Field-scale transport through unsaturated soil is influenced by surface and subsurface boundary conditions, and the spatial variability of state soil variables. The objective of this thesis is to examine the relative importance of the spatial redistribution of surface water versus spatial variability of soil properties on long-term transient water flow and transport under semi-arid conditions. The field-scale transport (34 yr) of a surface applied tracer (chloride), spatial variability of other pedogenic tracers, and surface water redistribution over a 19 mo fallow period were measured in a catchment basin. In 1966 and 1971, a chloride tracer (KCl) was surface applied to plots (6.1 m x 90 m, Chernozemic soil) near Saskatoon, Saskatchewan. In 2000 and 2001, 262 soil cores were taken along and perpendicular to one KCl strip. Soil layering at each core was recorded and samples were analysed for chloride concentration, electrical conductivity, bulk density and water content. Sulphate and nitrate concentrations were measured on selected cores. The site is level by common definitions, with a very slight concave depression (1.8% grade) midway along the KCl strip and a slight grade (¡Ü2.1%) perpendicular to the KCl strip. Measured water recharge indicated slight differences in surface slope had a marked effect on redistribution of water and spatial distribution of the chloride tracer. An estimated 90% of redistributed water was subsequently used by plants and 10% resulted in an increase in deep drainage. A varved layer had a strong influence on the subsurface redistribution of water and chloride below the root zone. There were sharp horizontal transitions between areas of slow and faster transport, which corresponded to sharp increases in catchment area and water recharge. Small surface depressions, which controlled pedogenic transport and soil formation, have been filled in by tillage translocation. Spatial variability of soil horizon thickness (and associated hydraulic properties) had little effect on transport of chloride after 34 yr. Computer simulations also suggest substantial surface redistribution of precipitation and snowmelt. In contrast to the measured chloride data, the model was sensitive to changes in hydraulic properties and horizon thickness in the root zone. Surface water redistribution was the primary factor controlling long-term transport.

Field-scale transport through unsaturated soil is influenced by surface and subsurface boundary conditions, and the spatial variability of state soil variables. The objective of this thesis is to examine the relative importance of the spatial redistribution of surface water versus spatial variability of soil properties on long-term transient water flow and transport under semi-arid conditions. The field-scale transport (34 yr) of a surface applied tracer (chloride), spatial variability of other pedogenic tracers, and surface water redistribution over a 19 mo fallow period were measured in a catchment basin. In 1966 and 1971, a chloride tracer (KCl) was surface applied to plots (6.1 m x 90 m, Chernozemic soil) near Saskatoon, Saskatchewan. In 2000 and 2001, 262 soil cores were taken along and perpendicular to one KCl strip. Soil layering at each core was recorded and samples were analysed for chloride concentration, electrical conductivity, bulk density and water content. Sulphate and nitrate concentrations were measured on selected cores. The site is level by common definitions, with a very slight concave depression (1.8% grade) midway along the KCl strip and a slight grade (¡Ü2.1%) perpendicular to the KCl strip. Measured water recharge indicated slight differences in surface slope had a marked effect on redistribution of water and spatial distribution of the chloride tracer. An estimated 90% of redistributed water was subsequently used by plants and 10% resulted in an increase in deep drainage. A varved layer had a strong influence on the subsurface redistribution of water and chloride below the root zone. There were sharp horizontal transitions between areas of slow and faster transport, which corresponded to sharp increases in catchment area and water recharge. Small surface depressions, which controlled pedogenic transport and soil formation, have been filled in by tillage translocation. Spatial variability of soil horizon thickness (and associated hydraulic properties) had little effect on transport of chloride after 34 yr. Computer simulations also suggest substantial surface redistribution of precipitation and snowmelt. In contrast to the measured chloride data, the model was sensitive to changes in hydraulic properties and horizon thickness in the root zone. Surface water redistribution was the primary factor controlling long-term transport.

