Choice of dispersion coefficients in reactive transport calculations on smoothed fields

Local dispersion dominates the mixing of compounds that are introduced separately into the subsurface and do not partition into any other than the aqueous phase. Thus, reactions between these compounds are controlled by dispersive mixing if they are not limited by kinetics. I quantify longitudinal dispersive mixing by the longitudinal effective dispersion coefficient of a conservative tracer introduced by a point-like injection [Water Resour. Res. 36 (12) (2000) 3591-3604]. In the upscaling of mixing-controlled reactive transport, I apply the mean velocity and the effective dispersion coefficient to the macroscopic transport calculations, whereas the reactive parameters on the macro-scale are identical to those on the local scale. The applicability of the approach is demonstrated for the transport of compounds undergoing a second-order irreversible bimolecular reaction. Ten realizations of a two-dimensional heterogeneous log-conductivity field are considered. Using the effective dispersion parameters, the overall mass balance is met in the ensemble average, whereas solute spreading is underestimated. I assess the lack of spreading by the difference between the expected macrodispersion and effective dispersion coefficients. I extend the approach to simulations on log-conductivity fields obtained by kriging of regularly spaced conductivity measurements. These fields contain the large-scale features of the true fields but do not resolve the small-scale variability. For the calculations on the kriged fields, the corresponding conditional covariance is substituted into the analytical expressions of effective dispersion, yielding a correction effective dispersion coefficient. The comparison between simulations on the fully resolved fields and on the kriged fields indicates that the approach is valid for wide plumes meeting the ergodicity condition. The high variability of mixing on small scales unresolved by kriging, however, leads to severe uncertainty when mixing-controlled reactions are predicted for narrow plumes.     

Numerical modeling of coupled variably saturated fluid flow and reactive transport with fast and slow chemical reactions

The couplings among chemical reaction rates, advective and diffusive transport in fractured media or soils, and changes in hydraulic properties due to precipitation and dissolution within fractures and in rock matrix are important for both nuclear waste disposal and remediation of contaminated sites. This paper describes the development and application of LEHGC2.0, a mechanistically based numerical model for simulation of coupled fluid flow and reactive chemical transport, including both fast and slow reactions in variably saturated media. Theoretical bases and numerical implementations are summarized, and two example problems are demonstrated. The first example deals with the effect of precipitation/dissolution on fluid flow and matrix diffusion in a two-dimensional fractured media. Because of the precipitation and decreased diffusion of solute from the fracture into the matrix, retardation in the fractured medium is not as large as the case wherein interactions between chemical reactions and transport are not considered. The second example focuses on a complicated but realistic advective-dispersive-reactive transport problem. This example exemplifies the need for innovative numerical algorithms to solve problems involving stiff geochemical reactions.     

Inverse modeling of multicomponent reactive transport through single and dual porosity media

Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.     

Estimating spatially-variable first-order rate constants in groundwater reactive transport systems

Numerical reactive transport models are often used as tools to assess aquifers contaminated with reactive groundwater solutes as well as investigating mitigation scenarios. The ability to accurately simulate the fate and transport of solutes, however, is often impeded by a lack of information regarding the parameters that define chemical reactions. In this study, we employ a steady-state Ensemble Kalman Filter (EnKF), a data assimilation algorithm, to provide improved estimates of a spatially-variable first-order rate constant λ through assimilation of solute concentration measurement data into reactive transport simulation results. The methodology is applied in a steady-state, synthetic aquifer system in which a contaminant is leached to the saturated zone and undergoes first-order decay. Multiple sources of uncertainty are investigated, including hydraulic conductivity of the aquifer and the statistical parameters that define the spatial structure of the parameter field. For the latter scenario, an iterative method is employed to identify the statistical mean of λ of the reference system. Results from all simulations show that the filter scheme is successful in conditioning the λ ensemble to the reference λ field. Sensitivity analyses demonstrate that the estimation of the λ values is dependent on the number of concentration measurements assimilated, the locations from which the measurement data are collected, the error assigned to the measurement values, and the correlation length of the λ fields.     

