Advances in Water Resources 36 (2012) 8697

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Advances in Water Resources

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Risk characterization for toxic chemicals transported in aquifers

Roko Andricevic , Veljko Srzic, Hrvoje Gotovac
University of Split, Civil and Architectural Engineering Faculty, Croatia

a r t i c l e

i n f o

Article history:
Available online 18 April 2011
Keywords:
Expected mass fraction
Exposure duration
Dilution effect
Risk assessment

a b s t r a c t
The risk characterization resulting from the introduction of toxic chemicals in a subsurface ow eld is
presented. The concept of concentration threshold is used to quantify the risk associated with non-carcinogenic chemicals introduced to the population by ingestion of groundwater as the exposure pathway.
The risk assessment methodology presented uses the expected mass fraction (EMF) concept with exposure duration to identify the distribution of dosage over different concentrations during the plume migration over the well location. The numerical simulation of the subsurface transport by advection and local
diffusion is used to produce the concentration plume that passes different locations of interest. The EMF
obtained presents the probability of the expected mass above some concentration threshold found at the
location of interest. The risk formulation is dened with the risk reliability (safety) and its complement,
the risk exceedance (failure) value. The risk characterization is obtained as a probability for exceeding the
human reference dose which is considered uncertain due to the necessary extrapolation between concentration used in toxicological studies and the concentration to which humans could be exposed in nature.
The nal risk assessment expression is derived in a closed form by coupling the expected mass fraction
with the safe human threshold concentration probability density function (pdf) inferred from the toxicological studies. The results indicate the importance of estimating the probability of a concentration mass
found at locations of interest together with its exposure duration. The exposure duration was revealed to
be an important parameter that needs to be estimated depending on the human concentration threshold
selected and the distance from the source. The results in terms of the risk safety and risk failure also indicate the dilution effect on the passing concentration plume in the subsurface as a function of the distance
and orientation from the source. Inclusion of uncertainty in the selection of the human concentration
threshold shows the important effect on the risk quantication.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
When a certain toxic contaminant is introduced into the
groundwater, either accidentally or through deep well injection,
the subsurface dispersion process leads to spreading and mixing,
which occur in aquifers with heterogeneous structure on different
scales. The subsurface concentration in plumes and clouds is inherently a random variable due to the stochastic nature of the velocity
uctuations. Contaminant spreading by heterogeneous velocity in
the subsurface is accompanied by the local diffusion process (dened below heterogeneity scale), which acts to dilute the contaminant mass. The key question for the exposure assessment in the
subsurface is how quickly the local diffusion process will be able
to dilute the contaminant mass in the subsurface by mixing it with
the larger aquifer volume.
The fact that so many toxic chemicals, each with a potential effect, are present in the environment, and particularly in groundwater, creates a situation in which it is difcult to determine all the
Corresponding author.
E-mail address: rokoand@gradst.hr (R. Andricevic).
0309-1708/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.advwatres.2011.04.009

possible effects, and it is even more difcult to evaluate the risk

associated with such exposure. The exact number of chemicals in
commerce today in the environment is uncertain, but estimates
range as high as 100,000 with up to 1000 new chemical compounds released each year [33]. The toxicological and environmental characteristics of only a fraction of these have actually been
examined in ecotoxicological studies. Chemicals of concern are
those whose exposure level within the toxicological studies shows
some adverse effects to the humans and/or the environment.
Consider the problem of trying to predict the exposure of a certain population to groundwater contamination originating from
the well eld used for the water supply. Groundwater is contaminated by some known toxic chemical either accidentally or
through the some landll leakage. At any given time, the groundwater concentration misses some of the supply wells completely
while others will receive the polluted groundwater at varying concentrations. The highest concentration will occur only in a small
volume, which can occur almost anywhere at any time, but rarely
at a given location. Thus, the statistical properties of concentration
uctuations in a dispersing plume are important for the risk
assessment in which there is a nonlinear relationship between

R. Andricevic et al. / Advances in Water Resources 36 (2012) 8697

the concentration and duration of exposure for a given harmful effect [2,11,35]. Establishing the statistics of the highest concentration requires either long term observations to assure observing
the highest concentration and estimate its frequency of occurrence
or requires many observers to ensure that the highest concentration at any given time will be observed.
The importance of predicting concentration uctuations in the
subsurface transport has been a topic of great interest in the
past [1,2,8,11,1315,1719,23,25,27,34,39,42]. Furthermore, to
address the issue of concentration probability density function
(pdf), even higher order statistical concentration moments needs
to be estimated as well [2,38]. The risk assessments approaches
usually were tied to the subsurface transport [3,31,35] or combined with the site characterization [5,6,32] and remediation
strategies [10]. For the purpose of assessing the risk and estimating the self-purication of groundwater the dilution of the
concentration eld has attracted particular attention [1,2,25,
27,31,34]. Estimating the concentration level to be used in the
risk quantication remains the challenging task. In the work of
Maxwell et al. [31] the concentration was averaged over 30-year
window placed on the peak of the breakthrough curve (BTC).
Later, in the study of de Barros and Rubin [5], the rst two
moments of the solute ux were used to express the rst two
moments of the carcinogenic risk conditioned on hydrogeological
and human physiological parameters.
This paper establishes a relationship between subsurface concentrations, which observers see most of the time (typical case),
and the highest concentrations, which have greater importance
but rarely occur. Events that occur more frequently represent the
norm. While the norm may still pose a health problem, it does
not require great statistical effort to effectively address. In fact,
when a frequently occurring danger is recognized, it can be deal
with, avoided or resolved. The rare infrequent events require more
effort to establish the appropriate measures. The subsurface dispersion problem and associated risk assessment requires assessing
the potential health dangers so that people can decide whether to
accept the risk, resolve the problem, or possibly decide that no
problem exists. Intermittent short exposures to high subsurface
concentration, with recovery time in between, may not cause any
harm. However, if the same exposure comes over too short a time
interval, with not enough recovery time, health problems may
result.
In this study, the case of a generic non-carcinogenic toxic substance with the ingestion of groundwater as the exposure pathway
to an individual is selected to demonstrate the use of EMF and the
exposure duration. Besides the ingestion of tap water, other exposure pathways such as inhalation (particularly for volatile contaminants) and dermal sorption (metal contaminants with sorptive
characteristics) may also contribute to overall risk. However, because ingestion is usually assumed to be the largest contributor
to risk, it is considered here as the only exposure pathway. The
methodology presented in this study can also be applied to other
exposure pathways, when a specic chemical is considered, and
carcinogenic endpoints.
Predicting the subsurface contamination eld and associated
risk requires knowledge about both the statistics of the contaminant and the way that people react to it at high or low concentrations, for long or short periods and with frequent or
infrequent exposure. The concentration distribution in time and
space is required. Using groundwater for a water supply for a
period of time may dilute very small volumes of very high concentrations to produce larger volumes of a tolerable concentration. Similarly, many points of high concentration close
together might, even when averaged, produce a dangerous
health effect, while the same points, spread out over time, produce no harm.

