Scott K. Hansen

Measurements and models of reactive transport in geological media

Reactive chemical transport plays a key role in geological media across scales, from pore scale to aquifer scale. Systems can be altered by changes in solution chemistry and a wide variety of chemical transformations, including precipitation/dissolution reactions that cause feedbacks that directly affect the flow and transport regime. The combination of these processes with advective-dispersive-diffusive transport in heterogeneous media leads to a rich spectrum of complex dynamics. The principal challenge in modeling reactive transport is to account for the subtle effects of fluctuations in the flow field and species concentrations; spatial or temporal averaging generally suppresses these effects. Moreover, it is critical to ground model conceptualizations and test model outputs against laboratory experiments and field measurements. This review emphasizes the integration of these aspects, considering carefully designed and controlled experiments at both laboratory and field scales, in the context of development and solution of reactive transport models based on continuum-scale and particle tracking approaches. We first discuss laboratory experiments and field measurements that define the scope of the phenomena and provide data for model comparison. We continue by surveying models involving advection-dispersion-reaction equation and continuous time random walk formulations. The integration of measurements and models is then examined, considering a series of case studies in different frameworks. We delineate the underlying assumptions, and strengths and weaknesses, of these analyses, and the role of probabilistic effects. We also show the key importance of quantifying the spreading and mixing of reactive species, recognizing the role of small-scale physical and chemical fluctuations that control the initiation of reactions.

Push-pull tracer tests: Their information content and use for characterizing non-Fickian, mobile-immobile behavior: INFORMATION CONTENT OF PUSH-PULL TESTS

Path reversibility and radial symmetry are often assumed in push-pull tracer test analysis. In reality, heterogeneous flow fields mean that both assumptions are idealizations. To understand their impact, we perform a parametric study which quantifies the scattering effects of ambient flow, local-scale dispersion and velocity field heterogeneity on push-pull breakthrough curves and compares them to the effects of mobile-immobile mass transfer (MIMT) processes including sorption and diffusion into secondary porosity. We identify specific circumstances in which MIMT overwhelmingly determines the breakthrough curve, which may then be considered uninformative about drift and local-scale dispersion. Assuming path reversibility, we develop a continuous time random walk-based interpretation framework which is flow-field agnostic and well suited to quantifying MIMT. Adopting this perspective, we show that the radial flow assumption is often harmless: to the extent that solute paths are reversible, the breakthrough curve is uninformative about velocity field heterogeneity. Our interpretation method determines a mapping function (i.e. subordinator) from travel time in the absence of MIMT to travel time in its presence. A mathematical theory allowing this function to be directly “plugged into” an existing Laplace-domain transport model to incorporate MIMT is presented and demonstrated. Algorithms implementing the calibration are presented and applied to interpretation of data from a push-pull test performed in a heterogeneous environment. A successful four-parameter fit is obtained, of comparable fidelity to one obtained using a million-node 3D numerical model. Finally, we demonstrate analytically and numerically how push-pull tests quantifying MIMT are sensitive to remobilization, but not immobilization, kinetics. This article is protected by copyright. All rights reserved.

An efficient method for asymptotic solution to some linear PDEs having arbitrary time-varying type I boundary conditions

An asymptotic technique is presented for a class of initial-boundary value problems (IBVP) having an arbitrary time-varying boundary condition. This class of IBVP is traditionally solved using the Laplace transform, meaning that governing equation and boundary condition (BC) are solved jointly in Laplace space. This is inconvenient for many applications, particularly inverse methods that require solution for large numbers of different BC, as any change in the BC means that an entirely new problem has to be solved. In this paper, the Weeks method for asymptotic inversion of the Laplace transform, along with some useful properties of the Laguerre functions, are combined in order to circumvent this problem. It is shown how, once a single Green’s function IBVP has been solved asymptotically by the Weeks method, it is possible to compute a solution for any other BC by algebraic manipulation alone. Efficient numerical implementation is discussed, and the method is used to solve a real contaminant transport problem from the literature. It is seen that computational performance is superior to a direct approach that requires multiple inversions.

Contaminant point source localization error estimates as functions of data quantity and model quality

We develop empirically-grounded error envelopes for localization of a point contamination release event in the saturated zone of a previously uncharacterized heterogeneous aquifer into which a number of plume-intercepting wells have been drilled. We assume that flow direction in the aquifer is known exactly and velocity is known to within a factor of two of our best guess from well observations prior to source identification. Other aquifer and source parameters must be estimated by interpretation of well breakthrough data via the advection-dispersion equation. We employ high performance computing to generate numerous random realizations of aquifer parameters and well locations, simulate well breakthrough data, and then employ unsupervised machine optimization techniques to estimate the most likely spatial (or space-time) location of the source. Tabulating the accuracy of these estimates from the multiple realizations, we relate the size of 90% and 95% confidence envelopes to the data quantity (number of wells) and model quality (fidelity of ADE interpretation model to actual concentrations in a heterogeneous aquifer with channelized flow). We find that for purely spatial localization of the contaminant source, increased data quantities can make up for reduced model quality. For space-time localization, we find similar qualitative behavior, but significantly degraded spatial localization reliability and less improvement from extra data collection. Since the space-time source localization problem is much more challenging, we also tried a multiple-initial-guess optimization strategy. This greatly enhanced performance, but gains from additional data collection remained limited.

Direct Breakthrough Curve Prediction From Statistics of Heterogeneous Conductivity Fields

This paper presents a methodology to predict the shape of solute breakthrough curves in heterogeneous aquifers at early times and/or under high degrees of heterogeneity, both cases in which the classical macrodispersion theory may not be applicable. The methodology relies on the observation that breakthrough curves in heterogeneous media are generally well described by lognormal distributions, and mean breakthrough times can be predicted analytically. The log-variance of solute arrival is thus sufficient to completely specify the breakthrough curves, and this is calibrated as a function of aquifer heterogeneity and dimensionless distance from a source plane by means of Monte Carlo analysis and statistical regression. Using the ensemble of simulated groundwater flow and solute transport realizations employed to calibrate the predictive regression, reliability estimates for the prediction are also developed. Additional theoretical contributions include heuristics for the time until an effective macrodispersion coefficient becomes applicable, and also an expression for its magnitude that applies in highly heterogeneous systems. It is seen that the results here represent a way to derive continuous time random walk transition distributions from physical considerations rather than from empirical field calibration.

Inferring subsurface heterogeneity from push-drift tracer tests

We consider the late-time tailing in a tracer test performed with a push-drift methodology (i.e., quasi-radial injection followed by drift under natural gradient). Numerical simulations of such tests are performed on 1000 multi-Gaussian 2D log-hydraulic conductivity field realizations of varying heterogeneity, each under eight distinct mean flow directions. The ensemble pdfs of solute return times are found to exhibit power law tails for each considered variance of the log-hydraulic conductivity field,

Forensic Misidentification of Aroclor Sources in Fractured Bedrock Due to “Chromatographic” Polychlorinated Biphenyl (PCB) Congener Separation

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Characterizing the impact of model error in hydrologic time series recovery inverse problems

. The tail exponent is found to relate straightforwardly to

CHROTRAN 1.0: A mathematical and computational model for in situ heavy metal remediation in heterogeneous aquifers

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Performance of a geocomposite liner for containing Jet A-1 spill in an extreme environment

and, within the parameter space we explored, to be independent of push-phase pumping rate and pumping duration. We conjecture that individual push-drift tracer tests in wells with screened intervals much greater than the vertical correlation length of the aquifer will exhibit quasi-ergodicity and that their tail exponent may be used to infer