Identification and reliability of microbial aerobic respiration and denitrification kinetics using a single-well push-pull field test

Methods to derive reaction rates of microbial processes are important since these processes are determining many chemical reactions influencing groundwater quality. Thereby, it is not only important to derive the parameters, but also to have a firm idea about the reliability with which these are determined. Analysis of residuals, sensitivity analyses and analysis of joint confidence intervals provide an interesting tool for this purpose. The method is illustrated in this paper using a push-pull test designed to derive aerobic respiration and denitrification. Therefore, a test solution containing dissolved oxygen and nitrate as reactive tracer and bromide as non-reactive tracer was injected in organic matter rich sediment. Afterwards, this test solution was extracted and water quality was monitored. ReacTrans, a finite-difference, axial-symmetric groundwater flow and solute transport model was developed to simulate the test and derive hydraulic, solute transport and chemical parameters. Aerobic respiration and denitrification were simulated with Michaelis-Menten kinetics. Maximum reaction rates (10.4 and 2.4 mmol/ld for aerobic respiration and denitrification respectively) and Michaelis constants (0.14 and 0.1 mmol/l for aerobic respiration and denitrification respectively) were determined. The reliability with which these parameters are derived is indicated by analysis of residuals, sensitivities and joint confidence intervals. This shows that the Michaelis-Menten parameters can be derived reliable with a push-pull test, whereas the test is insensitive to effective porosity and hydraulic conductivity. Because of the small scale of the test, longitudinal dispersivity was very small and therefore unidentifiable.     

Multidimensional, multicomponent, subsurface reactive transport in nonuniform velocity fields: code verification using an advective reactive streamtube approach

High performance computing has made possible the development of high resolution, multidimensional, multicomponent reactive transport models that can be used to analyze complex geochemical environments. However, as increasingly complex processes are included in these models, the accuracy of the numerical formulation coupling the nonlinear processes becomes difficult to verify. Analytical solutions are not available for realistically complex problems and benchmark solutions are not generally available for specific problems. We present an advective reactive streamtube (ARS) transport technique that efficiently provides accurate solutions of nonlinear multicomponent reactive transport in nonuniform multidimensional velocity fields. These solutions can be compared with results from Eulerian-based advection-dispersion-reaction models to evaluate the accuracy of the numerical formulation used. The ARS technique includes mixed equilibrium and kinetic complexation and precipitation-dissolution reactions subject to the following assumptions: (1) transport is purely advective (i.e., no explicit diffusion or dispersion), and (2) chemistry is described by a canonical system of reactions that evolves with time and is unaffected by position in space. Results from the ARS technique are compared with results from the massively parallel, multicomponent reactive transport model MCTRACKER on a test problem involving irreversible oxidation of organic carbon and reaction of the oxidation products with two immobile mineral phases, gypsum and calcite, and fifteen aqueous complexes. Truncation error, operator splitting error, and the nonlinear transformation of these errors in the high-resolution reactive transport model are identified for this problem.     

Concentration statistics for mixing-controlled reactive transport in random heterogeneous media

Uncertainty in the distribution of hydraulic parameters leads to uncertainty in flow and reactive transport. Traditional stochastic analysis of solute transport in heterogeneous media has focused on the ensemble mean of conservative-tracer concentration. Studies in the past years have shown that the mean concentration often is associated with a high variance. Because the range of possible concentration values is bounded, a high variance implies high probability weights on the extreme values. In certain cases of mixing-controlled reactive transport, concentrations of conservative tracers, denoted mixing ratios, can be mapped to those of constituents that react with each other upon mixing. This facilitates mapping entire statistical distributions from mixing ratios to reactive-constituent concentrations. In perturbative approximations, only the mean and variance of the mixing-ratio distribution are used. We demonstrate that the second-order perturbative approximation leads to erroneous or even physically impossible estimates of mean reactive-constituent concentrations when the variance of the mixing ratio is high and the relationship between the mixing ratio and the reactive-constituent concentrations strongly deviates from a quadratic function. The latter might be the case in biokinetic reactions or in equilibrium reactions with small equilibrium constant in comparison to the range of reactive-constituent concentrations. When only the mean and variance of the mixing ratio is known, we recommend assuming a distribution that meets the known bounds of the mixing ratio, such as the beta distribution, and mapping the assumed distribution of the mixing ratio to the distributions of the reactive constituents.     