87

This paper considers the conditional scenario in the subsurface

pollution problem: Given the accidental release of a toxic substance in the subsurface, how much danger does it cause? This
work looks at various probabilities in the outcome, such as mixing
and advection processes, concentration, dilution and different
doses. The ecotoxicological relationship between toxicity, concentration and duration forms the next step in the risk assessment and
the results of the present study can be very valuable to toxicological studies to overcome the large degrees of uncertainty usually
associated with unavoidable extrapolation [26]. A different function of concentration is introduced and termed the expected mass
fraction to estimate probability of actual mass found at a location
of interest and its exposure duration. The risk characterization is
presented as a probability of exceeding the human reference dose,
which is considered uncertain due to the use of safety factor in its
determination. The numerical setup is carefully designed to address the key subsurface transport mechanisms and is utilized to
demonstrate this methodology for the risk quantication for noncarcinogenic substances. The results indicate the importance of
estimating the probability of concentration uctuations at locations of interest together with their exposure duration. The choice
of human reference dose and its apparent estimation problems
[41] are clearly demonstrated. In addition, to its intrinsic scientic
interest, the methodology presented has strong practical relevance
in assessing the risk when the release, incidental or intentional, occurs in the subsurface ow.
2. The physical problem
The problem examined in this paper is the following: a nite
quantity of contaminant mass M0 is released in a heterogeneous
groundwater ow, and one wants to determine the resulting contaminant concentration eld and the resulting risk at the location
of interest. In this study, the contaminated and clean subsurface
uids will be regarded as continua.
Consider an incompressible and steady groundwater ow that
takes place through a heterogeneous aquifer and results in a divergence-free velocity eld, r  v(x, t) = 0, where v(x, t) is the velocity
eld dened on the continuum scale of the support volume surrounding x (e.g., the REV or Darcy scale) at time t. In the Eulerian
framework the mass conservation requires the resident scalar concentration c(x, t) to satisfy the advection-diffusive equation

@cx; t
r  v x; tcx; t r  Drcx; t;
@t

where c(x, t), is dened as the solute mass per aquifer volume (of
constant porosity) surrounding x at time t and D  D(x, t) is the local scale diffusion tensor commonly dened in subsurface as D(x,
t) = DmI + av(x, t) where Dm is an effective molecular diffusion and
a is a constant dispersivity tensor. A common approach to account
for local diffusion is to replace v(x, t) with the uniform ensemble
mean, v x; t Efv x; tg U or to set D as a constant. Without loss
of generality, the later is used here [e.g., 1,2,29].
The smallest length scales relevant to the subsurface dynamics
of the ow eld are not only considerably larger the molecular
mean-free path but also from the pore-scale. All variables in this
study will be assumed to have continuum scale resolution. In practice the subsurface concentration measurements are rarely made
at the continuum scale, but instead at a much larger scale over
which concentration gradients are small. All scales of subsurface
dynamics in a heterogeneous velocity eld are usually larger with
respect to the continuum scale.
Eq. (1) shows that there are two mechanisms available for the
contaminant solutes interaction with groundwater. One is the
advective term v  rc, and the other is the diffusive term Dr2c.

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R. Andricevic et al. / Advances in Water Resources 36 (2012) 8697

Local diffusion exists irrespective of the velocity eld. The advection works on relatively fast time scales and results in the thinning
of the contaminant plume in the ngers-lenses structure. The heterogeneous velocity eld will convey the solute mass into the
lenses and ngers containing the high velocity stream tubes, which
creates a large surface area with strong concentration gradients. It
is the advection that makes local diffusion in a porous media fundamentally different from diffusion in a solid. Along concentration
gradients, the local diffusion will act as a balancing force until a
certain balancing thickness is reached. This cut-off scale represents
the length scale at which local diffusion, spreading out the solute
mass, balances the reduction of the thickness of the lenses of solute
from the strain caused by the heterogeneous subsurface velocity.
Following [1,2], this physical scale denoted as k, corresponds to
the scale that is larger than the continuum scale but is smaller than
the integral scale IY of log-hydraulic conductivity eld, which commonly describes the underlying heterogeneous geologic media
structure. Due to the subsurface randomness of the geologic media,
a single realization of the ow and concentration eld is meaningless. Such intrinsic randomness prevents the use any deterministic
approach in the study of concentration problems, and approximations to ensemble averages are the only reproducible quantities
[e.g., 4,14,18,36].
3. The concentration probability density function
Evolution of a contaminant concentration in heterogeneous
subsurface velocity eld can be described with the use of the probability density function (PDF). The value of concentration c is
bounded between 0 and C0, where C0 is the highest release concentration, resulting in c to be a continuous variable in the region [0,
C0]. Since c is continuous random variable, there is a piecewise continuous non-negative probability density function p such that
R C0
pc; x; tdc 1. The corresponding absolute moments are
0

