and the presence of anthropogenic substances, such as pharmaceutical residues, are two examples of the current problems related to hydrological transport. The overall objective of this thesis is to increase the mechanistic understanding of the governing hydrological transport processes and their links to geomorphological and biogeochemical retention and attenuation processes. Specifically, this study aims to quantify the processes governing the transport and fate of waterborne contaminants on the point, stream reach, and watershed scales by evaluating time series obtained from stream tracer tests and water quality monitoring data. The process quantification was achieved by deriving formal expressions for the key transport characteristics, such as the central temporal moments of a unit solute response function and the spectral scaling function for time series of solute responses, which attributes the solute response in the Laplace and Fourier domains to the governing processes and spatial regions within the watershed. The results demonstrate that in addition to the hydrological and biogeochemical processes, the distribution of the load in the landscape and the geomorphological properties in terms of the distribution of transport pathway distances have defined effects on the solute response. Furthermore, the spatial variability between and along the transport pathways significantly affect the solute response. The results indicate that environments with high retention and attenuation intensity, such as stream-reaches with pronounced hyporheic zones, may often dominate the solute flux in the watershed effluent, especially for reactive solutes. The mechanistic-based framework along with the evaluation methodologies presented within this study describes how the results can be generalized in terms of model parameters that reflect the hydrology, geomorphology and biogeochemistry in the studied area. This procedure is demonstrated by the parameterization of a compartment-in-series model for phosphorous transport. / <p>QC 20140826</p>

La tomographie optique diffuse de fluorescence permet la reconstruction tridimensionnelle de fluorophores présents dans un tissu biologique. La modalité la plus simple de cette technique repose sur une illumination continue du milieu et s'intéresse aux mesures d'atténuation du faisceau incident en différentes positions. En raison de la forte diffusion des tissus, la modalité continue souffre d'une faible résolution en profondeur.On considère aujourd'hui que la modalité résolue en temps, qui fournit pour chaque photon détecté son temps de vol, permettrait l'étude de tissus plus épais, ouvrant ainsi la porte à des applications cliniques. L'objet de cette thèse est de chercher comment tirer profit de l'information temporelle et de quantifier son apport par rapport à la modalité continue.La tomographie optique diffuse de fluorescence est un problème inverse mal conditionné. Dans un contexte où tout écart au modèle doit être limité, nous nous intéressons tout d'abord au modèle direct et montrons que la densité de photons est un modèle satisfaisant de la quantité expérimentalement mesurée. Nous passons ensuite au crible la méthode de reconstruction fondée sur l'exploitation des moments temporels des mesures. Étudiant théoriquement les propriétés des moments, nous montrons que cette approche nécessite, pour s'avérer intéressante, la détection d'un nombre élevé de photons. Nous introduisons enfin une nouvelle approche permettant d'exploiter l'information temporelle pour un nombre de photons plus limité. Cette approche, reposant sur une transformation en ondelettes des mesures, offre une qualité de reconstruction accrue par rapport à celle offerte par l'approche des moments. / Fluorescence diffuse optical tomography enables the three-dimensional reconstruction of fluorescence markers injected within a biological tissue, with light in the near infrared range. The simple continuous modality uses steady excitation light and operates from the measurements at different positions of the attenuation of the incident beam. This technique is low-cost, non-ionizing, and easy to handle, but subject to low resolution for thick tissues due to diffusion. Hopefully, the time-resolved modality, which provides the time of flight of any detected photon, could overcome this limitation and pave the way to clinical applications. This thesis aims at determining the best way to exploit the time resolved information and at quantifying the advantages of this modality over the standard continuous wave one.Model deviations must be carefully limited when ill-posed problems as fluorescence diffuse optical tomography are considered. As a result, we have first addressed the modelling part of the problem. We have shown that the photons density models to good approximation the measurable quantity that is the quantity measured by an actual acquisition set-up. Then, the moment-based reconstruction scheme has been thoroughly evaluated by means of a theoretical analysis of the moments’ properties. It was found that the moment-based approach requires high photon counts to be profitable compared to the continuous wave modality. Last, a novel wavelet-based approach, which enables an improved reconstruction quality, has been introduced. This approach has shown good ability to exploit the temporal information at lower photon counts.