Analytical solutions for reactive transport under an infiltration-redistribution cycle

Transport of reactive solute in unsaturated soils under an infiltration-redistribution cycle is investigated. The study is based on the model of vertical flow and transport in the unsaturated zone proposed by Indelman et al. [J. Contam. Hydrol. 32 (1998) 77], and generalizes it by accounting for linear nonequilibrium kinetics. An exact analytical solution is derived for an irreversible desorption reaction. The transport of solute obeying linear kinetics is modeled by assuming equilibrium during the redistribution stage. The model which accounts for nonequilibrium during the infiltration and assumes equilibrium at the redistribution stage is termed partial equilibrium infiltration-redistribution model (PEIRM). It allows to derive approximate closed form solutions for transport in one-dimensional homogeneous soils. These solutions are further applied to computing the field-scale concentration by adopting the Dagan and Bresler [Soil Sci. Soc. Am. J. 43 (1979) 461] column model. The effect of soil heterogeneity on the solute spread is investigated by modeling the hydraulic saturated conductivity as a random function of horizontal coordinates. The quality of the PEIRM is illustrated by calculating the critical values of the Damk?hler number which provide the achievable accuracy in estimating the solute mass in the mobile phase. The distinguishing feature of transport during the infiltration-redistribution cycle as compared to that of infiltration only is the finite depth of solute penetration. For irreversible desorption, the maximum solute penetration W/theta(r) is determined by the amount of applied water W and the residual water content theta(r). For sorption-desorption kinetics, the maximum depth of penetration z(r)(e, infinity ) also depends on the ratio between the rate of application and the column-saturated conductivity. It is shown that z(r)(e, infinity ) is bounded between the depths W/(theta(r)+K(d)) and W/theta(r) corresponding to the maximum solute penetration for equilibrium transport and for irreversible desorption, respectively. This feature of solute penetration explains the unusual phenomena of plume contraction after an initial period of spreading [Lessoff, S.C., Indelman, P., Dagan, G., 2002. Solute transport in infiltration-redistribution cycles in heterogeneous soils. In Raats, P.A.C., Smiles, D.,Warrick, A.W. (Eds), Environmental Mechanics: Water, Mass and Energy Transport in the Biosphere. American Geophysical Union, pp. 133-144]. Unlike transport under equilibrium conditions, when the solute is completely concentrated at the front, the solute under nonequilibrium conditions is spread out behind the front. Heterogeneity leads to additional spreading of the plume.     

Solute transport properties of compacted Ca-bentonite used in FEBEX project

The present Spanish concept of a deep geological high level waste repository includes an engineered clay barrier around the canister. The clay presents a very high sorption capability for radionuclides and a very small hydraulic conductivity, so that the migration process of solutes is limited by sorption and diffusion processes. Therefore, diffusion and distribution coefficients in compacted bentonite (i.e. in "realistic" liquid to solid ratio conditions) are the main parameters that have to be obtained in order to characterise solute transport that could be produced after the canister breakdown. Through-Diffusion (TD) and In-Diffusion (ID) experiments with HTO, Sr, Cs and Se were carried out using compacted FEBEX bentonite, which is the reference material for the Spanish concept of radioactive waste disposal. Experiments were interpreted by means of available analytical solutions that allow the estimation of diffusion coefficients and, in some cases, distribution coefficients. Analytical solutions are simple to use, but rely on hypotheses that do not hold in all the experiments. These experiments were interpreted also using an automatic parameter estimation code that overcomes the limitations of analytical solutions. Numerical interpretation allows the simultaneous estimation of porosity, diffusion and distribution coefficients, accounts for the role of porous sinters and time-varying boundary concentrations, and can use different types of raw concentration data.     

Implications of non-equilibrium transport in heterogeneous reactive barrier systems: evidence from laboratory denitrification experiments

Organic substrates in reactive barrier systems are often heterogeneous material mixtures with relatively large contrasts in hydraulic conductivity and porosity over short distances. These short-range variations in material properties imply that preferential flow paths and diffusion between regions of higher and lower hydraulic conductivity may be important for treatment efficiency. This paper presents the results of a laboratory column experiment where denitrification is investigated using a heterogeneous reactive substrate (sawdust mixed with sewage sludge). Displacement experiments with a non-reactive solute at three different flow rates are used to estimate transport parameters using a dual porosity non-equilibrium model. Parameter estimation from breakthrough curves produced relatively consistent values for the fraction of the porosity consisting of mobile water (β) and the mass transfer coefficient (α), with average values of 0.27 and 0.42 d(-1), respectively. The column system removes >95% of the influent nitrate at low and medium flow, but only 50-75% of the influent nitrate at high flow, suggesting that denitrification kinetics and diffusive mass transfer rates are limiting the degree of treatment at lower hydraulic residence times. Reactive barrier systems containing dual porosity media must therefore consider mass transfer times in their design; this is often most easily accommodated by adjusting flowpath length.     