mn x; t

C0

c pc; x; t dc

of ci = Mi/udAdt for the ith sample. If the entire time at x0 is sampled, the random variable, dosage, is obtained

dx0

cx0 ; t dt

where t0 is the initial release time. When the dosage is multiplied

with the withdrawn water ux, d(x0)udA, it gives the total mass
withdrawn as a plume passes the well location at x0. The expected
R1
value from (3) is easily obtained and dx0 t0 cx0 ; tdt denes
the expected total mass passing the well location.
4.1. Introduction of the expected mass fraction in contaminant
hydrogeology
In this section, the expected mass fraction (EMF) concept of
Heagy and Sullivan [24], originally introduced in atmospheric turbulent diffusion, will be described, implemented into the subsurface pollution problems, and further extended to dene the
average exposure duration for a selected concentration threshold
to be used for the risk characterization. Consider the same example
of a plume passing the well location x0 as described in the previous
section. Assume the case of a sampled groundwater volume udAdt
having a mass M yielding the concentration of c = M/udAdt for
that sample. Summing up all such samples at x0 having a concentration c 6 c 6 c + dc for a single realization, the exposure duration, during which c occurs, is

DTc ; x0

4. Contaminant concentration reduction

In an earlier work, Andricevic [1] utilized the concept of spatially integrated moments to illustrate the intuitive advantage of
using concentration values throughout the entire plume in each
realization to derive the rst two moments of the concentration
eld. In this study a similar advantage in the form of temporal integration is explored for more conventional measurements made as
the plume passes the xed point, x0, in space.
Consider a plume passing the well location x0 where groundwater is withdrawn with a constant speed u through the screened
interval of area dA for a sample time dt. The withdrawn groundwater volume is udAdt and contains a mass Mi to give a concentration

cx0 ; tdcx0 ; t  c dt

such that DTudA is the total sampled volume for c, which has a corresponding mass equal to cudADT. If the expected value is taken
over many plume realizations, the average exposure duration for
a xed c is obtained

DTc ; x0

c x0 ; tpc ; x0 ; tdt

Setting n = 1 above, one obtains the ensemble mean (location) of the

PDF. The lowest order moment, the mean m1 x; t cx; t, is the
easiest to predict and to measure in the heterogeneous subsurface
transport problems. The mean is relatively insensitive to temporal
and spatial resolution and requires fewest realizations in numerical
experiments to converge to an adequate approximation to an
ensemble average value [1,22,25]. For each higher ordered moment
approximately and order of magnitude more realizations are required. The mean concentration is also insensitive to the local diffusion in contrast to the higher moments. Since the only mixing
mechanism between the contaminant uid and surrounding
groundwater takes place through local diffusion, the concentration
mean is a very poor indicator of the concentration reduction and
presents no relevance to the risk assessment procedures.

t0

This average exposure time or average exposure volume, DTudA, has

to be normalized with the expected total mass dx0 udA found at x0
to nally reveal a measure, the expected mass fraction, given for
any concentration value with

f c; x0

DTc; x0 udA
dx0 udA

dx0 1

cpc; x0 ; tdt

such that f(c; x0)dc presents the probability that the expected fraction of the expected total mass is found between c and c + dc when a
contaminant plume passes the xed location x0. This function of
R
R1
concentration has pdf property, f c; x0 dc 1 0 cx0 ; tdt 1,
dx0
and has corresponding moments

Mfn x0

Z
0

C0

cn f c; x0 dc

R1
mn1 dt
R0 1
m1 dt
0

1
dx0

Z
0

C0

cn1 pc; x0 ; tdc dt

In many practical problems one is concerned with concentration

exceeding some threshold level. For example the value
R C0
f c; x0 dc 0:1 represents the 10% of the total mass passing
c
the well location at x0 that has higher concentrations than c. Thus,
the EMF in (6) describes the manner in which the contaminant mass
is distributed over the range of concentration values seen at x0. Besides the new measure of concentration exposure, the exposure
duration DT(c; x0) provides information of practical importance
regarding the exposure time for some concentration level of interest. Because the concentration c(x0, t) and therefore f(c; x0) are

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R. Andricevic et al. / Advances in Water Resources 36 (2012) 8697

fV c; x0

Z
Vx0

R1
0

cpc; x0 ; tdt
dVx0
 0
dx

Measurements taken over volume V(x0) will have quite different

moments in (2) for n > 1 due to the known sensitivity of higher concentration moments to time and space averaging and to local diffusion [1,2,25,36,42].
In addition, by measuring or modeling lower-order moments in
(7) the EMF can easily be retrieved using moment inversion. The
estimates of the EMF have variability comparable with estimates
of dosage in (3). Since (3) involves an integral over time, as the
plume evolves relatively fewer realizations will approximate
ensemble average statistics on dosage compared to the one-point
concentration statistics. It is important to note that for a small
sources and non-ergodic plumes only concentration statistics
(on-point and/or EMF) in the relative frame of reference [e.g., 2]
will yield the actual concentration exposure someone may experience if positioned on the plume pathway. On the other hand, the
concentration statistics in the absolute frame of reference combine
the plume meandering created from large scale heterogeneity and
small scale heterogeneity responsible for internal plume structure.
Although we use in this study the internal uctuation structure
(free of meandering), which is critical for risk assessment, the
plume meandering for a xed-point observer provides an additional estimate of uncertainty in experiencing such concentration
exposure and should serve as a tool for early detection monitoring
network and for establishing the environmental protection zones
which is also related to the environmental risk management.
5. Risk characterization
The classical Paracelsus statement [30] that all substances are
poisons and only the right dose differentiates a poison from a remedy represents the central theme in risk assessment and risk management. For the risk assessment in the case of non-carcinogenic
substances, the concept of threshold is commonly used. A toxic
threshold means that individuals exposed for some period of time
to concentration above the threshold will experience some adverse
health effects. Finding out what constitutes a safe level of exposure is a difcult task considering the large number of chemicals in
commerce today. To identify possible toxic effects associated with
chemical exposure, the epidemiological studies or animal experimentation (toxicological studies) are commonly done. This information is then used to develop exposure limits and to assess the
risk as a result of the concentration exposure in the environment.
Information obtained from these studies is summarized in developing the doseresponse relationship.
In this study the focus is to present the EMF concept in the risk
assessment and demonstrate the importance of estimating the actual exposure duration for each concentration level. To demonstrate this feature of EMF we selected to deal with generic toxic
substance and non-carcinogenic endpoint exposed through the
ingestion pathway only. The toxicity threshold needed for assessing the non-carcinogenic risk was also selected as a good example
to demonstrate the parametric uncertainty in the risk assessment
study. However, if one has specic contaminants in case, there
are no restrictions for the presented method to be applied in the
case of carcinogenic endpoint and/or other pathways by estimating
additional necessary parameters and coefcients attributable to
that specic contaminants in hand.
The most important purpose of performing toxicological studies
(acute and/or chronic) is to establish a causeeffect relationship
between exposure to a toxic substance and an observed effect (of-

