A small-scale filed experiment was conducted on a hillslope plot within the Georgia Piedmont, USA, with the aim of elucidating the hydrological processes which generate storm runoff and its chemistry. Intensive hydrometric and chemical sampling enabled the collection of detailed observations of hillslope processes during rainstorms. The passage of water was traced through a one-dimensional profile in the hillslope, where rainfall, throughfall, forest floor soil water, soil water at 15, 40, 50 and 70 cm depths, groundwaters and streamwaters were monitored, either manually or automatically. Chemical samples for each water type were also collected. From analysis of hydrometric data, several hydrological flowpaths were detected that contribute water to storm runoff. Direct channel rainfall is operative in all storms, although its detection is difficult. Overland flow is in operation at some locations on the hillslope, specially in topographic lows. Macropore and mesopore flow occurred and may lead to groundwater displacement. Groundwater ridging also occurred. Each flowpath was found to vary in its operation, according to a series of controls, namely seasonality, antecedent moisture conditions, rainfall magnitude, duration and intensity, and the timing between rainstorms. Conservative tracers (chloride and temperature) were employed to investigate the contribution of 'old' and 'new' water to storm runoff. The variation in chloride concentrations in samples collected either sequentially or manually at each flowpath was monitored throughout storms. Rainfall, comprising 'new' water, was found to exhibit a distinct chloride chemistry. Most samples contained < 20 μeq/l Cl⁻. A similar trend was observed for samples of through fall and forest floor soil water. Groundwaters and matrix soil waters contained two to three times greater chloride concentrations than in the 'new' waters, due to evaporative mechanisms. Hence, 'new' water could be distinguished from 'old' water on the basis of chloride chemistry. Similarly, the temperature profile of 'new' and 'old' waters were significantly different. During the summer, rainfall ('new' water) is warmer than groundwater ('old' water), and during the winter, the reverse is true. Hence, both chloride and temperature were instrumental in distinguishing 'old' from 'new' waters. Direct channel rainfall, overland flow and macropore flow were important flowpaths for the rapid transport of 'new' water through the system during the growing season. Overland flow contributed some 'old' water during the dormant season. Although macropore flow allowed rapid transit of 'new' water to depth, this led to a groundwater displacement mechanism, which ultimately led to the rapid contribution of 'old' water to storm runoff. The combination of hydrometric and tracer data enabled a conceptual hydrological model to be developed of the responses of the hillslope to storm events.

No description available.

La modélisation des écoulements et du transport dans les milieux poreux est un domaine actif pour, notamment, progresser dans la compréhension du transfert des polluants dans les sols. Les sols présentent fréquemment des hétérogénéités comme des macropores (provoqués par la faune, la flore ou des fissures) et un certain nombre de modèles numériques utilisent les concepts de double ou de multi-perméabilité pour tenir compte de tous les types d’écoulements susceptibles de coexister dans de tels systèmes. Cependant, les modèles classiques semblent sous-estimer l’effet de la macroporosité sur l’écoulement et le transfert préférentiels et restreindre la zone d’écoulement préférentiel au seul volume occupé par la macroporosité. Diverses études expérimentales antérieures à cette thèse ont questionné cette hypothèse. Cette étude se propose de comprendre l’établissement de l’écoulement et du transport préférentiel et en particulier les mécanismes d’échange d’eau et de masse entre un macropore et une matrice poreuse environnante en condition saturée. Pour cela, des traçages de l’eau sont réalisés pour un milieu poreux modèle constitué de billes de verre, traversé par un macropore synthétique et mis en place en colonnes de laboratoire. Elution et transfert dans les colonnes sont caractérisés par suivi de la concentration en sortie et par imagerie par résonance magnétique. Un modèle numérique développé sur la base de la méthode de Boltzmann sur réseau est utilisé pour simuler numériquement des écoulements dans un système macroporé et identifier les mécanismes d’écoulements préférentiels à l’échelle de pores. Les données expérimentales montrent que le transfert du traceur est fortement dépendant du débit d’injection ainsi que du coefficient de diffusion dans l’eau. À fort débit, le transfert semble s’effectuer exclusivement dans le macropore, avec très peu d’échange avec la matrice. Pour des débits plus faibles, la percée présente une inflexion suivie d’un pic. Les images IRM montrent alors un échange significatif de traceur entre le macropore et la matrice poreuse environnante. Les simulations numériques sont utilisées pour calculer le champ de vitesse de l’écoulement dans le système en fonction du débit. Les modélisations numériques montrent que l’écoulement préférentiel est étendu dans la matrice poreuse sur une zone de même dimension que le diamètre moyen des grains indépendamment de la taille du macropore et du débit, dans la gamme de débits simulés. Ces résultats expérimentaux