Description of hydrogeologic heterogeneity and evaluation of radionuclide transport at an underground nuclear test

Realistic models of contaminant transport in groundwater demand detailed characterization of the spatial distribution of subsurface hydraulic properties, while at the same time programmatic constraints may limit collection of pertinent hydraulic data. Fortunately, alternate forms of data can be used to improve characterization of spatial variability. We utilize a methodology that augments sparse hydraulic information (hard data) with more widely available hydrogeologic information to generate equiprobable maps of hydrogeologic properties that incorporate patterns of connected permeable zones. Geophysical and lithologic logs are used to identify hydrogeologic categories and to condition stochastic simulations using Sequential Indicator Simulation (SIS). The resulting maps are populated with hydraulic conductivity values using field data and Sequential Gaussian Simulation (SGS). Maps of subsurface hydrogeologic heterogeneity are generated for the purpose of examining groundwater flow and transport processes at the Faultless underground nuclear test, Central Nevada Test Area (CNTA), through large-scale, three-dimensional numerical modeling. The maps provide the basis for simulation of groundwater flow, while transport of radionuclides from the nuclear cavity is modeled using particle tracking methods. Sensitivity analyses focus on model parameters that are most likely to reduce the long travel times observed in the base case. The methods employed in this study have improved our understanding of the spatial distribution of preferential flowpaths at this site and provided the critical foundation on which to build models of groundwater flow and transport. The results emphasize that the impacts of uncertainty in hydraulic and chemical parameters are dependent on the radioactive decay of specific species, with rapid decay magnifying the effects of parameters that change travel time.     

An overview of uncertainties in modelling groundwater solute transport

Model predictions are uncertain because of uncertainties on future and/or anthropogenic stresses, parameter values and conceptual models. The first two groups of problems can be addressed through rather systematic methods (scenario analysis, error transmission techniques, automatic calibration algorithms, etc.). However, conceptual uncertainties are rarely given adequate attention. The objective of this paper is to synthesize conceptual difficulties associated with transport. These include: (1) processes that are significant at small scales may not be relevant at large scales; (2) inversely, new processes (e.g., dispersion) emerge in response to increase in scale and the way to represent them may depend on the assumed model structure; (3) the observed shapes of both breakthrough curves and pollutant plumes are not well represented by the classical transport equation; (4) porosities and dispersivities derived from field tracer tests often exhibit a directional dependence; etc. Though not directly related to solute transport, scale effects on hydraulic conductivity may also affect solute transport modelling. When these anomalies are examined, it is concluded that they are directly or indirectly caused by heterogeneity. Current approaches for dealing with heterogeneity can be divided into stochastic and deterministic. Stochastic methods have been successful in explaining qualitatively some anomalies of solute transport, but they appear to be far from reaching a stage at which they can be used routinely for solving realistic field problems. On the other hand, when applied with care, deterministic methods have been successfully used in actual problems. Yet, it can be argued that they fail to account for small-scale variability of concentrations so that they would become ineffective when dealing with nonlinear processes, such as chemical reactions. Relevance of on-going research for overcoming these difficulties is discussed.     

Upscaling heterogeneity in aquifer reactivity via exposure-time concept: forward model

Reactive properties of aquifer solid phase materials play an important role in solute fate and transport in the natural subsurface on time scales ranging from years in contaminant remediation to millennia in dynamics of aqueous geochemistry. Quantitative tools for dealing with the impact of natural heterogeneity in solid phase reactivity on solute fate and transport are limited. Here we describe the use of a structural variable to keep track of solute flux exposure to reactive surfaces. With this approach, we develop a non-reactive tracer model that is useful for determining the signature of multi-scale reactive solid heterogeneity in terms of solute flux distributions at the field scale, given realizations of three-dimensional reactive site density fields. First, a governing Eulerian equation for the non-reactive tracer model is determined by an upscaling technique in which it is found that the exposure time of solution to reactive surface areas evolves via both a macroscopic velocity and a macroscopic dispersion in the artificial dimension of exposure time. Second, we focus on the Lagrangian approach in the context of a streamtube ensemble and demonstrate the use of the distribution of solute flux over the exposure time dimension in modeling two-dimensional transport of a solute undergoing simplified linear reversible reactions, in hypothetical conditions following prior laboratory experiments. The distribution of solute flux over exposure time in a given case is a signature of the impact of heterogeneous aquifer reactivity coupled with a particular physical heterogeneity, boundary conditions, and hydraulic gradient. Rigorous application of this approach in a simulation sense is limited here to linear kinetically controlled reactions.     

