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Computers & Geosciences 52 (2013) 155–163

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Computers & Geosciences


journal homepage: www.elsevier.com/locate/cageo

A residence-time-based transport approach for the groundwater


pathway in performance assessment models
Bruce A. Robinson n, Shaoping Chu
Los Alamos National Laboratory, Mail Stop A127, Los Alamos, NM 87545, USA

a r t i c l e i n f o abstract

Article history: This paper presents the theoretical development and numerical implementation of a new modeling
Received 30 August 2011 approach for representing the groundwater pathway in risk assessment or performance assessment
Received in revised form model of a contaminant transport system. The model developed in the present study, called the
30 August 2012
Residence Time Distribution (RTD) Mixing Model (RTDMM), allows for an arbitrary distribution of fluid
Accepted 3 September 2012
Available online 26 September 2012
travel times to be represented, to capture the effects on the breakthrough curve of flow processes such
as channelized flow and fast pathways and complex three-dimensional dispersion. Mathematical
Keywords: methods for constructing the model for a given RTD are derived directly from the theory of residence
Residence time distribution time distributions in flowing systems. A simple mixing model is presented, along with the basic
Mixing model
equations required to enable an arbitrary RTD to be reproduced using the model. The practical
Performance assessment
advantages of the RTDMM include easy incorporation into a multi-realization probabilistic simulation;
Groundwater pathway
computational burden no more onerous than a one-dimensional model with the same number of grid
cells; and straightforward implementation into available flow and transport modeling codes, enabling
one to then utilize advanced transport features of that code. For example, in this study we incorporated
diffusion into the stagnant fluid in the rock matrix away from the flowing fractures, using a generalized
dual porosity model formulation. A suite of example calculations presented herein showed the utility of
the RTDMM for the case of a radioactive decay chain, dual porosity transport and sorption.
Published by Elsevier Ltd.

1. Introduction a more efficient abstraction of this model is required for use in


a systems model.
The groundwater pathway is an important component of Contaminant transport assessment requiring predictions of
systems models predicting risk in applications such as contami- arrivals at a location downstream is conveniently formulated in
nated sites and nuclear waste repositories. Often, risk- or terms of the travel time or residence time distribution (RTD).
performance-assessment (RA or PA) models consist of a network The RTD is a compact way to describe the composite behavior of
of subsystem models describing the behavior of physical or fluid moving through a groundwater flow system, even when the
chemical barriers to contaminant migration, transport through underlying processes of heterogeneous flow, fast pathways, and
porous media, and the arrival of contaminants at a receptor such hydrodynamic dispersion are complex and uncertain. Represent-
as a wellbore or a compliance boundary. These arrivals typically ing these complexities with a computationally simple model such
are converted from mass flux or concentration to a dose, or to as the one-dimensional advection-dispersion equation (1D-ADE)
some other measure of human or ecological risk. Groundwater may not provide the needed flexibility to examine, say, prefer-
models can be very computationally demanding, especially when ential channeling in a fractured medium or highly heterogeneous,
used in a probabilistic framework involving stochastic distribu- multi-dimensional flow systems. By adopting an RTD-based
tions for uncertain parameters and Monte Carlo analyses for approach, the essential features of the flow system can be
quantification of overall system uncertainty (e.g. Arnold et al., represented, and in the case of linear solute transport processes,
2003; Arnold et al., 2008; Robinson et al., 2003). It is often the the information is sufficient to obtain a unique prediction of
case that even if a large-scale, multi-dimensional groundwater solute breakthrough (Robinson and Viswanathan, 2003). Even for
flow and contaminant transport process model is developed, nonlinear reaction processes, the RTD is still a fundamental
determinant of transport behavior, because it captures the degree
of spreading in time of a mass input. Therefore, modeling
methods based on the RTD provide an attractive approach for
n
Corresponding author. Tel.: þ1 505 667 1910; fax: þ1 505 667 5450. representing results from large-scale, complex process models of
E-mail address: robinson@lanl.gov (B.A. Robinson). the groundwater pathway. Alternatively, in generic studies for

0098-3004/$ - see front matter Published by Elsevier Ltd.


http://dx.doi.org/10.1016/j.cageo.2012.09.001
156 B.A. Robinson, S. Chu / Computers & Geosciences 52 (2013) 155–163