ten on rodents in the laboratory) to arrive at the safe exposure level. The typical doseresponse curve illustrates the relationship
between the dose and observed effects, and it is shown schematically in Fig. 1. The reference threshold (RfD) level is a dose usually
derived from the NOAEL (No-Observed-Adverse-Effect-Level) or
LOAEL (Lowest-Observed-Adverse-Effect-Level) [26,41]. Therefore,
the human RfD used for quantifying risk in the environment must
be extrapolated from the test results. This extrapolation is done by
introducing a safety factor (or uncertainty factor). This safety factor
ranges from 10 to 1000 as a result of unavoidable extrapolation
from rodent to human concentration levels (interspecies variability), variability within the human population (intraspecies variability), and other uncertainties associated with the data set. This
extrapolated human RfD is converted in the maximum contaminant level (MCL) and herein denoted as cs. As a consequence of this
procedure, cs is a random variable having a pdf with a scale parameter (e.g., variance) resulting from the uncertainty associated with
a chosen safety factor.
To determine the exposure of an individual drinking the
groundwater at well location x0, which contains some concentration level of a toxic substance, the intake dose ID is commonly estimated as a total dose TD (attributable to all routs of exposure)
divided by body weight BW and averaging time AT (set to ED for
non-carcinogenic or to 70 years for carcinogenic substances [40])
using the following expression

IDc; x0

TD
cx0 ; t  CR  ED  EF

BW  AT
BW  AT

where CR is the contact rate at which the groundwater contacts the

body, EF is the exposure frequency and ED is the exposure duration.
In this study we assume that the source of drinking water originates
directly from the well [e.g., 31] so that CR represents the withdrawal rate u dA and TD is attributable to the ingestion only. For
constituents that are systematic toxicants, the human health risk
can be expressed in terms of the hazard quotient (or performance
function)

HQ

IDc; x0 ICx0

RfD
cs

10

where IC denotes intake concentration obtained by conversion of ID

with BW and udA. Thus, herein both IC and cs are considered

Toxicological studies

Response

dened on a continuum scale, all other values averaged over the

sampling area/volume centered at x0 are easily obtained as

Maximum Contaminant
Level

LOAEL

NOAEL
p(cS)

Dose
Fig. 1. Doseresponse
uncertainty.

curve

with

extrapolation

problem

and

associated

R. Andricevic et al. / Advances in Water Resources 36 (2012) 8697

C0

Rf x0 ProbHQ P 1

cs

f c; x0 pcs dcdcs

11

C0

C0

f c; x0 pcs dcdcs

12

cs

where p(cs) denotes the uncertainty in determination of the MCL

threshold. Unless otherwise instructed from the toxicological studies, the f(c; x0) and p(cs) are often statistically independent and the
above risk expressions can be further reduced to

Rs x0

C0

F c cs ; x0 pcs dcs Ecs F c cs ; x0 

13

F cs cf c; x0 dc Ec F cs c

14

Rf x0

C0

where Fc() and F cs  are the cumulative distribution functions (cdf)

of random c and cs, respectively, Ecs F c cs ; x0  is the expected value
of the cdf of random concentration over all possible ranges of the cs,
and Ec F cs c is the expected value of the cdf of random cs over all
possible ranges of concentrations. The estimated risk of exceedance,
Rf(x0), is given as a probability of IC/cs P 1 at x0.
There are two important points in the above risk expressions.
First, with EMF the actual probability of the expected mass fraction
that will be exceeding the cs by estimating the average duration
time over which exposure above cs has occurred can be determined. This estimate of the average exposure time, in turn, denes
the average contaminant mass to be exceeded over the selected
threshold at the point of interest. Thus, there is no need to use a
xed 30-year period for ED as often used in practice [5,31,40,41].
Second, by having the risk exceedance presenting the probability
of mass introduced to an individual by ingestion, the corresponding dosage resulting from the selected exposure pathways can be
determined by multiplying the risk exceedance with the average
dosage yielding a total dosage dT(x0) of toxic chemicals that will
be on average exceeding the cs at location x0 as

dT x0 dx0 Ec F cs c

15

This total dosage exceeding cs when compared with a doseresponse curve provides the method to analyze and further study
exposure adjustments that are often necessary in selecting the
accurate human RfD [e.g., 41] for different routes of exposure. Multiplying dT(x0), as obtained above, with a groundwater withdrawal
ux, dT(x0)udA, yields a total mass of chemicals that will on average
be present at x0 with a concentration c > cs. The toxicological impact
in many cases will depend only on the amount of contaminant mass
at concentration values above a prescribed threshold value. In the
case of deterministic maximum contaminant level, the total dosage
RC
simplies to dx0 cs 0 f c; x0 dc.
A similar procedure can be applied for other exposure pathways
when specic chemicals are considered. For example, in the case of
volatile and/or sorptive contaminant the presented methodology
can be applied by modifying (9) for other pathways. In addition,
the carcinogenic endpoint can also be considered by replacing
(10) with the probability of an individual developing cancer, over