et numériques montrent que l’influence du macropore sur les transferts doit être étendue dans la matrice poreuse sur une zone de la taille des grains pour l’écoulement et sur une zone dépendant du coefficient de diffusion du traceur ainsi que du temps de séjour moyen de celui-ci pour le transfert des solutés / Flow and transport modeling through porous media is of primary concern nowadays, especially in order to progress in the understanding of pollutant transfers through soils. Soils present frequently heterogeneities such as macropores (caused by fauna, flora or cracks) and several numerical models use double or multi permeability concepts in order to take into account all flow types that may exist in such porous systems. Nevertheless, classical models seem underestimate the macropore effect on preferential flow and transport by restricting the preferential flow zone only to the volume occupied by the macroporosity. Various experimental studies prior to this thesis have questioned this hypothesis. This study proposes to understand the establishment of preferential flow and transport and in particular the mechanism of flow and solute exchanges between a synthetic macropore and a surrounding porous matrix in saturated condition. For this purpose, water tracing are realized for a model porous media constituted by glass beads, crossed by a synthetic macropore and implemented in laboratory columns. Breakthrough and transport in columns are characterized by monitoring the concentration at the end of the column by magnetic nuclear resonance. A numerical model developed on the basis of lattice-Boltzmann method is used to simul ate flow in macroporous system and identify preferential flow mechanisms at pore scale. Experimental data show that tracer transport is strongly dependent on injection flow rate and the diffusion coefficient in water. At high flow rate, the transport seems to occur exclusively in the macropore, with very little masse exchange with the porous matrix. At lower flow rates, the breakthrough exhibits an inflexion followed by a peak. The MRI images show a significant mass exchange of tracer between the macropore and the surrounding porous matrix. The numerical simulations are used to calculate the flow field in a porous system as a function of flow rate. They show that preferential flow is extended in porous matrix into a zone of same dimension the mean diameter of beads regardless of macropore size or injected flow rate, in the range of simulated flow rates. These experimental and numerical results show that macropore influence on transport should be extended through the surrounding porous matrix into a zone of the same size of grains diameter for flow and into a zone depending on diffusion coefficient as well as mean residence time of the studied tracer for solute transport

This dissertation focuses on understanding the complex interactions between hydrological and geochemical processes, and specifically how these interactions are affected by subsurface heterogeneity across scales. Heterogeneity in the form of macropores and fractures provide preferential flowpaths and affect contaminant transport. Biogeochemical processes are also strongly affected by such heterogeneities. Any lithological layering or interface (e.g. plume fringe, wetland-aquifer boundary, etc.) increases biogeochemical activity around that interface. Hydrologic conditions, rainfall events, drainage patterns, and pH variations are also dominant controls on redox processes and thereby affect contaminant distribution and migration. An inherent limitation of modeling fate and transport of contaminants in the subsurface is that the interactions among biogeochemical processes are complex and non-linear. Therefore, this research investigates the effect of hydrological variations and physical heterogeneity on coupled biogeochemical processes across column and landfill scales. Structural heterogeneity in the form of macropore distributions (no macropore, single macropore, and multiple macropores) in experimental soil columns is investigated to accurately model preferential flow and tracer transport. This research is crucial to agricultural systems where soil and crop management practices modify soil structure and alter macropore densities. The comparison between deterministic and stochastic approaches for simulating preferential flow improved the characterization of interface parameters of the dual permeability model, and outlined the need for efficient sampling algorithms or additional datasets to yield unique (equifinal) soil hydraulic parameters. To evaluate the effect of heterogeneity on redox processes, repacked soil columns with homogeneous and heterogeneous (layered) profiles from soil cores collected at the Norman Landfill site, Oklahoma, USA were employed. Results indicate that heterogeneity in the form of textural layering is paramount in controlling redox processes in the layered column. To evaluate the effect of hydrologic conditions on redox processes, temporal data at the Norman landfill site was used. Results indicate that seasonal hydrologic variations exert dominant control over redox-sensitive concentrations. An integrated MCMC algorithm was devised to upscale linked biogeochemical processes from the column to the field scale. Results indicate that heterogeneity and hydrologic processes are paramount in controlling effective redox concentrations at the Norman landfill site.