which detailed models are not available, an RTD-based approach pathway. In hydrology, advective transport is governed by velo-
is also appropriate because it provides a more flexible way to city variability caused by subsurface heterogeneities, leading to a
represent flow complexities than a simplified 1D-ADE. range of transport times within the system. Theoretical dispersion
The theory and numerical procedures for characterizing trans- studies and characterization of complex subsurface structures
port in porous media via an RTD-based approach has been the and hydrologic pathways are methods for creating models
subject of previous studies. For example, Robinson and Tester that capture this variability. Beyond advection effects, solute
(1984) observed the dynamics of a fractured geothermal reservoir interactions with the porous media, colloid-facilitated transport,
through the measured RTD in a series of tracer tests, and and diffusion into dead-end pore space adjacent to the flowing
Robinson and Tester (1986) showed how flow maldistribution porosity are physical–chemical processes impacting the distribu-
in a heterogeneous flow system can be quantified using the tion of solute travel times. This section provides the theory for
tracer-determined RTD. Similarly, Becker and Charbeneau creating a reduced model through the use of RTD theory to
(2000) and Becker and Shapiro (2003) take a residence-time- capture advective travel time variability, after which the methods
based approach to the interpretation of interwell tracer tests. In for including other transport processes is presented.
addition, Rainwater et al. (1987), Dagan and Cvetkovic (1996), Consider a system in which a steady or quasi-steady state flow
and Ginn (2001) all developed techniques for folding reactive field is established for the groundwater pathway. Contaminant is
transport into a residence-time-based model. Finally, Robinson typically input at a source, characterized with a time-dependent
and Viswanathan (2003) showed how an arbitrary distribution of source-release model, and the mass flux crossing the far-field
travel times could be incorporated directly into a computationally boundary is the computed result from the groundwater pathway.
efficient model in a manner that also allowed the effects of small- Dispersive and diffusive processes, as well as preferential
scale mixing to be bounded. channeling and percolation through pathways of various perme-
In all implementations of an RTD-based approach, the RTD abilities, lead to a distribution of travel times of the fluid at the
characterizes the range of travel times from flow paths of far-field boundary. In the RTD mixing model approach, the
different velocities which arise as a result of the heterogeneities residence time distribution (also called the exit age distribution,
within the flow system. A wide variety of methods have been after Danckwerts, 1953) of a conservative solute is defined as
developed to characterize the RTD in real systems, including: the follows:
1D-ADE; nonideal flow and solute interchange between f(t)dt is the fraction of injected mass arriving at the far-field
mobile and immobile fluid (e.g. Tang et al., 1981; Maloszewski boundary with residence times between t and t þdt.
and Zuber, 1993; Amin and Campana, 1996); two-region models The integral of this density function, F(t), is given by
Rt
designed to represent preferential flow with different mean FðtÞ ¼ 0 f ðtÞdt.
velocities in each region (e.g. Destouni et al., 1994; Erickson and In the development that follows, it is assumed that the pathways
Destouni, 1997); and numerical solutions of explicitly defined that contaminants take in traveling from inlet to outlet can be
heterogeneous fields based on characterization information of a approximated as a steady state, closed flow system. Under this
subsurface system. In advocating for the use of more complex steady state assumption, the relationship between the distribu-
models to represent laboratory-scale tracer transport in soil tion of residence times at the far-field boundary and the distribu-
monoliths, Gupta et al. (1999) illustrated the general point tion of ages of molecules in the flow system is given by:
adopted in the present study that the decoupling of advective
1FðaÞ
processes via a Lagrangian representation of the system facilitates IðaÞ ¼ ð1Þ
t
the incorporation of additional diffusion and reactive transport
processes while honoring the available information on the flow where a is the age of a parcel of fluid (the elapsed time since it
system. entered the system), t is the mean residence time, and the
In this paper, the previous work of Robinson and Viswanathan internal age distribution I(a) is defined as:
(2003) is used as the basis for a new computational method, I(a)da is the fraction of the molecules in the system with ages
called the RTD mixing model (RTDMM), which provides an between a and a þ da.
efficient and flexible way to capture the essential features of the The mean residence time t, computed as the first moment of the
groundwater pathway. Advective travel times are input directly residence time distribution, is related to the flow rate Q and fluid
into the model in the form of an RTD, allowing other transport volume V of the flow system as follows:
processes such as diffusion into stagnant zones and sorption to be Z 1
readily included. Rather than attempting to replace or improve t¼ tf ðtÞdt ¼ Q =V ð2Þ
0
upon the aforementioned methodologies for representing the
flow system, the approach developed in the present study With these basic relationships in place, we now present a
accommodates an advective RTD of arbitrary complexity, such simple physical model capable of reproducing an arbitrary RTD.
that the additional diffusion or reactive processes can be incor- Models of this sort have long been the focus of theoretical
porated readily. As such, this model may provide an attractive developments in the field of chemical reaction engineering. For
approach for representing the transport behavior in a system for example, Zwietering (1958) proposed two related mixing models
which advective processes are captured using any one of the that each reproduce a given RTD, and theoretically bound the
models listed above, or some alternative method. In the sections behavior of nonlinear reactions in liquid-phase systems. One of
that follow, we provide a derivation of the computational method, these mixing models, developed for solute transport and
discuss its implementation in a flow and transport computer extended to sorption by Robinson and Viswanathan (2003), is
code, and present a set of illustrative results using the method. shown in Fig. 1. The pathway is a plug flow model in which fluid
enters on the right hand side, and exits at various locations along
its length. Within the plug flow system, fluid mixing is perfect
2. Residence time distribution theory across the cross section, and there is no axial mixing along the
length. The manifolds on the sides of the models are zero-volume
This section summarizes the RTD theory, originally outlined in pathways that provide the means for fluid and solute to be drawn
Robinson and Viswanathan (2003), as applied to the development from the model, mixed, and instantaneously transmitted to the
of a computationally efficient model for the groundwater outlet. Thus, the physical transport, and if applicable, reaction and
B.A. Robinson, S. Chu / Computers & Geosciences 52 (2013) 155–163 157