6. Numerical application
To examine the behavior of the EMF pdf, its related moments
and the corresponding risk characterization, 2-D numerical experiments were performed. The recently presented simulation methodology, referred to as the Adaptive Fup Monte Carlo MethodAFMCM [22], supports the EulerianLagrangian formulation, which
separates the ow from the transport problem and consists of the
following common steps [23]: (1) the generation of a large number
of log-conductivity realizations with a predetermined correlation
structure, (2) the numerical approximation of the log-conductivity
eld, (3) the numerical solution of the ow equation with prescribed boundary conditions to produce head and velocity approximations, (4) the evaluation of the displacement position and travel
time for a large number of the particles using the random walk particle tracking method, (5) the repetition of steps 24 for all realizations and (6) the statistical evaluation of concentration values.
The AFMCM methodology is based on Fup basis functions with
compact support (related to the other localized basis functions
such as splines or wavelets) and the Fup collocation transform
(FCT), which is closely related to the discrete Fourier transform
needed for the multi-resolution representation of all ow and
transport variables. Fup basis functions and the FCT are presented
in [21]. Other improved Monte Carlo (MC) methodology steps were
also utilized: (a) the Fup regularized transform (FRT) for data or
function (e.g., log-conductivity) approximations in the same multi-resolution fashion as FCT, but computationally more efcient,
(b) the adaptive Fup collocation method (AFCM) for approximation
of the ow differential equation, (c) the random walk particle
tracking algorithm based on the RungeKutta-Verner explicit time
integration scheme and FRT and (d) MC statistics represented by
Fup basis functions. All aforementioned MC methodology components are presented in [23].
For illustrating the application of the expected mass fraction pdf
for risk characterization in porous media, a two-dimensional steady state and uniform-in-the-average ow eld with a basic conguration are considered, as illustrated in Fig. 2, imposing the
following ow boundary conditions: left and right boundaries are
prescribed a constant head, while the top and bottom are no-ow
boundaries. Moreover, classic multi-Gaussian lnK heterogeneity
elds with exponential correlation model are used, which are completely dened by the rst two statistical moments and three basic
parameters: mean, variance and integral scale. This ow conguration as related to a multi-Gaussian lnK eld has been extensively
studied in the literature [among others 8,12,16,20,23,43]. Fig. 2
NO - FLOW
Ly=32Iy
INNER COMPUTATIONAL DOMAIN

32Iy

y
0

27Iy
17Iy
13Iy 14Iy

0Iy
12Iy

22Iy

32Iy
22Iy

CONSTANT HEAD

Rs x0 ProbHQ < 1

a lifetime, under the assumption that a linear relationship exists

between exposure to the contaminant and the risk of cancer [e.g.,
5,31].

SOURCE AREA

random. In the considered case, the f(c; x0) describes the distribution of contaminant mass over different concentration values using
the average exposure duration (5) seen at x0 and provides new insight in the variables needed to estimate ID and/or IC. The f(c;
x0)dc multiplied with dx0 udA and scaled with averaging time AT
and BW of exposed individual presents the probability of the intake
dose in concentration interval c and c + dc at location x0.
The risk to an individual is dened as the probability of the hazard quotient HQ exceeding one. Following the terminology of Andricevic and Cvetkovic [3] we dene the risk reliability (safety),
Rs, and risk exceedance (failure), Rf expressed as:

CONSTANT HEAD

90

52Iy

20Iy
18Iy
16Iy
14Iy
12Iy
10Iy

52Iy

Lx=64Iy

x
NO - FLOW
Fig. 2. Numerical model setup.

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R. Andricevic et al. / Advances in Water Resources 36 (2012) 8697

Xp t Dt  Xp t AXp ; t  Dt BXp ; t  DwDt

16

where A is a drift vector, B is a tensor dening the strength of local

diffusion, and Dw is a Wienner process vector of independent normally distributed random variables with zero mean and unit variance. According to the displacement position of particles, the ux
averaged concentration is calculated and monitored at arbitrary
control planes denoted by x and transversal positions denoted by
y. The ux injection mode is considered in which particles are separated by a distance inversely proportional to the specied ow rate
between them [15]. All simulations use NP = 16,000 particles,
NMC = 1000 Monte Carlo realizations with a source area (hx = 0.25IY;
hy = 4IY).
Within the numerical simulations, the moments of dosage can
be numerically measured using the following expression:

M gn x0

7. Results
7.1. Exposure concentration results
The results are presented for different locations downstream of
the source area along the horizontal centerline (see Fig. 2) and
three locations at the transversal line located at 10IY measured
from the source. The EMF pdf in (6) is calculated by differentiating
(18) and is presented in Fig. 3 for the horizontal centerline and in
Fig. 4 for the transversal line. As stated, the f(c; x0)dc describes the
expected fraction of dx0 found between the concentration interRC
val c and c + dc. Furthermore, the area c0 f c; x0 dc denes the
fraction of the total mass passing the well location at x0 with a concentration higher than c.
Because the plume moves past the well location, the EMF pdf
shows the shift to smaller concentrations for downstream points
along the centerline. The dilution effect occurs when D 0 and

40
x0(13Iy,16Iy)
x0(18Iy,16Iy)
x0(22Iy,16Iy)
x0(32Iy,16Iy)
x0(52Iy,16Iy)