<p>Understanding of the processes affecting solute transport in flowing water is important for the possibility to predict the evolution with time of polluted stream systems. </p><p>This thesis presents tracer experiment methodology and model developments for solute transport in streams, with special focus on retention processes and their effect on solute stream transport. Results are presented from a tracer experiment in the Säva Stream, Uppland County, Sweden, where both a conservative (³H as tritiated water) and a reactive (⁵¹Cr as trivalent chromium ion) tracer were injected simultaneously. The time and length scales of the experiment were prolonged compared to previous studies, which allowed for new critical tests of different model concepts. </p><p>It was found that the hyporheic exchange greatly affected the solute transport of both tracers. However, the retention of chromium was significantly more pronounced. About 76% of the injected chromium was lost from the stream water phase directly after the passage of the pulse 30 km downstream of the injection point. The inventory of chromium in the sediments indicated that the main part was retrieved in the hyporheic zone. </p><p>Both a diffusive and an advective hyporheic exchange model were developed and evaluated versus independent observations in the stream water and hyporheic zone. Analytical expressions for the central temporal moments of the breakthrough curve and semi-analytical solutions for the solute concentration in the Laplace domain were derived. Both models were found useful in representing the observations.</p><p>For the transport of the reactive solute, it was found essential to consider a kinetic sorption on to particulate matter in the hyporheic zone. The time needed for a wash-out of 75% of the maximum uptake in the hyporheic zone was found to be ~85 times longer for the reactive solute, compared to the conservative solute. Neglecting the sorption kinetics in the transport model yielded significant errors in the central temporal moments, which implied an incorrect description of the wash-out process from the hyporheic zone. Independent observations in the stream water and hyporheic zone as well as choice of evaluation method are essential for a correct interpretation of the processes.</p><p>A first attempt was also made to link model parameters such as the residence time in the hyporheic zone with measurable parameters of the stream. Such a relationship offers the possibility to generalize results for other streams and stream conditions. A generic study of the transport of an inert solute in the Lule River, Sweden, using this kind of relationship, indicated that the hyporheic exchange can have a large practical implication.</p>

<p>The overall objective of the current study is to develop a quantitative understanding of the effects of spatial variability in physical and geochemical properties of crystalline rock on the migration of radionuclides along a single fracture in bedrock. A stochastic model was developed to describe the transport of solutes in fractured rock. The model describes the migration of radionuclides along a one-dimensional path and includes the transversal diffusion into the rock matrix and sorption kinetics. By using a Lagrangian method of description we can extend the model to the description of a two-dimensional transport problem in single fractures. </p><p>This study presents the first analysis of the impact of heterogeneous mass transfer on the transport of radionuclides in rock fractures, where most of the relevant rock properties such as aperture, porosity, effective diffusivity, sorption capacity and maximum diffusion depth are defined as being spatially random. The stochastic analysis performed here reflects the uncertainty in our knowledge of the properties associated with a discrete sampling technique in site investigations.</p><p>Geostatistics of the main parameters was determined experimentally on a large number of rock samples taken from the Swedish crystalline basement. The knowledge of the covariance functions of the main rock properties is then used as a basis for a stochastic analysis. By combining the small perturbation approach with the spectral method the problem could be solved in terms of closed form solutions for the central temporal moments of the residence time probability density function. </p><p>In order to be able to distinguish between the effects of various mechanisms from the effects of heterogeneity on the migration of radionuclides, it was necessary to perform independent studies of the effect of the variation of the dispersion coefficient on the aspect ratio of a rectangular flow section and the effect of adsorption kinetics on the migration. </p><p>Finally, the effect of the heterogeneous rock properties on the solute transport observed in a limited number of migration experiments corresponds fairly well to the theoretical effect expected on the basis of the experimentally determined auto-covariance functions. </p>