Variably saturated flow and multicomponent biogeochemical reactive transport modeling of a uranium bioremediation field experiment

Three-dimensional, coupled variably saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport and biogeochemical reactions controlling uranium behavior under pulsed acetate amendment, seasonal water table variation, spatially variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. While the simulation of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado was generally consistent with behaviors identified in previous field experiments at the Rifle IFRC site, the additional process and property detail provided several new insights. A principal conclusion from this work is that uranium bioreduction is most effective when acetate, in excess of the sulfate-reducing bacteria demand, is available to the metal-reducing bacteria. The inclusion of an initially small population of slow growing sulfate-reducing bacteria identified in proteomic analyses led to an additional source of Fe(II) from the dissolution of Fe(III) minerals promoted by biogenic sulfide. The falling water table during the experiment significantly reduced the saturated thickness of the aquifer and resulted in reactants and products, as well as unmitigated uranium, in the newly unsaturated vadose zone. High permeability sandy gravel structures resulted in locally high flow rates in the vicinity of injection wells that increased acetate dilution. In downgradient locations, these structures created preferential flow paths for acetate delivery that enhanced local zones of TEAP reactivity and subsidiary reactions. Conversely, smaller transport rates associated with the lower permeability lithofacies (e.g., fine) and vadose zone were shown to limit acetate access and reaction. Once accessed by acetate, however, these same zones limited subsequent acetate dilution and provided longer residence times that resulted in higher concentrations of TEAP reaction products when terminal electron donors and acceptors were not limiting. Finally, facies-based porosity and reactive surface area variations were shown to affect aqueous uranium concentration distributions with localized effects of the fine lithofacies having the largest impact on U(VI) surface complexation. The ability to model the comprehensive biogeochemical reaction network, and spatially and temporally variable processes, properties, and conditions controlling uranium behavior during engineered bioremediation in the naturally complex Rifle IFRC subsurface system required a subsurface simulator that could use the large memory and computational performance of a massively parallel computer. In this case, the eSTOMP simulator, operating on 128 processor cores for 12h, was used to simulate the 110-day field experiment and 50 days of post-biostimulation behavior.     

Reactive solute transport in macroscopically homogeneous porous media: analytical solutions for the temporal moments

In this work, we investigate one-dimensional solute transport affected by rate-limited sorption, first-order mass transfer, and first-order transformation. Analytical expressions are obtained for the temporal moments of the solute in the solution phase. The effect of various rate coefficients on the temporal moments is examined. It was found that, in the presence of transformation reactions, the mean arrival time, and the spread and skewness of the breakthrough curves, are not monotonic functions of the rate coefficients. These solutions will be useful as a preliminary analysis tool for ascertaining the relative importance of various processes under given conditions. They may also be used to analyze the accuracy of various numerical techniques used for simulation of reactive transport.     

Groundwater flow, multicomponent transport and biogeochemistry: development and application of a coupled process model

A research tool for modeling the reactive flow and transport of groundwater contaminants in multiple dimensions is presented. Arbitrarily complex coupled kinetic–equilibrium heterogeneous reaction networks, automatic code generation, transfer-function based solutions, parameter estimation, high-resolution methods for advection, and robust solvers for the mixed kinetic–equilibrium chemistry are some of the features of reactive flow and transport (RAFT) that make it a versatile research tool in the modeling of a wide variety of laboratory and field experiments. The treatment of reactions is quite general so that RAFT can be used to model biological, adsorption/desorption, complexation, and mineral dissolution/precipitation reactions among others. The integrated framework involving automated code generation and parameter estimation allows for the development, characterization, and evaluation of mechanistic process models. The model is described and used to solve a problem in competitive adsorption that illustrates some of these features. The model is also used to study the development of an in situ Fe(II)-zone by encouraging the growth of an iron-reducing bacterium with lactate as the electron donor. Such redox barriers are effective in sequestering groundwater contaminants such as chromate and TCE.     