Fig. 1. Schematic diagram of RTDMM for the transport model of the groundwater pathway. The mixing model consists of fluid and solute entering on the right hand side,
and leaving and mixing instantaneously via the manifolds along the side of the model. The diagram in the upper right illustrates the fluid balance within a control volume
and expression relating the outlet flow rate to the manifold to the RTD function.

diffusion processes, takes place only within the plug flow model. volume V1/V is given by
By contrast, the manifold is an idealized construct enabling a Z a1 Z a1
prescribed RTD to be reproduced, but does not represent a ½1FðaÞ
V 1 =V ¼ IðaÞda ¼ da ð3Þ
physical section of the pathway. This mixing model, which forms 0 0 t
the underlying basis for the RTDMM, enforces the latest possible
With all terms except a1 known, it may be solved for by
mixing of fluid of different residence time; a simple reversal of all
interpolation. Proceeding along the pathway, the range of ages
flows reproduces the same distribution of residence times, but
associated with each cell is recursively determined for a given
yields the earliest possible mixing. Regardless of the flow direc-
control volume grid using an expression similar to Eq. (3) with the
tion, an essential element in the development of the RTDMM is
integral performed between ai  1 and ai. This range of ages is also
the fact that the placement and flow rates of the side exits are not
the range of residence times of fluid leaving the cell, so the outlet
arbitrary: for a given RTD, there is a unique arrangement of these
flow rate associated with each cell i is computed numerically
paths. This fact is used in the development of the model in the
using:
next section.
qi ¼ Q f ðaÞDa ¼ Q ½Fðai ÞFðai1 Þ ð4Þ

3. Model development In summary, in the construction of the RTDMM, the control


volumes in the numerical grid represent a given range of ages,
3.1. Construction of RTD-based mixing models computed from the prescribed RTD using the relationships
defined above. The output from the model at a given time is
Robinson and Viswanathan (2003) showed how to build a determined by mixing all exit fluid and computing its concentra-
numerical grid and assign the locations and flow rates of the side tion or mass flux.
exits for the system in Fig. 1 in such a way that a given RTD can be We note in passing that this model is an end member that
reproduced. In this paper, we modify the process for building the prescribes the latest possible mixing of fluid with different
model so that, for a given one-dimensional, control-volume finite residence times. Robinson and Viswanathan (2003) showed that
difference grid, the flow rates of the side exits can be uniquely the opposite extreme of early mixing can be represented by
defined so as to produce the prescribed RTD. The derivation uses reversing all flows in the model: the manifold becomes an
the relationship in Eq. (1) for the internal age distribution and the entrance manifold, and all fluid leaves at the right end of the
minimum mixing model of Fig. 1. This distribution is an age model. This result follows from Zwietering’s original theoretical
inventory for the internal contents of the flow system: this development, which demonstrated the fundamental equivalence
relationship therefore enables a direct mapping onto a control- of the internal age and life expectancy distributions in steady
volume finite-difference numerical grid for the case of plug flow state, continuous flow systems. As explained in Robinson and
within the model. As indicated in Fig. 1, fluid of different ages is Viswanathan (2003), if nonlinear reactions are included, the
segregated along the flow path, with a of zero at the inlet on the impact of uncertain small-scale mixing processes, relevant for
right end of the model and increasing a to the left. Starting at the nonlinear reactive transport systems, can be assessed in a
right end of the model, the fluid in this cell of volume V1 has an bounding way using these two models as end members. Further-
age between 0 and a1, where a1 is the age for which the fractional more, once the minimum-mixing model described here is
158 B.A. Robinson, S. Chu / Computers & Geosciences 52 (2013) 155–163