30

f(c;x 0)

shows a 2-D computational domain for steady-state and unidirectional ow simulations of 64IY  32IY, where IY denotes the integral
scale. The random eld generator HYDRO-GEN [9] generates lnK
elds for mild lnK variance equal to unity; for simplicity, the porosity is assumed uniform.
Transport simulations are performed in the inner computational domain (40IY  20IY) to avoid the non-stationary inuence
from the ow boundary conditions (Fig. 2). The injected tracer
mass is divided into a given number of particles that carry an equal
fraction of total mass. Particles are injected along the source line
and followed downstream by advective steps due to the variability
of the velocity eld and dispersive steps dened by a constant local
diffusion tensor with a Peclet number equal to 1000. The random
walk particle tracking formulation used in this study follows the
same expression used in [7,8,11,17,28,29,3739]:

20

cn x0 ; t dt:

17

10

With n 6 5 the calculation of the absolute EMF moments Mfn x0

from (7) can be made. Then, using the inversion of lower moments
(e.g., the maximum entropy formalism), the estimate of the EMF pdf
f(c, x0) as dened in (6) can be obtained. The estimation procedure
in terms of the EMF cumulative distribution function can be also
achieved directly from the numerical experimental record

1
Mg1

0.25

0.5

0.75

C/C0
Fig. 3. EMF pdf evaluated along the horizontal centerline.

Hc  cx0 ; tdt

18

20

where H(c) is the Heaviside unit step function.

In conclusion, the AFMCM methodology enables modeling of
ow and transport processes in heterogeneous porous media in a
signicantly different way than classical conventional methods.
Firstly, each variable such as log-conductivity, head, velocity or
concentration has a particular adaptive grid describing all its spatial and temporal scales within the prescribed level of accuracy.
There are no classical discretization, numerical integrations or remeshing. Only new Fup basis functions can be added in sensitive
subdomains according to numerical adaptive criteria. Furthermore,
the most signicant property of this methodology is the continuity
of all variables and derivatives, which is particularly important for
the velocity eld and accurate random walk particle tracking procedure. Classic nite element methods require a special hybrid formulation [28] to ensure a continuous velocity eld. However, even
with these additional efforts, it is difcult to obtain continuity of
velocity dependent dispersion tensor, which still requires continuous derivatives of velocity. However, AFMCM naturally enables a
very accurate random walk procedure, providing an accurate concentration eld that is a basic input for the EMF calculation.

x0(22Iy,14Iy)
x0(22Iy,16Iy)
x0(22Iy,18Iy)

18
16
14
12

f(c;x 0)

Fc; x0

10
8
6
4
2

0.1

0.2

0.3

0.4

0.5

C/C0
Fig. 4. EMF pdf evaluated along the transversal line located at 10IY from the source.

92

R. Andricevic et al. / Advances in Water Resources 36 (2012) 8697

needs time (or downstream distance) to develop and is manifested

by reduced concentration values of the EMF pdf at farther downstream locations. The calculated EMF pdf for each location represents the distribution of concentration values that, on average,
can be experience at the sampling point. This new measure for
groundwater contamination, which is more simple than the one

point pdf p(c; x, t), represents the way the contaminant plume is
diluted by examining the shift of the area under f(c; x0) to smaller
concentration values.
For the hypothetical case of D = 0, the large scale velocity variations (larger than the plume size) could advect the plume such
that it could completely miss the well location. However, the

0.080
0.400
0.075
Exposure duration (30 years)

0.070
0.350

Exposure duration (30 years)

0.065
0.060
0.300
0.055
0.050
0.250

c(x0,t)
c(X
,t)
0

0.045
0.040
0.200
0.035
0.030
0.150
0.025
0.020
0.100
0.015
0.010
0.050
0.005
0.000

10000
5000

20000
10000

30000
15000

t (days)
Fig. 5a. Calculation of averaged concentration for a single realization of BTC at x0 = (13IY, 16IY).

0.080
0.100
0.075
0.090
0.070
0.065
0.080

Exposure duration (30 years)

Exposure duration (30 years)

0.060
0.070
0.055

c(x0,t)
c(X
,t)
0

0.050
0.060
0.045
0.040
0.050
0.035
0.040
0.030
0.025
0.030
0.020
0.020
0.015
C

0.010
0.010
0.005
0.000
10000
0

10000
15000

20000

30000
25000

t (days)
Fig. 5b. Calculation of averaged concentration for a single realization of BTC at x0 = (22IY, 16IY).

93

R. Andricevic et al. / Advances in Water Resources 36 (2012) 8697

0.080
0.060
0.075
0.055
0.070
0.050
0.065

Exposure duration (30 years)

Exposure duration (30 years)

0.060
0.045

c(x
c(X00,t)

0.055
0.040
0.050
0.035
0.045
0.040
0.030
0.035
0.025
0.030
0.020
0.025
0.020
0.015
0.015
0.010
0.010
0.005
0.005

0.000
0.000
20000
0

2500010000

30000

20000 35000

30000
40000

(days)
tt(day)
Fig. 5c. Calculation of averaged concentration for a single realization of BTC at x0 = (32IY, 16IY).

plume may pass the well location through the plume center of
mass, resulting in the source concentration. In the real case of
D 0, the concentration record will be distributed between 0
and C0 depending on the location and diffusion strength. Fig. 4
shows the EMF pdf for three transversal locations horizontally at
10IY from the source. The range of concentration values present
at these locations is between 0 and 0.3C0 with very slight variations among EMF pdfs. Because the source transversal dimension
is equal to the distance between the farthest locations on the transversal line, the EMF pdf is not expected to vary signicantly. For
smaller source size or larger distance between points at the trans-

versal line a further shift towards smaller concentration values of

the EMF is expected.
A common approach in calculating ID is to use the average concentration value based on the 30 years xed window, set at the
peak of the breakthrough curve [e.g., 5,31,32]. Fig. 5 depicts the calculation of averaging the concentration in a single realization for
three horizontal distances from the source (x0 = 1IY, 10IY, 20IY).
After calculating this averaged concentration over all realizations
and selecting the maximum value (as a worst case scenario), it is
compared in Fig. 6 with the EMF distribution for the same three
locations of x0. There is a clear difference between the maximum