The overall objective of the current study is to develop a quantitative understanding of the effects of spatial variability in physical and geochemical properties of crystalline rock on the migration of radionuclides along a single fracture in bedrock. A stochastic model was developed to describe the transport of solutes in fractured rock. The model describes the migration of radionuclides along a one-dimensional path and includes the transversal diffusion into the rock matrix and sorption kinetics. By using a Lagrangian method of description we can extend the model to the description of a two-dimensional transport problem in single fractures. This study presents the first analysis of the impact of heterogeneous mass transfer on the transport of radionuclides in rock fractures, where most of the relevant rock properties such as aperture, porosity, effective diffusivity, sorption capacity and maximum diffusion depth are defined as being spatially random. The stochastic analysis performed here reflects the uncertainty in our knowledge of the properties associated with a discrete sampling technique in site investigations. Geostatistics of the main parameters was determined experimentally on a large number of rock samples taken from the Swedish crystalline basement. The knowledge of the covariance functions of the main rock properties is then used as a basis for a stochastic analysis. By combining the small perturbation approach with the spectral method the problem could be solved in terms of closed form solutions for the central temporal moments of the residence time probability density function. In order to be able to distinguish between the effects of various mechanisms from the effects of heterogeneity on the migration of radionuclides, it was necessary to perform independent studies of the effect of the variation of the dispersion coefficient on the aspect ratio of a rectangular flow section and the effect of adsorption kinetics on the migration. Finally, the effect of the heterogeneous rock properties on the solute transport observed in a limited number of migration experiments corresponds fairly well to the theoretical effect expected on the basis of the experimentally determined auto-covariance functions.

Understanding of the processes affecting solute transport in flowing water is important for the possibility to predict the evolution with time of polluted stream systems. This thesis presents tracer experiment methodology and model developments for solute transport in streams, with special focus on retention processes and their effect on solute stream transport. Results are presented from a tracer experiment in the Säva Stream, Uppland County, Sweden, where both a conservative (3H as tritiated water) and a reactive (51Cr as trivalent chromium ion) tracer were injected simultaneously. The time and length scales of the experiment were prolonged compared to previous studies, which allowed for new critical tests of different model concepts. It was found that the hyporheic exchange greatly affected the solute transport of both tracers. However, the retention of chromium was significantly more pronounced. About 76% of the injected chromium was lost from the stream water phase directly after the passage of the pulse 30 km downstream of the injection point. The inventory of chromium in the sediments indicated that the main part was retrieved in the hyporheic zone. Both a diffusive and an advective hyporheic exchange model were developed and evaluated versus independent observations in the stream water and hyporheic zone. Analytical expressions for the central temporal moments of the breakthrough curve and semi-analytical solutions for the solute concentration in the Laplace domain were derived. Both models were found useful in representing the observations. For the transport of the reactive solute, it was found essential to consider a kinetic sorption on to particulate matter in the hyporheic zone. The time needed for a wash-out of 75% of the maximum uptake in the hyporheic zone was found to be ~85 times longer for the reactive solute, compared to the conservative solute. Neglecting the sorption kinetics in the transport model yielded significant errors in the central temporal moments, which implied an incorrect description of the wash-out process from the hyporheic zone. Independent observations in the stream water and hyporheic zone as well as choice of evaluation method are essential for a correct interpretation of the processes. A first attempt was also made to link model parameters such as the residence time in the hyporheic zone with measurable parameters of the stream. Such a relationship offers the possibility to generalize results for other streams and stream conditions. A generic study of the transport of an inert solute in the Lule River, Sweden, using this kind of relationship, indicated that the hyporheic exchange can have a large practical implication.