In this study, mechanical properties of Al-Zn alloys were conducted, with various parameters including Zn contents, grain size, and tensile strain rate. Experimental samples were all manufactured with friction stir processing method. Samples of Al-Zn alloys with the grain size of 1.5£gm, 1£gm, or 0.5£gm and five Zn concentration were pulled in tension at strain rate of 10-3s-1,10-4s-1 and 10-5s-1 . The data set were then used to draw engineering and true tensile stress vs. strain curves , flowing stress vs. Zn contents curves, Hall-Petch equation curves, m vs. Zn contents curves and m vs. grain size curves. Quantitative analysis were conducted to discover that solid solute softening and inverse Hall-Petch relation were present in Al-Zn alloys, which were more prominent at slower tensile strain rate when grain size was less than 1£gm and the Zn contents was higher than 10wt%. Quantitative analysis of strain rate sensitivity (m) showed the trends of increasing value of m with higher Zn contents and smaller grain sizes when solid solute softening and inverse Hall-Petch relation were present. The high grain-boundary diffusion coefficient of Zn which accelerates the efficiency of dynamic recovery are considered the main reason. The effect gets more prominent with increasing Zn contents , smaller grain size , and slower tensile strain rate. For Zn concentration higher than 10wt%, dynamic recovery may drive inverse Hall-Petch relation to appear when grain size is about 1£gm large.

Up-to-date methods of numerical modelling of random fields were applied to investigate some features of solute transport in saturated porous media with stochastic hydraulic conductivity. The paper describes numerical experiments which were performed and presents the first results.

<p>Poly(vinyl alcohol) and polyethylene polymer systems werebuilt in order to study their transport properties (diffusion).First a verification of the AMBER force field was conducted fora poly(vinyl alcohol) system built from a chain with 145repeating units. NPT-molecular dynamics simulations attemperatures between 400 and 527 K were performed. The resultsof the simulations were compared withpressure-volume-temperature data, solubility parameter, X-rayscattering pattern and data for the characteristic ratio. Thefractional free volume distribution was computed and thediffusion characteristics of water in the polymer werestudied.</p><p>Further another poly(vinyl alcohol) system, with 600repeating units, was used to study oxygen diffusion in dry andwet poly(vinyl alcohol). In these systems the focus was toinvestigate the oxygen paths relative to the backbone and alsothe effect of water on the diffusion coefficients. Jump mapsand correlation function between the velocity of the oxygen wascalculated. The water has a huge impact on the oxygen diffusionand the preferred paths.</p><p>A larger molecule (limonene) was studied in a polyethylenematrix consisting of 6000 anisotropic united atoms. A 100 nslong trajectory was recorded and also shortertrajectories atdifferent temperatures, which gave the temperature dependenceof the diffusion coefficients. Correlation functions for thelimonene molecule shows that it rotates and tumbles when movingthru the matrix.</p><p>The main results from the molecular dynamics simulationsshowed that diffusion of larger molecules are possible and alsothat molecular dynamics simulations can predict plasticizationeffects.</p><p>A new fast experimental method for determining diffusioncoefficients with non iso thermal thermogravimetry weredeveloped. The advantage is that the experiments only takesminutes instead of days with a small effect on theaccuracy.</p>