Intentional amendment of soil with charcoal (called biochar) is a promising new approach to sequester atmospheric carbon dioxide and increase soil fertility. However, the environmental properties of biochars can vary with production conditions, making it challenging to engineer biochars that are simultaneously optimized for carbon sequestration, nutrient storage, and water-holding capacity. For this reason, I have undertaken a systematic study to (a) determine the pyrolysis conditions that lead to biochars with desired chemical and physical properties, and (b) find how these properties affect the water-holding capacity and nutrient adsorption in biochar-soil mixtures. First, a library of biochars was produced in a custom-built pyrolysis reactor under precisely controlled conditions. The chemical and physical structures of the produced biochars were characterized with various analytical techniques including 13C NMR, XPS, EA and BET pore surface analysis. My results suggest that the chemical composition and pore structure of biochars are determined not just by the maximum heat treatment temperature, but also by several other factors that include the pyrolysis heating rate, treatment time at the maximum temperature and particle size. I also tested a new approach that combines thermogravimetric reactivity measurements, diffusion-reaction theory and structural models to achieve a better characterization of the complicated multi-scale pore structure of biochars. The structural models treat biochars as porous solids having micro- and macropores of different shapes and exhibiting widely ranging pore-size distributions. Simulations results are then compared to experimental data to identify the presence of ordered or random pore networks and test their size distributions and connectivity. I then developed a multi-solid one-dimensional model that can use experimentally determined biochar properties to predict their field performance in beds packed with soil/biochar mixtures. The model used a system of coupled partial differential equations to describe the dynamic adsorption/elution of ammonium nitrate, a model fertilizer, in columns packed with biochar/soil mixtures and perfused with aqueous solutions of the fertilizer. The PDE system was solved using orthogonal collocation on finite elements. My chromatographic model accounted for all the important processes occurring in this system, including external mass transfer between the fluid phase and the solid particles, as well as intraparticle diffusion and adsorption of the solute on the pore surface area of the sorbents. To our knowledge, this is the first chromatographic model that accounted explicitly for the presence of two solid phases with widely different pore structures and adsorption capacities. A systematic parametric study was carried out to determine the importance of each system parameter. The adsorption equilibrium parameters and the intraparticle effective diffusivity of ammonium had the most significant effect on environmental performance. To complete the theoretical analysis, I also developed a model to describe the saturation and drainage of water from the packed column. The model accounted for all the important processes occurring in this system: (a) water exchange between the interstitial pore region and two different smaller pore regions and (b) water flow inside the larger pore region and the two different smaller pore regions. The transient mass balances led to a system of partial differential equations that was solved using block centered finite difference.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第22277号 / 理博第4591号 / 新制||理||1659(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 竹腰 清乃理, 教授 吉村 一良 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