implemented, the changes to a computer code required to containing the parameters ‘‘on the fly’’ at the beginning of each
implement the maximum-mixing model are trivial. realization.
To use the RTDMM as the basis for an abstraction model, f(t) A final detail concerns the methods by which the RTD of a
and its integral, F(t), must be provided to establish the mixing conservative, non-diffusing solute is included as input to the
model flow rates. Then, transport of a contaminant is modeled by RTDMM. A provision was added to the FEHM code to allow the
including reaction with the porous medium and matrix diffusion RTD to be specified either as a tabular representation of the
(described below). This pathway can be constructed using vir- breakthrough curve of travel times, or in the form of a para-
tually any reactive transport code that allows for fluid and solute meterized model describing the RTD. The first method provides a
sources/sinks to be specified arbitrarily at each computational convenient way to generate RTD curves directly from a ground-
grid cell. The validity of this implementation to reproduce a given water process model or any other analytical or numerical scheme,
RTD was demonstrated previously in Robinson and Viswanathan using particle tracking or other methods. The second method,
(2003), and additional model comparisons are provided below. used in the present study, provides the option to use a normal or
Then, if reactive chemistry is included in the model, it is no more lognormal distribution to represent the RTD, enabling travel time
computationally demanding than the usual one-dimensional uncertainty to be examined generically, without reference to an
transport models developed with such codes. However, in this underlying process model.
deceptively simple and computationally efficient model, the RTD In summary, the RTDMM is an RTD-based approach that
of the system is fully preserved, thereby enabling flexibility in the provides an alternative to the construction of a physically-based
representation of the distribution of advective travel times model such as the 1D-ADE, models employing solute interchange
through the groundwater pathway. between mobile and immobile fluid, or two-region models with
In an extension of our previous work, the generalized dual flow in parallel pathways. The distinction is that the pathway is
porosity model (GDPM) presented in Zyvoloski et al. (2008) is constructed directly from the RTD curve itself, enabling an RTD of
applied herein to represent diffusion and sorption from the arbitrary complexity to be represented. As such, the intention is
primary porosity, such as a fracture network, into the rock matrix. not that the RTDMM replace any of these other options, but rather
In applying the GDPM formulation after constructing the RTDMM, that it be used in situations in which it is more convenient to
we are taking the approach that the heterogeneous flow processes specify the RTD directly. Examples may include flow systems in
are captured as a distribution of fluid residence times, and the which the RTD is measured using a conservative tracer, or a
purely solute-driven process of molecular diffusion into stagnant complex RTD curve derived from a multi-dimensional flow and
regions of the porous medium are treated separately. The GDPM transport simulator.
method, described and validated in Zyvoloski et al. (2008),
assumes one-dimensional transport into and out of a matrix
connected to each primary porosity node in the RTD mixing 4. Demonstration calculations
model, and allows multiple, closely spaced matrix nodes to be
used to capture sharp concentration gradients immediately adja- This section provides some basic verification calculations to
cent to the primary (fracture) flow medium. The model domain of demonstrate the correct functioning of the code, and then
primary porosity and one-dimensional matrix nodes is repre- demonstrates the use of the RTDMM with matrix diffusion to
sented in integrated finite difference form. The present study simulate groundwater transport for a specific application. The
represents, to our knowledge, the first attempt to couple a goal of the application is to demonstrate the groundwater trans-
residence-time-based conceptual model for advection to a matrix port model for a series of model runs similar to those that will be
diffusion mass exchange model. performed in a full Monte Carlo analysis. All of the features
developed to integrate FEHM with GoldSim to execute a model
for the groundwater pathway are demonstrated, including: a
3.2. Code implementation details multiple species reactive transport model; the ability to para-
meterize an arbitrary distribution of travel times within the
To implement the RTDMM, provisions were developed within primary pathway; generalized dual porosity formulation to
the computer code FEHM (Zyvoloski et al., 1997) to easily input include diffusion in dead-end pathways. Following a simple
an arbitrary RTD, or a parameterized RTD model such as a normal sensitivity analysis, an uncertainty analysis model run is pre-
or lognormal RTD. This choice enabled the model to take advan- sented by conducting a Monte Carlo simulation with the RTDMM,
tage of FEHM’s reactive transport module (Viswanathan et al., using GoldSim as the simulation driver.
1998; Robinson et al., 2000) and the GDPM model (Zyvoloski
et al., 2008) to solve reactive transport with matrix diffusion. To 4.1. Verification
facilitate probabilistic simulations, FEHM was also coupled to the
GoldSim software (GoldSim Technology 2010), thereby opening This section illustrates, through a few examples, the correct
the possibility of easily performing Monte Carlo simulations with functioning of the code in reproducing an RTD and incorporating a
parameters passed from GoldSim to FEHM for each realization. To matrix diffusion formulation for a given advective RTD.
accomplish this, GoldSim invokes FEHM at each time step To verify that the model reproduces an arbitrary RTD, the
through a call to FEHM as a dynamic link library (dll), and cedes general approach is to generate that RTD using a separate model,
control of the calculation to FEHM for calculation of the transport or to simply define its functional form (e.g. assume a lognormal
process in the RTDMM. If sub-timesteps are required for numer- RTD without reference to a physical flow system), and show that
ical convergence or accuracy, FEHM performs this time step the current method reproduces that RTD when it is provided as
adjustment. At the end of each GoldSim time step, FEHM passes input to a RTDMM simulation of a pulse or step input of tracer.
back to GoldSim any mass reaching the outlet of the model, and For verification purposes, we present the following cases: a
retains in memory the current concentration distributions so that 1D-ADE model; a lognormal RTD characterized by its lognormal
the calculation can resume for the next GoldSim time interval. mean and standard deviation; and a two-region model similar to
Finally, the ability to change flow and transport parameters from that suggested by Gupta et al. (1999), consisting of a pair of
one realization to the next is implemented using a separate dll parallel 1D-ADE models that mix at the outlet, yielding a bimodal
called by GoldSim that writes the appropriate FEHM input file RTD. Fig. 2 presents the 1D-ADE model and the lognormal model
B.A. Robinson, S. Chu / Computers & Geosciences 52 (2013) 155–163 159