Contaminant transport in a municipal drinking water supply: a steady-state approach to estimate rate and uncertainty

Contaminant transport is generally considered to be a key factor when assessing and classifying the environmental risk of polluted areas. In the study presented here, a steady-state approach was applied to obtain estimates of the transit time and concentration of the pesticide metabolite BAM (2,6-dichlorobenzoamide) at a site where it is contaminating a municipal drinking water supply. A Monte Carlo simulation technique was used to quantify the uncertainty of the results and to evaluate the sensitivity of the used parameters. The adopted approach yielded an estimated median transit time of 10 y for the BAM transport from the polluted site to the water supply. Soil organic carbon content in the unsaturated zone and the hydraulic conductivity in the saturated zone explained 44% and 23% of the uncertainty in the transit time estimate, respectively. The sensitivity analysis showed that the dilution factor due to regional groundwater flow and the soil organic carbon content at the polluted site explained 53% and 31% of the uncertainty of concentration estimates, respectively. In conclusion, the adopted steady-state approach can be used to obtain reliable first estimates of transit time and concentration, but to improve concentration predictions of degrading contaminants, a dynamic model is probably required.     

Development of a fuzzy-stochastic nonlinear model to incorporate aleatoric and epistemic uncertainty

Site uncertainties significantly influence groundwater flow and contaminant transport predictions. Aleatoric and epistemic uncertainty are both identified in site characterization and represented using proper uncertainty theories. When one theory best represents one parameter whereas a different theory may be more suitable for another parameter, the hybrid propagation of aleatoric (random) and epistemic (nonrandom) uncertainties will occur. The computational challenges of joint propagation of aleatoric and epistemic uncertainty through groundwater flow and contaminant transport models are significant. A fuzzy-stochastic nonlinear model was developed in this paper to incorporate these two types of uncertain site information and reduce the computational cost. The results show that (1) the computational cost using the nonlinear model is reduced compared with that of using the sparse grid algorithm and Monte Carlo methods; (2) the uncertainty of hydraulic conductivity (K) significantly influences the water head and solute distribution at the observation wells compared to other uncertain parameters, such as the storage coefficient and the distribution coefficient (K_d); and (3) the combination of multiple uncertain parameters substantially affects the simulation results. Neglecting site uncertainties may lead to unrealistic predictions.     

Uncertainty in Nonpoint Source Pollution Models and Associated Risks

The usefulness of water quality simulation models for environmental management is explored with a focus on prediction uncertainty. The specific objective is to demonstrate how the usability of a flow and transport model (here: MACRO) can be enhanced by developing and analyzing its output probability distributions based on input variability. This infiltration-based model was designed to investigate preferential flow effects on pollutant transport. A statistical sensitivity analysis is used to identify the most uncertain input parameters based on model outputs. Probability distribution functions of input variables were determined based on field-measured data obtained under alternative tillage treatments. Uncertainty of model outputs is investigated using a Latin hypercube sampling scheme (LHS) with restricted pairing for model input sampling. Probability density functions (pdfs) are constructed for water flow rate, atrazine leaching rate, total accumulated leaching, and atrazine concentration in percolation water. Results indicate that consideration of input parameter uncertainty produces a 20% higher mean flow rate along with two to three times larger atrazine leaching rate, accumulated leachate, and concentration than that obtained using mean input parameters. Uncertainty in predicted flow rate is small but that in solute transport is an order of magnitude larger than that of corresponding input parameters. Macropore flow is observed to contribute to the variability of atrazine transport results. Overall, the analysis provides a quantification of prediction uncertainty that is found to enhance a user's ability to assess risk levels associated with model predictions.     

Uncertainty in Nonpoint Source Pollution Models and Associated Risks

The usefulness of water quality simulation models for environmental management is explored with a focus on prediction uncertainty. The specific objective is to demonstrate how the usability of a flow and transport model (here: MACRO) can be enhanced by developing and analyzing its output probability distributions based on input variability. This infiltration-based model was designed to investigate preferential flow effects on pollutant transport. A statistical sensitivity analysis is used to identify the most uncertain input parameters based on model outputs. Probability distribution functions of input variables were determined based on field-measured data obtained under alternative tillage treatments. Uncertainty of model outputs is investigated using a Latin hypercube sampling scheme (LHS) with restricted pairing for model input sampling. Probability density functions (pdfs) are constructed for water flow rate, atrazine leaching rate, total accumulated leaching, and atrazine concentration in percolation water. Results indicate that consideration of input parameter uncertainty produces a 20% higher mean flow rate along with two to three times larger atrazine leaching rate, accumulated leachate, and concentration than that obtained using mean input parameters. Uncertainty in predicted flow rate is small but that in solute transport is an order of magnitude larger than that of corresponding input parameters. Macropore flow is observed to contribute to the variability of atrazine transport results. Overall, the analysis provides a quantification of prediction uncertainty that is found to enhance a user's ability to assess risk levels associated with model predictions.