Preferential flow paths are areas of substantially higher permeability than surrounding media. Macropores and soil pipes are a type of preferential flow path where conduit-like voids in the subsurface are typically greater than three millimeters in diameter. They are known to occur in agricultural and forest soils, often as a result of biological and physical processes. Macropores also exist in stream banks and have the potential to enhance the exchange of water and solutes between the channel and riparian groundwater, yet the geographic distribution of bank macropores is unknown. Here we determined the abundance, distribution, and geometry of naturally occurring surface-connected macropores in the banks of 20 streams across five physiographic provinces in the Eastern United States. We identified a total of 1,748 macropores, which were present in all 20 streams, with 3.8 cm average width, 3.3 cm average height, 11.5 cm average depth, and 27.9 cm average height above water surface elevation. Macropore abundance, distribution and geometry were statistically different between physiographic provinces, stream orders, and soil textures, with the latter being the most important. Macropores tended to be larger and more abundant in soils with a high cohesiveness and a low hydraulic conductivity compared to soils with a low cohesiveness and high hydraulic conductivity. As a result, streams with greater longitudinal heterogeneity of soil texture also had greater heterogeneity of macropore density. However, macropore size and height above baseflow water surface elevation also increased with stream order and therefore stream size. This work represents the first attempt to characterize macropores across a variety of riverine systems and presents evidence that macropores may play an important role in hyporheic exchange within stream banks. These results may have water quality implications, where macropores may enhance hyporheic exchange yet reduce the filtering capacity of riparian buffer zones. / MS

L'objectif de ce travail est de contribuer à l'amélioration des mécanismes d'imprégnation d'un renfort fibreux par une résine polymère dans les procédés de mise en œuvre de matériaux composites de type LCM (Liquid Composite Molding). Les études théoriques et expérimentales réalisées se sont focalisées sur les anomalies d'imprégnation pouvant apparaître lors des écoulements. Les défauts couramment observés sont des vides pouvant s'assimiler à des bulles et provenant, en partie, d'une compétition entre les régimes gouvernant les écoulements intra-mèche et inter-mèches. L'analyse de la formation et du transport des bulles au sein d'une structure fibreuse demeure délicate à réaliser du fait de l'architecture complexe de la préforme. Afin de s'exonérer des difficultés rencontrées lors de la visualisation au sein du renfort et pour répondre à cette problématique de vide créé, nous avons fait le choix d'étudier les mécanismes d'imprégnation ainsi que la formation et le transport de bulles dans des réseaux modèles. Une analyse multi-échelles a été adoptée pour nos expérimentations faisant appel à une approche micro et millifluidique où les forces de mouillabilité sont prépondérantes. Les résultats obtenus montrent, dans un premier temps, l'influence de ces forces dans les mécanismes de génération et de transport de bulles et permet de justifier certaines observations proposées dans ce sujet. Un modèle simple basé sur des configurations d'inter-connectivités micropore/macropore a été proposé. Ce modèle permet d'envisager différentes analyses paramétriques selon des configurations géométriques et des régimes d'écoulement variés. Sur cette base, il est possible de prendre en compte différents facteurs et de les comparer à certaines contributions de la littérature dans le domaine de l'imprégnation des milieux fibreux et de la mise en œuvre des composites.