supplied as input to the code, the method correctly constructs the


model and assigns the flow rates so as to reproduce the RTD for
the pulse input of a passive tracer.
Beyond demonstrating that the RTDMM correctly reproduces
the desired RTD, it is necessary to test the functioning of the code
for the more complex situation of diffusion into dead-end pore
space, as represented by a system consisting of flow through
fractures, with diffusion into the rock matrix. For this situation,
both the FEHM model and the analytical solution of Tang et al.
(1981) are used. Fig. 2 compares the analytical solution to the
RTDMM model for the cases of advection and longitudinal
dispersion in the fractures, and diffusion into the surrounding
rock matrix, with and without sorption on the matrix material. In
the GDPM model formulation, the matrix consists of a local one-
dimensional grid of 29 computational grid cells spaced to capture
the concentration gradients due to diffusion near the primary
porosity, as well as deep into the matrix blocks. Sorption in the
matrix is modeled using an equilibrium, linear sorption (Kd)
model. Sorption is assumed to be negligible on the fracture walls
of the primary porosity. The RTDMM model takes the 1D-ADE
RTD (with no matrix diffusion or sorption) as input, and simulates
the output concentration at the end of the flow path in the
presence of matrix diffusion. By contrast, the curve labeled
Fig. 2. Comparison of RTDMM results to expected breakthrough curves for a
constant concentration input. 1D-ADE: RTDMM compared to a numerical solution
‘‘Original model’’ is a simple 1D-ADE model (as opposed to the
for a 1D-ADE solution; Lognormal RTD: RTDMM compared to a lognormal RTD RTDMM approach) with matrix diffusion included. Both of these
breakthrough curve; 1D-ADE, matrix diffusion: RTDMM compared to Tang et al. are compared to the Tang et al. (1981) analytical solution. The fact
(1981) analytical solution and a numerical 1D-ADE solution with matrix diffusion that the RTDMM matches both the 1D-ADE based model and the
included; 1D-ADE, matrix diffusion and sorption: RTDMM compared to Tang et al.
analytical solution demonstrates the correct implementation of
(1981) analytical solution and a numerical 1D-ADE solution with matrix diffusion
and linear equilibrium sorption on the rock matrix included. the FEHM GDPM formulation as an integral component of the
RTDMM model implementation.

4.2. Simple sensitivity analysis

This demonstration simulation consists of a four-species radio-


nuclide decay chain:
243
Am-239 Pu-235 U-231 Pa
with radionuclide half lives of 7.37  103 y, 2.41  104 y,
7.04  108 y, and 3.25  104 y, respectively. The transport path-
way is taken to be a fractured rock, represented using the GDPM
formulation with a primary porosity consisting of transport
through fractures, and diffusion and sorption within the rock
matrix. Within the fractures, the RTDMM is employed with a
lognormal distribution of travel times within the fracture domain.
This choice demonstrates a significant benefit of the RTDMM:
the ability to capture a wide distribution of travel times to study
the influence of fast pathways through the groundwater pathway,
while retaining the simplicity and convenience of a parameter-
ized model.
Because this demonstration is illustrative, a simplified source
term consisting of a constant unit source of 243Am at the inlet of
the pathway is employed, with no source of 239Pu, 235U, or 231Pa
(these species are present due to in-growth, however). In an
Fig. 3. Comparison of the RTDMM results to the input RTD (labeled ‘‘Original actual RA or PA analysis, a source term release model would also
model’’) developed from a two-region model consisting of parallel flow through be developed, perhaps with uncertainty represented, and each
two 1D-ADE pathways. Response is for a pulse input of tracer, and concentrations
species would likely have a source.
are normalized such that the mass output is equivalent for the two models.
Parameters in these example calculations are provided in
Table 1. For each uncertain parameter, the ‘‘base case’’ simulation
results (along with the matrix diffusion results, which are is defined as the model with mean or median values selected for
described subsequently); Fig. 3 shows the results of the two- each parameter. Then, a series of individual model runs were
region model for a pulse input of solute. The 1D-ADE and performed to examine model sensitivities when each parameter is
lognormal models are compared for a constant concentration individually varied plus or minus two standard deviations from
step input of tracer, which requires that the RTDMM be compared the mean value. Fig. 4 shows the sensitivity to uncertainties in the
to F(t), the integral of the input RTD. The curves labeled ‘‘Original hydrologic parameters (mean residence time and lognormal
model’’ represent the desired result to which the RTDMM results standard deviation of residence time), and Fig. 5 is a similar set
are compared. The close agreement verifies that when the RTD is of figures for uncertainty in diffusion and sorption parameters.
160 B.A. Robinson, S. Chu / Computers & Geosciences 52 (2013) 155–163

Table 1
Input hydrologic and transport parameters used in the demonstration calculations.