130

130

120

120
5

110

20

110

f(c;x0)
p(c;x0,tu/Iy=1)

100

f(c;x0)
p(c;x0,tu/Iy=10)

100
4

60

cMAX

50
1

40

f(c;x0) & p(c;x0,t)

70

f(c;x0) & p(c;x0,t)

80

80
70
60
50

cMAX
10

40

30

30
0

0.25

0.5

0.75

C/C0

20

0.1

0.2

0.3

0.4

C/C0

20

10
0

15

90
f(c;x0) & p(c;x0,t)

f(c;x0) & p(c;x0,t)

90

10

0.25

0.5

0.75

C/C0
Fig. 6a. Comparison between p(c; x0, tu/IY = 1), f(c; x0) and cMAX at x0 = (13IY, 16IY).

0.25

0.5

0.75

C/C0
Fig. 6b. Comparison between p(c; x0, tu/IY = 1), f(c; x0) and cMAX at x0 = (22IY, 16IY).

R. Andricevic et al. / Advances in Water Resources 36 (2012) 8697

0.007
x0(13Iy,16IY)
x0(22Iy,16IY)
x0(32Iy,16IY)

0.006
0.0015
0.0014

0.005

0.0013
0.0012
0.0011

Exposure duration pdf

concentration obtained using a xed averaging window compared

to the possible concentration values which can be found at x0. The
EMF utilizes the actual ED in (5) to obtain the expected mass fraction above any concentration threshold selected. Each concentration threshold will have a different ED resulting from physical
transport parameters used in modeling the plume migration and
will consequently directly inuence the risk quantication. To further demonstrate the actual variability in the exposure duration
Fig. 7 shows the ED pdf for cs = 0.05, 0.1 and 0.2 and for three horizontal locations x0 = 1IY, 10IY, 20IY. The expected shift of ED to
smaller values farther from the source, is expected and demonstrates how important it is to work with the actual duration of
exposure instead of a xed averaging window. The common practice of using a xed 30 year averaging duration exposure window
may be misleading in actual concentrations that will be present
at the selected locations.

Exposure duration pdf

94

0.004

0.003

0.0010
0.0009
0.0008
0.0007
0.0006
0.0005
0.0004

0.002

0.0003
0.0002
0.0001
0.0000

0.001

500

1000

1500

2000

2500

3000

3500

Exposure duration (days)

130

120

2500

5000

7500

10000

Exposure duration (days)

30

110

f(c;x0)
p(c;x0,tu/Iy=20)

100

Fig. 7b. Exposure duration pdf for cs/C0 = 0.1 evaluated at three downstream
locations at 1IY, 10IY and 20IY from the source along the centerline.

25

20

f(c;x0) & p(c;x0,t)

80
70
60

cMAX

0.007

15

x0(13Iy,16IY)
x0(22Iy,16IY)
x0(32Iy,16IY)

0.006

10

50
0.0030
5

30

0.05

0.1

0.15

0.2

0.25

0.3

C/C0

20
10
0

0.25

0.5

0.75

C/C0

0.005
0.0025

Exposure duration pdf

40

Exposure duration pdf

f(c;x0) & p(c;x0,t)

90

0.004

0.003

0.002

0.0020

0.0015

0.0010

0.0005

Fig. 6c. Comparison between p(c; x0, tu/IY = 1), f(c; x0) and cMAX at x0 = (32IY, 16IY).
0.0000

0.001

500

1000

1500

2000

2500

Exposure duration (days)

0.007
x0(13Iy,16IY)

x0(22Iy,16IY)
x0(32Iy,16IY)

0.006

5000

7500

10000

Fig. 7c. Exposure duration pdf for cs/C0 = 0.2 evaluated at three downstream
locations at 1IY, 10IY and 20IY from the source along the centerline.

0.0011
0.0010

Exposure duration pdf

Exposure duration pdf

2500

Exposure duration (days)

0.0012

0.005

0.004

0.003

0.002

0.0009

7.2. Risk characterization results

0.0008
0.0007
0.0006
0.0005
0.0004
0.0003
0.0002
0.0001
0.0000

0.001

500

1000 1500 2000 2500 3000 3500 4000

Exposure duration (days)

2500

5000

7500

10000

Exposure duration (days)

Fig. 7a. Exposure duration pdf for cs/C0 = 0.05 evaluated at three downstream
locations at 1IY, 10IY and 20IY from the source along the centerline.

Using the calculated EMF, the associated non-carcinogenic risk

exceedance in (12) is evaluated for several points downstream
along the horizontal centerline. Fig. 8 depicts the case when the
safe human concentration cs is set to a deterministic value. Subsequently, all cs values used are normalized with the initial uniform
concentration C0. For larger values of cs, the risk exceedance (failure) decreases, which is also the case for well locations located farther downstream. This example shows how sensitive the selection
of the MCL threshold is on the Rf(x0). In Fig. 9, Rf(x0) is shown as a
function of cs at the transversal line located horizontally at 10IY
from the source. It can be easily envisioned that by calculating
the risk exceedance for a grid of observation points in the transport
domain, the contour lines of the same risk exceedance value

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R. Andricevic et al. / Advances in Water Resources 36 (2012) 8697

100

100
x0(13Iy,16Iy)
x0(14Iy,16Iy)
x0(17Iy,16Iy)
x0(22Iy,16Iy)
x0(27Iy,16Iy)
x0(32Iy,16Iy)
x0(52Iy,16Iy)

90

pdf(cS) = LN[0.2; 0.06]

70

70

60

60

50

50

40

40

30

30

20

20

10

10

0.1

0.2

0.3

pdf(cS) = LN[0.3; 0.09]

80

R f(x0) (%)

R f(x0) (%)

80

y = 16Iy ; CV = 0.3
pdf(cS) = LN[0.1; 0.03]

90

0
12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52

0.4

x(IY)

cS/C0
Fig. 8. Rf(x0) evaluated along the horizontal centerline for different deterministic cs
values.