[ES] El desarrollo de los biosensores está permitiendo llevar a cabo análisis bioquímicos cada vez más rápidos, de manera mucho más sencilla y utilizando una menor cantidad de muestra. Esto está dando lugar a aplicaciones en las que se monitorizan parámetros de manera continua y autónoma, aumentando la eficiencia y reduciendo los costes. El tema principal de esta Tesis ha sido el desarrollo y la evaluación de biosensores que se basan en técnicas de transducción óptica, fabricados en silicio poroso, un material nanoestructurado que puede llegar a alcanzar una gran sensibilidad. El trabajo ha consistido en el estudio de la fabricación y la caracterización de membranas de silicio poroso obtenidas a partir de substratos tipo p de baja resistividad. Para ello se ha desarrollado un modelo matemático realista que permite simular el comportamiento del transductor y calcular sus parámetros experimentales. Gracias a esto, se han estudiado propiedades del material como el efecto térmico, llevando a caracterizar el efecto termo-óptico del silicio poroso en el rango infrarrojo del espectro. Además, se ha analizado la infiltración de la muestra en el transductor con el objetivo de mejorar su funcionamiento. Por este motivo, se han examinado diferentes morfologías de poros y se ha implementado un flujo activo durante el sensado, en el cual la sustancia a analizar fluye a través de la membrana porosa, resolviendo problemas de rellenado del sensor y mezclado con otras sustancias. / [CAT] El desenvolupament dels biosensors està permetent realitzar anàlisis bioquímics cada vegada més ràpids, de manera molt més senzilla i utilitzant una menor quantitat de mostra. Això està donant lloc a aplicacions en les quals es monitoritzen paràmetres de manera contínua i autònoma, augmentant l'eficiència i reduint els costos. El tema principal d'aquesta Tesis ha sigut el desenvolupament i l'avaluació de biosensors basats en tècniques de transducció òptica, fabricats en silici porós, un material nanoestructurat que pot arribar a aconseguir una gran sensibilitat. El treball ha consistit en l'estudi de la fabricació i la caracterització de membranes de silici porós obtingudes a partir de substrats tipus p de baixa resistivitat. Per a fer-ho, s'ha desenvolupat un model matemàtic realista que permet simular el comportament del transductor i calcular els seus paràmetres experimentals. Gràcies a això, s'han estudiat propietats del material com l'efecte tèrmic, el que ha permés caracteritzar l'efecte termo-òptic del silici porós en el rang infraroig de l'espectre. A més, s'ha analitzat la infiltració de la mostra en el transductor amb l'objectiu de millorar el seu funcionament. Per aquest motiu, s'han examinat diferents morfologies de porus i s'ha implementat un flux actiu durant el sensat, en el qual la substància a analitzar fluïx a través de la membrana porosa, resolent problemes d'ompliment del sensor i mesclat amb altres substàncies. / [EN] The development of biosensors is leading to faster and simpler analyses of biochemical samples, using them in lower quantities. Over the last years, these advances have allowed the emergence of applications where parameters can be monitored continuously and autonomously, increasing the efficiency and reducing the costs. This Thesis has focused on the development and evaluation of biosensors based on optical transducers, which are fabricated with porous silicon, a nanostructured material that is able to reach a high sensitivity. In this work, the fabrication and characterization of porous silicon membranes using heavily doped p-type silicon wafers have been studied. A realistic mathematical model has been developed in order to simulate the transducer's behavior and calculate the experimental parameters. This has led to the study of physical properties such as the thermal effect, where we were able to characterize the thermo-optic coefficient in the near-infrared range. Moreover, the penetration of the sample into the structure has been analyzed. For this purpose, several pore morphologies were examined and an active flow has been implemented during the sensing experiments, where the substance of interest flows through the porous membrane, to solve problems such as the partial filling of the sensor or the mixture of different substances during the experiments. / Martín Sánchez, D. (2019). Desarrollo de biosensores fotónicos basados en membranas de silicio poroso [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/125695 / TESIS

Land application of wastes has become increasingly popular, to promote nutrient recycling and environmental protection, with soil functioning as a partial barrier between wastes and groundwater. Dairy shed effluent (DSE), may contain a wide variety of pathogenic micro-organisms, including bacteria (e.g. Salmonella paratyphyi, Escherichia coli. and Campylobacter), protozoa and viruses. Groundwater pathogen contamination resulting from land-applied DSE is drawing more attention with the intensified development of the dairy farm industry in New Zealand. The purpose of this research was to investigate the fate and transport of bacterial indicator-faecal coliform (FC) from land-applied DSE under different irrigation practices via field lysimeter studies, using two water irrigation methods (flood and sprinkler) with contrasting application rates, through the 2005-2006 irrigation season. It was aimed at better understanding, quantifying and modelling of the processes that govern the removal of microbes in intact soil columns, bridging the gap between previous theoretical research and general farm practices, specifically for Templeton soil. This study involved different approaches (leaching experiments, infiltrometer measurements and a dye infiltration study) to understand the processes of transient water flow and bacterial transport; and to extrapolate the relationships between bacterial transport and soil properties (like soil structure, texture), and soil physical status (soil water potential ψ and volumetric water content θ). Factors controlling FC transport are discussed. A contaminant transport model, HYDRUS-1D, was applied to simulate microbial transport through soil on the basis of measured datasets. This study was carried out at Lincoln University’s Centre for Soil and Environmental Quality (CSEQ) lysimeter site. Six lysimeters were employed in two trials. Each trial involved application of DSE, followed by a water irrigation sequence applied in a flux-controlled method. The soil columns were taken from the site of the new Lincoln University Dairy Farm, Lincoln, Canterbury. The soil type is Templeton fine sandy loam (Udic-Ustochrept, coarse loamy, mixed, mesic). Vertical profiles (at four depths) of θ and ψ were measured during leaching experiments. The leaching experiments directly measured concentrations of chemical tracer (Br⁻ or Cl⁻) and FC in drainage. Results showed that bacteria could readily penetrate through 700 mm deep soil columns, when facilitated by water flow. In the first (summer) trial, FC in leachate as high as 1.4×10⁶ cfu 100 mL⁻¹ (similar to the DSE concentration), was detected in one lysimeter that had a higher clay content in the topsoil, immediately after DSE application, and before any water irrigation. This indicates that DSE flowed through preferential flow paths without significant treatment or reduction in concentrations. The highest post-irrigation concentration was 3.4×10³ cfu 100 mL⁻¹ under flood irrigation. Flood irrigation resulted in more bacteria and Br⁻ leaching than spray irrigation. In both trials (summer and autumn) results showed significant differences between irrigation treatments in lysimeters sharing similar drainage class (moderate or moderately rapid). Leaching bacterial concentration was positively correlated with both θ and ψ, and sometimes drainage rate. Greater bacterial leaching was found in the one lysimeter with rapid whole-column effective hydraulic conductivity, Keff, for both flood and spray treatments. Occasionally, the effect of Keff on water movement and bacterial transport overrode the effect of irrigation. The ‘seasonal condition’ of the soil (including variation in initial water content) also influenced bacterial leaching, with less risk of leaching in autumn than in summer. A tension infiltrometer experiment measured hydraulic conductivity of the lysimeters at zero and 40 mm suction. The results showed in most cases a significant correlation between the proportion of bacteria leached and the flow contribution of the macropores. The higher the Ksat, the greater the amount of drainage and bacterial leaching obtained. This research also found that this technique may exclude the activity of some continuous macropores (e.g., cracks) due to the difference of initial wetness which could substantially change the conductivity and result in more serious bacterial leaching in this Templeton soil. A dye infiltration study showed there was great variability in water flow patterns, and most of the flow reaching deeper than 50 cm resulted from macropores, mainly visible cracks. The transient water flow and transport of tracer (Br⁻) and FC were modelled using the HYDRUS-1D software package. The uniform flow van Genuchten model, and the dual-porosity model were used for water flow and the mobile-immobile (MIM) model was used for tracer and FC transport. The hydraulic and solute parameters were optimized during simulation, on the basis of measured datasets from the leaching experiments. There was evidence supporting the presence of macropores, based on the water flow in the post-DSE application stage. The optimised saturated water content (θs) decreased during the post-application process, which could be explained in terms of macropore flow enhanced by irrigation. Moreover, bacterial simulation showed discrepancies in all cases of uniform flow simulations at the very initial stage, indicating that non-equilibrium processes were dominant during those short periods, and suggesting that there were strong dynamic processes involving structure change and subsequently flow paths. It is recommended that management strategies to reduce FC contamination following application of DSE in these soils must aim to decrease preferential flow by adjusting irrigation schemes. Attention needs to be given to a) decreasing irrigation rates at the beginning of each irrigation; b) increasing the number of irrigations, by reducing at the same time the amount of water applied and the irrigation rate at each irrigation; c) applying spray irrigation rather than flood irrigation.