Parametera Stochastic parameter type Base case value Distribution parameters

Flow parameters
Mean of Ln travel time distribution, mln Normal distribution for mln 18.87676 (ln(s)) 18,87676, 0.8
Std. Dev. of Ln travel time distribution, sln Normal distribution for sln ¼ sln =mln 0.026487 0.026487, 7.946  10  3

Geometric parameters
Aperture (m) Constant 1  10  3 1  10  3
Fracture spacing (m) Constant 5 5
Free-water diffusion coefficient Dfree (m2/s), 243
Am Constant 9.49  10  10 9.49  10  10
Dfree (m2/s), 239Pu Constant 1.30  10  9 1.30  10  9
Dfree (m2/s), 235U Constant 6.64  10  10 6.64  10  10
Dfree (m2/s), 239Pa Constant 6.04  10  10 6.04  10  10
Diffusive tortuosity tD, all species Normal distribution for tD ¼ D=Dfree 0.0144 0.0144, 4.176  10  3
Matrix sorption coefficient Kd (cc/g), 243Am Cumulative distribution function CDF 400 (100,0) (400,0.5) (1000,1)
Kd (cc/g), 239Pu CDF 100 (10,0) (100,0.5) (200,1)
Kd (cc/g), 235U CDF 0.2 (0,0) (0.2, 0.5) (3,1)
Kd (cc/g), 231Pa Truncated normal distribution 5500 Range: 103–104, 5500, 1500

a
Parameter values were selected as representative of a fractured rock under oxidizing conditions. Actual values used in an analysis would be site-specific, depending
on the hydrologic and geochemical conditions at the site. For illustrative purposes, values from the Yucca Mountain Project nuclear waste repository have been adopted in
this study (SNL, 2008).

1 1 1

0.1 0.1 0.1


Normalized Breakthrough

Normalized Breakthrough

Normalized Breakthrough
0.01 0.01 0.01

0.001 0.001 0.001

0.0001 0.0001 0.0001

0.00001 0.00001 0.00001


1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05 1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05 1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05
Time since release, years Time since release, years Time since release, years

1 1 1

0.1 0.1 0.1


Normalized Breakthrough

Normalized Breakthrough

Normalized Breakthrough

0.01 0.01 0.01

0.001 0.001 0.001

0.0001 0.0001 0.0001

0.00001 0.00001 0.00001


1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05 1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05 1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05
Time since release, years Time since release, years Time since release, years

Fig. 4. Sensitivity analyses varying the far field model parameters plus and minus two standard deviations from their mean values. Left column: 243Am, Center column:
239
Pu, right column: 235U. Solid curves: base case parameters. Dotted curves: parameters reduced by two standard deviations. Dashed curves: parameters increased by two
orders of magnitude. Top row: mean residence time is varied. Bottom row: log of standard deviation of residence time is varied.

In each set of six figures, a row denotes the change in a particular the input is able to reach the outlet before decaying. This fraction
parameter, and a column denotes a particular radionuclide (left is strongly influenced by the early-arriving portion of the inven-
column: 243Am, center column: 239Pu, right column: 235U, 231Pa tory, as influenced by the parameters of the lognormal RTD. This
not shown). In each individual figure, the base case simulation is is seen in the bottom row of Fig. 4, which indicates that for
the solid curve, the dotted curve is the parameter reduced by two smaller spreads in the lognormal distribution of residences times,
standard deviations, and the dashed curve is the parameter there is a lessening of the early breakthroughs of 243Am, which in
increased by two standard deviations. turn leads to a smaller fraction of the mass arriving at the outlet
The top row of Fig. 4 indicates that uncertainty in the mean before decaying. By contrast, most parameters have a very small
residence time has a large influence on the breakthrough curve effect on the breakthrough of 235U because the breakthrough of
through the far field model. The largest effect is on 243Am, with a this weakly sorbing radionuclide is controlled principally by the
moderate effect on 239Pu, and a small effect on 235U. The dramatic transport delays of the parent species as well as radioactive decay.
effect on 243Am is controlled by the degree to which a portion of Essentially, 235U travels rapidly through the model once it is
B.A. Robinson, S. Chu / Computers & Geosciences 52 (2013) 155–163 161

1 1 1

0.1 0.1 0.1


Normalized Breakthrough

Normalized Breakthrough

Normalized Breakthrough
0.01 0.01 0.01

0.001 0.001 0.001

0.0001 0.0001 0.0001

0.00001 0.00001 0.00001


1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05 1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05 1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05
Time since release, years Time since release, years Time since release, years

1 1 1

0.1 0.1 0.1


Normalized Breakthrough

Normalized Breakthrough

Normalized Breakthrough
0.01 0.01 0.01

0.001 0.001 0.001

0.0001 0.0001 0.0001

0.00001 0.00001 0.00001


1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05 1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05 1e-02 1e-01 1e+00 1e+01 1e+02 1e+03 1e+04 1e+05
Time since release, years Time since release, years Time since release, years