Fig. 10. Rf(x0) evaluated along the horizontal centerline for uncertain cs described
with LN pdf with CV = 0.3.

40

100

x = 22Iy ; CV = 0.3
pdf(cS) = LN[0.1; 0.03]
pdf(cS) = LN[0.2; 0.06]

x0(22Iy,14Iy)
x0(22Iy,16Iy)
x0(22Iy,18Iy)

90

pdf(cS) = LN[0.3; 0.09]

80
30

60

R f(x0) (%)

R f(x0) (%)

70

50

20

40
30
10

20
10
0

0.1

0.2

0.3

0.4

cS/C0

0
12

14

16

18

20

y(IY)

Fig. 9. Rf(x0) evaluated at transversal line located 10IY from the source for different
deterministic cs values.

Fig. 11. Rf(x0) evaluated along the transversal line located at 10IY from the source
for uncertain cs described with LN pdf with CV = 0.3.

surrounding the source area as a function of different cs values can

be obtained.
In the case of an uncertain cs value, which is a more realistic
practical situation, Fig. 10 shows the risk exceedance, Rf(x0), along
the centerline. The uncertainty in cs is described with a log-normal
distribution with a mean and variance corresponding to the xed
coefcient of variation that reects, among other things, the uncertainty in extrapolating toxicological studies (see Fig. 1). By comparing Figs. 8 and 10 it can be seen that including the uncertainty in
describing cs results in increased Rf(x0). The increased risk exceedance value is more signicant for the well locations points farther
downstream. The often unavoidable uncertainty present in the
determination of cs plays an important role in assessing the risk value. Fig. 11 depicts the similar behavior of Rf(x0) evaluated at the
transversal line at 10IY from the source. Observation points away

from the horizontal centerline show slightly decreased risk values

which will be even more pronounced in the case of a smaller
source size when the plume meandering is more pronounced.
For all risk exceedance values evaluated using (12), the distance
from the source, velocity uctuations, and magnitude of local diffusion play the key role in diluting the contaminant plume and
therefore present the key mechanisms for the self-purication of
contaminated groundwater. In this study, only conservative contaminants were considered. Because the new dilution measure in
terms of EMF does not have physical assumptions built into it,
there is no restrictions on including chemical reactions, density effects and other physical mass transfer processes, which might be
present in the subsurface. Most of these processes can be included
within the numerical model and will consequently alter the nal
risk exceedance values. Because the lower order moments of

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R. Andricevic et al. / Advances in Water Resources 36 (2012) 8697

concentration statistics can directly lead to the EMF estimate, the

approach by Maxwell et al. [31,32] and de Barros and Rubin [5],
who combined the site characterization parameters in the concentration statistics, can also be combined with the proposed
approach.

on the different chemical compounds present in the groundwater, the doseresponse characteristics will vary widely over a
range of different concentration levels present in the supply
well. This uncertainty in dening the actual response of using
the contaminated groundwater (considering different exposure
pathways) should be examined during the risk assessment
procedure.

8. Concluding remarks
The problem of the dilution of a contaminant plume in groundwater is introduced with a probabilistic measure, the expected
mass fraction, which is coupled with the estimation of the safe human threshold to assess the non-carcinogenic risk exceedance for
consuming the groundwater at a supply well. Many studies have
examined different subsurface transport processes and source conditions to evaluate their inuence on the concentration plume
characteristics. Often there are signicant discrepancies found,
which are essentially due to the different assumptions adopted
in modeling the release and dispersion processes. Generally, when
risk assessment is the goal, the mean concentration values do not
relate to the dilution problem. Clearly, there is a need for reliable
prediction of concentration uctuations and ultimately the concentration pdf.
The 3D inclusion in the numerical exercise could in general lower the concentration values particularly for a porous media with a
mild heterogeneity due to the enhanced dispersion process. Consequently, the risk would be reduced as well. However, the three
dimensionality modeling in case of high heterogeneous subsurface
also creates more chances for preferential pathways, where more
contaminant mass will be conveyed through those lenses and ngers and could present extreme events that depending on their
duration at may cause the increased risk. This is a reason why together the exposure duration and the high concentration values,
with respect to the selected cs, contribute to the risk assessment.
The one point concentration pdf, p(c; x, t), is strongly affected by
the release conditions and is usually composed of a mixed part,
which results from the in-plume mixing at scales of the plume size,
and an unmixed ambient uid part that is produced by plume
meandering, producing intermittent periods of zero concentration
for some period of time. The challenge is to dene a dilution measure that can be compiled from measurements and still contains
some relevant information. The presented expected mass fraction
has relevant information on the contaminant dilution and exposure duration and has direct relation to the toxicological impact
from the contaminated environmental media.
If there were no local diffusion, the single supply well will be affected by the source concentration C0 only in case in which the
source concentration will pass over the well for some amount of
time. To assess the contamination probability and determine what
fraction of the plume would contaminate the supply well, an npoint joint pdf of concentration in space and time is required. This
measure is impractical even for numerical examples. The expected
mass fraction is a compromise measure that can actually be measured and provide information relevant to the classical dosage. The
EMF is the expected average outcome and as such, it gives direct
information on the dilution problem and exposure duration experienced at any location of interest.
The information contained in the EMF has much to do with
the quantication of the toxicological impact because it
describes the fraction of mass distributed in the range of concentration values that will be seen at the supply well for some time.
When it is coupled with the safe human threshold obtained from
the toxicological studies, the closed-form expression for evaluating the risk exceedance or risk safety value is found. The uncertainty considered in the determination of cs is an important
factor and can signicantly affect the total risk value. Depending

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