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>

Local displacement efficiency in miscible floods is significantly affected by mixing taking place in the medium. Laboratory experiments usually measure flow-averaged ("cup mixed") effluent concentration histories. The core-scale averaged mixing, termed as dispersion, is used to quantify mixing in flow through porous media. The dispersion coefficient has the contributions of convective spreading and diffusion lumped together. Despite decades of research there remain questions about the nature and origin of dispersion. The main objective of this research is to understand the basic physics of solute transport and mixing at the pore scale and to use this information to explain core-scale mixing behavior (dispersion). We use two different approaches to study the interaction between convective spreading and diffusion for a range of flow conditions and the influence of their interaction on dispersion. In the first approach, we perform a direct numerical simulation of pore scale solute transport (by solving the Navier Stokes and convection diffusion equations) in a surrogate pore space. The second approach tracks movement of solute particles through a network model that is physically representative of real granular material. The first approach is useful in direct visualization of mixing in pore space whereas the second approach helps quantify the effect of pore scale process on core scale mixing (dispersion). Mixing in porous media results from interaction between convective spreading and molecular diffusion. The converging-diverging flow around sand grains causes the solute front to stretch, split and rejoin. In this process the area of contact between regions of high and low solute concentrations increases by an order of magnitude. Diffusion tends to reduce local variations in solute concentration inside the pore body. If the fluid velocity is small, diffusion is able to homogenize the solute concentration inside each pore. On the other hand, in the limit of very large fluid velocity (or no diffusion) local mixing because of diffusion tends to zero and dispersion is entirely caused by convective spreading. Flow reversal provides insights about mixing mechanisms in flow through porous media. For purely convective transport, upon flow reversal solute particles retrace their path to the inlet. Convective spreading cancels and echo dispersion is zero. Diffusion, even though small in magnitude, causes local mixing and makes dispersion in porous media irreversible. Echo dispersion in porous media is far greater than diffusion and as large as forward (transmission) dispersion. In the second approach, we study dispersion in porous media by tracking movement of a swarm of solute particles through a physically representative network model. We developed deterministic rules to trace paths of solute particles through the network. These rules yield flow streamlines through the network comparable to those obtained from a full solution of Stokes' equation. In the absence of diffusion the paths of all solute particles are completely determined and reversible. We track the movement of solute particles on these paths to investigate dispersion caused by purely convective spreading at the pore scale. Then we superimpose diffusion and study its influence on dispersion. In this way we obtain for the first time an unequivocal assessment of the roles of convective spreading and diffusion in hydrodynamic dispersion through porous media. Alternative particle tracking algorithms that use a probabilistic choice of an out-flowing throat at a pore fail to quantify convective spreading accurately. For Fickian behavior of dispersion it is essential that all solute particles encounter a wide range of independent (and identically distributed) velocities. If plug flow occurs in the pore throats a solute particle can encounter a wide range of independent velocities because of velocity differences in pore throats and randomness of pore structure. Plug flow leads to a purely convective spreading that is asymptotically Fickian. Diffusion superimposed on plug flow acts independently of convective spreading causing dispersion to be simply the sum of convective spreading and diffusion. In plug flow hydrodynamic dispersion varies linearly with the pore-scale Peclet number. For a more realistic parabolic velocity profile in pore throats particles near the solid surface of the medium do not have independent velocities. Now purely convective spreading is non-Fickian. When diffusion is non-zero, solute particles can move away from the low velocity region near the solid surface into the main flow stream and subsequently dispersion again becomes asymptotically Fickian. Now dispersion is the result of an interaction between convection and diffusion and it results in a weak nonlinear dependence of dispersion on Peclet number. The dispersion coefficients predicted by particle tracking through the network are in excellent agreement with the literature experimental data. We conclude that the essential phenomena giving rise to hydrodynamic dispersion observed in porous media are (i) stream splitting of the solute front at every pore, thus causing independence of particle velocities purely by convection, (ii) a velocity gradient within throats and (iii) diffusion. Taylor's dispersion in a capillary tube accounts for only the second and third of these phenomena, yielding a quadratic dependence of dispersion on Peclet number. Plug flow in the bonds of a physically representative network accounts for the only the first and third phenomena, resulting in a linear dependence of dispersion upon Peclet number. / text

No description available.

It is well known that water molecules at room temperature tend to form ‘iceberg’ structures around the hydrocarbon chains of surfactant molecules dissolved in water. The entropy reduction (times the absolute temperature T) associated with the iceberg structure can be considered as the net driving force for self-assembly. More recently, many investigators measured long-range attractive forces between hydrophobic surfaces, which are likely to result from structuring of the water molecules in the vicinity of the hydrophobic surfaces. Similarly, the hydrophobic nature of most gas hydrate formers may induce ordering of water molecules in the vicinity of dissolved solutes. In the present work, the surface forces between thiolated gold surfaces have been measured using an atomic force microscope (AFM) to obtain information on the structure of the thin films of water between hydrophobic surfaces. The results have been used to develop a new concept for the formation of gas hydrates.

No description available.