[1] Non-Fickian (or anomalous) transport of contaminants has been observed at field and laboratory scales in a wide variety of porous and fractured geological formations. Over many years a basic challenge to the hydrology community has been to develop a theoretical framework that quantitatively accounts for this widespread phenomenon. Recently, continuous time random walk (CTRW) formulations have been demonstrated to provide general and effective means to quantify non-Fickian transport. We introduce and develop the CTRW framework from its conceptual picture of transport through its mathematical development to applications relevant to laboratoryand field-scale systems. The CTRW approach contrasts with ones used extensively on the basis of the advectiondispersion equation and use of upscaling, volume averaging, and homogenization. We examine the underlying assumptions, scope, and differences of these approaches, as well as stochastic formulations, relative to CTRW. We argue why these methods have not been successful in fitting actual measurements. The CTRW has now been developed within the framework of partial differential equations and has been generalized to apply to nonstationary domains and interactions with immobile states (matrix effects). We survey models based on multirate mass transfer (mobile-immobile) and fractional derivatives and show their connection as subsets within the CTRW framework.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2005RG000178

Modeling non‐Fickian transport in geological formations as a continuous time random walk

Fifty years of hyporheic zone research have shown the important role played by the hyporheic zone as an interface between groundwater and surface waters. However, it is only in the last two decades that what began as an empirical science has become a mechanistic science devoted to modeling studies of the complex fluid dynamical and biogeochemical mechanisms occurring in the hyporheic zone. These efforts have led to the picture of surface-subsurface water interactions as regulators of the form and function of fluvial ecosystems. Rather than being isolated systems, surface water bodies continuously interact with the subsurface. Exploration of hyporheic zone processes has led to a new appreciation of their wide reaching consequences for water quality and stream ecology. Modern research aims toward a unified approach, in which processes occurring in the hyporheic zone are key elements for the appreciation, management, and restoration of the whole river environment. In this unifying context, this review summarizes results from modeling studies and field observations about flow and transport processes in the hyporheic zone and describes the theories proposed in hydrology and fluid dynamics developed to quantitatively model and predict the hyporheic transport of water, heat, and dissolved and suspended compounds from sediment grain scale up to the watershed scale. The implications of these processes for stream biogeochemistry and ecology are also discussed.

Hyporheic flow and transport processes: Mechanisms, models, and biogeochemical implications

Among the current problems that hydrogeologists face, perhaps there is none as challenging as the characterization of fractured rock (Faybishenko and Benson 2000). This paper discusses issues associated with the quantification of flow and transport through fractured rocks on scales not exceeding those typically associated with single- and multi-well pressure (or flow) and tracer tests. As much of the corresponding literature has focused on fractured crystalline rocks and hard sedimentary rocks such as sandstones, limestones (karst is excluded) and chalk, so by default does this paper. Direct quantification of flow and transport in such rocks is commonly done on the basis of fracture geometric data coupled with pressure (or flow) and tracer tests, which therefore form the main focus. Geological, geophysical and geochemical (including isotope) data are critical for the qualitative conceptualization of flow and transport in fractured rocks, and are being gradually incorporated in quantitative flow and transport models, in ways that this paper unfortunately cannot describe but in passing. The hydrogeology of fractured aquifers and other earth science aspects of fractured rock hydrology merit separate treatments. All evidence suggests that rarely can one model flow and transport in a fractured rock consistently by treating it as a uniform or mildly nonuniform isotropic continuum. Instead, one must generally account for the highly erratic heterogeneity, directional dependence, dual or multicomponent nature and multiscale behavior of fractured rocks. One way is to depict the rock as a network of discrete fractures (with permeable or impermeable matrix blocks) and another as a nonuniform (single, dual or multiple) continuum. A third way is to combine these into a hybrid model of a nonuniform continuum containing a relatively small number of discrete dominant features. In either case the description can be deterministic or stochastic. The paper contains a brief assessment of these trends in light of recent experimental and theoretical findings, ending with a short list of prospects and challenges for the future.

Trends, prospects and challenges in quantifying flow and transport through fractured rocks

The state of the groundwater inverse problem is synthesized. Emphasis is placed on aquifer characterization, where modelers have to deal with conceptual model uncertainty (notably spatial and temporal variability), scale dependence, many types of unknown parameters (transmissivity, recharge, boundary conditions, etc.), nonlinearity, and often low sensitivity of state variables (typically heads and concentrations) to aquifer properties. Because of these difficulties, calibration cannot be separated from the modeling process, as it is sometimes done in other fields. Instead, it should be viewed as one step in the process of understanding aquifer behavior. In fact, it is shown that actual parameter estimation methods do not differ from each other in the essence, though they may differ in the computational details. It is argued that there is ample room for improvement in groundwater inversion: development of user-friendly codes, accommodation of variability through geostatistics, incorporation of geological information and different types of data (temperature, occurrence and concentration of isotopes, age, etc.), proper accounting of uncertainty, etc. Despite this, even with existing codes, automatic calibration facilitates enormously the task of modeling. Therefore, it is contended that its use should become standard practice.