Fig. 5. Sensitivity analyses varying the far field model parameters plus and minus two standard deviations from their mean values. Left column: 243Am, Center column:
239
Pu, right column: 235U. Solid curves: base case parameters. Dotted curves: parameters reduced by two standard deviations. Dashed curves: parameters increased by two
orders of magnitude. Top row: diffusive tortuosity is varied. Bottom row: all sorption coefficients are varied.

generated from decay of 239Pu, so changes in its transport To gain further insight into the underlying uncertainties that
parameters or the flow rate through the system have a relatively control the results, the importance analysis feature in the Gold-
small effect. The influence of uncertainties in the diffusion and Sim software is used. The importance measure, a metric with a
sorption parameters (Fig. 5) are similar to those for the mean normalized value between 0 and 1, represents the fraction of the
residence time. These parameters impart a delay in the travel variance in a result that is explained by the uncertainty in a
time that acts in a similar manner to an increase in mean particular variable. This measure is useful in identifying non-
residence time. For the parameter ranges selected here, the linear, non-monotonic relationships between an input variable
magnitude of the differences is less for the diffusion and sorption and the result, which conventional correlation coefficients may
parameters than for the travel time parameters. not reveal. To ensure that 500 is a sufficient number of realiza-
tions, additional simulation runs using 100, 1000, and 2000
realizations were performed. Significant differences were found
4.3. Monte Carlo analysis in the 100 and 500 realization cases; however, average differences
in the importance measure were only about 3% when comparing
Using the same basic model setup, we ran a suite of Monte the 500 realization case to the 1000 or 2000 realization cases,
Carlo simulation runs with values for the seven uncertain hydro- suggesting that there are statistically insignificant differences in
logic and transport parameters (the two flow parameters, tortu- the model runs for the cases with greater than 500 realizations.
osity for matrix diffusion, and the sorption Kd values for each Therefore, the 500-realization case is presented below.
species) sampled from stochastic distributions. Results presented In this example, the ‘‘result’’ we use to examine the impor-
below are for a simulation consisting of 500 Monte Carlo realiza- tance of different parameters is the total cumulative arrival of a
tions, with each realization run to a simulation time of 200 ky. species at the outlet at a particular time (i.e. the y-value of the
Note that, as described below, convergence testing using different breakthrough curve at the selected time). To gain further insight,
numbers of realizations indicated that 500 realizations was we selected three times at which to do the importance analysis:
sufficient to obtain stable results. Descriptions of the 12 para- 103, 104, and 105 y. For illustration, we discuss the results for
235
meters are provided in Table 1. The mass fluxes reaching the U. Fig. 7 shows the uncertainty in sorption coefficient for 235U
outlet boundary in response to the unit input of 243Am were (KdU235) dominating the influence on 235U breakthrough for the
analyzed using the statistical analysis and breakthrough display earlier times (103 and 104 y), even to the extent that it becomes a
capabilities of GoldSim. A description of a few representative more influential uncertain parameter than the mean travel time.
results follows. This result changes for the longest time frame, with uncertainty in
Fig. 6 shows the composite uncertainty range for 243Am mean travel time (LnorMean) dominating by the end of simula-
breakthrough accounting for uncertainties in all parameters. This tion. The Kd values of the parent species in the decay chain also
range of breakthroughs represents how the uncertainty in the appear as somewhat important to the uncertainty in 235U break-
parameters associated with this species would propagate through through, reflecting the fact that retardation of the parent species
a probabilistic systems analysis, impacting bottom-line results lead to greater or lesser amounts of decay to 235U their transport
such as dose. through the system. Thus, while a complete presentation of this
162 B.A. Robinson, S. Chu / Computers & Geosciences 52 (2013) 155–163

1.0e00

1.0e-02

1.0e-04

(g/y r)
1.0e-06

1.0e-08

1.0e-10
1.0e-02 1.0e00 1.0e02 1.0e04 1.0e06
Time (yr)

Percentiles
Greatest Result 95% Percentile 75% Percentile
25% Percentile 5% Percentile Least Result
Mean Median

243
Fig. 6. Uncertainty ranges in the output mass flux time-history curve for Am based on the 500 realization Monte Carlo simulation.

Fig. 7. Importance analysis of the input parameters with respect to uncertainties in the 235U output mass flux. Larger values for a parameter denote that the uncertainties
in that parameter have a larger influence on the overall uncertainty in the output mass flux.

