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>

The applicability and adequacy of three modeling approaches to describe and predict breakthough curves (BTCs) for non-reactive solutes in statistically homogeneous porous media were numerically and experimentally investigated. Modeling approaches were: the convection-dispersion equation (CDE) with scale-dependent dispersivity, mobile-immobile model (MIM), and the fractional convection-dispersion equation (FCDE). In order to test these modeling approaches, a prototype laboratory column system was designed for conducting miscible displacement experiments with a free-inlet boundary. Its performance and operating conditions were rigorously evaluated. When the CDE with scale-dependent dispersivity is solved numerically for generating a BTC at a given location, the scale-dependent dispersivity can be specified in several ways namely, local time-dependent dispersivity, average time-dependent dispersivity, apparent time-dependent dispersivity, apparent distance-dependent dispersivity, and local distance-dependent dispersivity. Theoretical analysis showed that, when dispersion was assumed to be a diffusion-like process, the scale-dependent dispersivity was locally time-dependent. In this case, definitions of the other dispersivities and relationships between them were directly or indirectly derived from local time-dependent dispersivity. Making choice between these dispersivities and relationships depended on the solute transport problem, solute transport conditions, level of accuracy of the calculated BTC, and computational efficiency The distribution of these scale-dependent dispersivities over scales could be described as either as a power-law function, hyperbolic function, log-power function, or as a new scale-dependent dispersivity function (termed as the LIC). The hyperbolic function and the LIC were two potentially applicable functions to adequately describe the scale dependent dispersivity distribution in statistically homogeneous porous media. All of the three modeling approaches described observed BTCs very well. The MIM was the only model that could explain the tailing phenomenon in the experimental BTCs. However, all of them could not accurately predict BTCs at other scales using parameters determined at one observed scale. For the MIM and the FCDE, the predictions might be acceptable only when the scale for prediction was very close to the observed scale. When the distribution of the dispersivity over a range of scales could be reasonably well-defined by observations, the CDE might be the best choice for predicting non-reactive solute transport in statistically homogeneous porous media. / Ph. D.

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