Inverse problem in hydrogeology

[1] A fractal mobile/immobile model for solute transport assumes power law waiting times in the immobile zone, leading to a fractional time derivative in the model equations. The equations are equivalent to previous models of mobile/immobile transport with power law memory functions and are the limiting equations that govern continuous time random walks with heavy tailed random waiting times. The solution is gained by performing an integral transform on the solution of any boundary value problem for transport in the absence of an immobile phase. In this regard, the output from a multidimensional numerical model can be transformed to include the effect of a fractal immobile phase. The solutions capture the anomalous behavior of tracer plumes in heterogeneous aquifers, including power law breakthrough curves at late time, and power law decline in the measured mobile mass. The MADE site mobile tritium mass decline is consistent with a fractional time derivative of order γ = 0.33, while Haggerty et al.'s [2002] stream tracer test is well modeled by a fractional time derivative of order γ = 0.3.

/pdf/fractal-mobile-immobile-solute-transport-1wsr28p5cz.pdf

Fractal mobile/immobile solute transport

Matrix diffusion has become widely recognized as an important transport mechanism. Unfortunately, accounting for matrix diffusion complicates solute-transport simulations. This problem has led to simplified formulations, partly motivated by the solution method. As a result, some confusion has been generated about how to properly pose the problem. One of the objectives of this work is to find some unity among existing formulations and solution methods. In doing so, some asymptotic properties of matrix diffusion are derived. Specifically, early-time behavior (short tests) depends only on φ
 m
 
2
R

 m
 
D

 m
  / L

 m
 
2, whereas late-time behavior (long tracer tests) depends only on φ

 m
 
R

 m
 , and not on matrix diffusion coefficient or block size and shape. The latter is always true for mean arrival time. These properties help in: (a) analyzing the qualitative behavior of matrix diffusion; (b) explaining one paradox of solute transport through fractured rocks (the apparent dependence of porosity on travel time); (c) discriminating between matrix diffusion and other problems (such as kinetic sorption or heterogeneity); and (d) describing identifiability problems and ways to overcome them.

On matrix diffusion: formulations, solution methods and qualitative effects

A discussion on validation of hydrogeological models

Many optimization problems in engineering require coupling a mathematical programming process to a numerical simulation. When the latter is non-linear, the resulting computer time may become unaffordably large because three sequential procedures are nested: the outer loop is associated to the optimization process, the middle one corresponds to the time marching scheme and the innermost loop is required for solving iteratively the non-linear system of equations at each time step. We propose four techniques for reducing CPU time. First, derive the initial values of state variables at each time (innermost loop) from those computed at the previous optimization iteration (outermost loop). Second, select time increment on the basis of those used for the previous optimization iteration. Third, define convergence criteria for the simulation problem on the basis of the optimization process, so that they are only as stringent as really needed. Finally, computations associated to the optimization are shown to be greatly reduced by adopting Newton–Raphson, or a variant, for solving the simulation problem. The effectiveness of these techniques is illustrated through application to three examples involving automatic calibration of non-linear groundwater flow problems. The total number of iterations is reduced by a factor ranging between 1·7 and 4·6. Copyright © 1999 John Wiley & Sons, Ltd.

Computational techniques for optimization of problems involving non-linear transient simulations

Considering concentration data during the calibration of aquifer models improves the reliability of results because identifiability may be improved parameter uncertainty can be reduced, and concentration data are usually cheap to obtain so that large amounts of data can often be taken into account. The drawbacks arise from the numerical and conceptual difficulties associated to solute transport. While these may lead to intractable problems in some cases, they can be overcome in others. An algorithm for estimation of flow and solute transport, including matrix diffusion and adsorption processes, is presented. The formulation of the problem is based in Maximum Likelihood Estimation theory, in which prior information in model parameters can be included. Prior information may come from qualitative sources or may be hard-data based, including geostatistically based. Minimization of the objective function is achieved by Gauss-Newton type algorithms, which work very well after suitable modifications. One example is presented in order to illustrate the efficiency of the proposed algorithm.

Germán Galarza

Papers

On matrix diffusion: formulations, solution methods and qualitative effects

A discussion on validation of hydrogeological models

Computational techniques for optimization of problems involving non-linear transient simulations

Inverse modelling of coupled flow and solute transport problems.

An approach to process identification: application to solute transport through clays.