model is outside the scope of this paper, the illustrative results directly from a process model, using particle tracking or other
show the power of the RTDMM for enabling the groundwater methods, or by otherwise defining the RTD using a simple,
pathway to be represented in a robust yet computationally parameterized representation of travel times such as a normal
efficient manner. or lognormal distribution.
There are important potential benefits to RTDMM approach.
First, in a probabilistic simulation study in which a different RTD
5. Conclusions is specified for each realization, the flow rates unique to that RTD
can be mapped onto the same grid, with no other adjustments.
This paper presents the theoretical development and numerical Second, the model is easily implemented in any flow and trans-
implementation of a new modeling approach for representing the port modeling code that is capable of accepting prescribed fluid
groundwater pathway in an RA or PA model of a contaminant and solute source terms at multiple grid cells. Third, once the flow
transport system. The model developed in the present study, model is set up, the computational burden of the calculation is no
called the RTD Mixing Model (RTDMM), allows for an arbitrary more onerous than a one-dimensional model with the same
distribution of fluid travel times to be represented, to capture, number of grid cells, even though the model is able to represent
albeit indirectly, the effects of flow processes such as channelized a wide variety of travel time distributions. Finally, for codes that
flow and fast pathways and complex three-dimensional disper- also have reactive transport or other advanced transport options,
sion. This opens the door to be able to specify the RTD curve implementation of the RTDMM makes these features immediately
B.A. Robinson, S. Chu / Computers & Geosciences 52 (2013) 155–163 163

available. For example, use of the FEHM computer code allowed Becker, M.W., Charbeneau, R.J., 2000. First-passage-time transfer functions for
us to incorporate reactive transport and diffusion into the groundwater tracer tests conducted in radially convergent flow. Journal of
Contaminant Hydrology 40, 299–310.
stagnant fluid in the rock matrix away from the flowing fractures, Becker, M.W., Shapiro, A.M., 2003. Interpreting tracer breakthrough tailing from
using that code’s generalized dual porosity model formulation. different forced-gradient tracer experiment configurations in fractured bed-
A suite of example calculations verified the correct implemen- rock. Water Resources Research 39 (1), 1024, http://dx.doi.org/10.1029/
tation of the method, and showed its utility for the case of a 2001WR001190.
Dagan, G., Cvetkovic, V., 1996. Reactive transport and immiscible flow in geologic
radioactive decay chain, dual porosity transport and sorption. Our media I. General theory. Proceedings of the Royal Society of London, Series A
examples utilized the option of specifying an RTD with lognormal 452, 285–301.
distribution, which results in a very wide distribution of travel Danckwerts, P.V., 1953. Continuous flow systems: distribution of residence times.
Chemical Engineering Science 2, 1–13.
times that might be more representative of a highly heteroge- Destouni, G., Sassner, M., Jensen, K.H., 1994. Chloride migration in heterogeneous
neous, fractured medium than the traditional 1D-ADE model. soil 2. Stochastic modeling. Water Resources Research 30 (3), 747–758.
Similarly, two-region or other models often yield complex, Erickson, N., Destouni, G., 1997. Combined effects of dissolution kinetics, second-
perhaps bimodal RTD curves, yet the RTDMM can implement this ary mineral precipitation, and preferential flow on copper leaching from
mining waste rock. Water Resources Research 33 (3), 471–483.
type of model with no additional computational burden than is Ginn, T.R., 2001. Stochastic-convective transport with nonlinear reactions and
encountered with the 1D-ADE model. Finally, though not the mixing: finite streamtube ensemble formulation for multicomponent reaction
focus of the present study, it would be possible to use the systems with intra-streamtube dispersion. Journal of Contaminant Hydrology
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GoldSim Technology Group, 2010. Goldsim Probabilistic Simulation Environment
tive tracer as direct input to the RTDMM, so that more complex User’s Guide, Version 10.5, December, 2010.
reactive tracers can be modeled. In this way, the advective Gupta, A., Destouni, G., Jensen, M.B., 1999. Modelling tritium and phosphorus
processes would be captured directly without the preliminary transport by preferential flow in structured soil. Journal of Contaminant
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groundwater tracer tests. Water Resources Research 23, 1901–1910.
presenting a multi-realization result that used the importance Robinson, B.A., Tester, J.W., 1984. Dispersed fluid flow in fractured reservoirs: an
sampling method provided by GoldSim to investigate the degree analysis of tracer-determined residence time distributions. Journal of Geo-
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Robinson, B.A., Tester, J.W., 1986. Characterization of flow maldistribution using
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ques for modeling multicomponent ground-water transport based upon
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Acknowledgments ttp://dx.doi.org/10.1029/2003WR002368.
Robinson, B.A., Li, C.H., Ho, C.K., 2003. Performance assessment model develop-
ment and analysis of radionuclide transport in the unsaturated zone, Yucca
Funding for portions of this work was provided by the Mountain, Nevada. Journal of Contaminant Hydrology 62–3, 249–268.
Department of Energy, Office of Nuclear Energy Advanced Fuel SNL, 2008. Particle Tracking Model and Abstraction of Transport Processes. MDL-
Cycle Initiative. The authors thank the anonymous reviewers of NBS-HS-000020 REV 02 ADD 02. Sandia National Laboratories, Las Vegas,
Nevada.
our manuscript for their constructive and thorough reviews, Tang, D.H., Frind, E.O., Sudicky, E.A., 1981. Contaminant transport in fractured
which enabled us to strengthen the paper considerably. porous media: analytical solution for a single fracture. Water Resources
Research 17 (3), 555–564.
Viswanathan, H.S., Robinson, B.A., Valocchi, A.J., Triay, I.R., 1998. A reactive
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