Journal of Contaminant Hydrology 251 (2022) 104097

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Journal of Contaminant Hydrology

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

Evaluating the effectiveness of a geostatistical approach with groundwater

flow modeling for three-dimensional estimation of a contaminant plume
Shizuka Takai a, b, *, Taro Shimada a, Seiji Takeda a, Katsuaki Koike b
a
Nuclear Safety Research Center, Japan Atomic Energy Agency, 2-4 Shirakata, Tokai, Ibaraki 319-1195, Japan
b
Department of Urban Management, Graduate School of Engineering, Kyoto University, Katsura C1-2-215, Kyoto 615-8540, Japan

A R T I C L E I N F O A B S T R A C T

Keywords: When assessing the risk from an underground environment that is contaminated by radioactive nuclides and
Contaminant plume estimation hazardous chemicals and planning for remediation, the contaminant plume distribution and the associated un­
Geostatistical inversion certainty from measured data should be estimated accurately. While the release history of the contaminant
Gibbs sampling
plume may be unknown, the extent of the plume caused by a known source and the associated uncertainty can be
Groundwater contamination
Groundwater flow
calculated inversely from the concentration data using a geostatistical method that accounts for the temporal
correlation of its release history and groundwater flow modeling. However, the preceding geostatistical ap­
proaches have three drawbacks: (1) no applications of the three-dimensional plume estimation using concen­
tration data from multiple depths in real situations, (2) no constraints for the estimation of the plume
distribution, which can yield negative concentration and large uncertainties, and (3) few applications to actual
cases with multiple contaminants. To address these problems, the non-negativity constraint using Gibbs sampling
was incorporated into the geostatistical method with groundwater flow modeling for contaminant plume esti­
mation. This method was then tested on groundwater contamination in the Gloucester landfill in Ontario,
Canada, using three-dimensional contaminant transport model and concentration data from multiple depths. The
method was applied to three water soluble organic contaminants: 1,4-dioxane, tetrahydrofuran, and diethyl
ether. The effectiveness of the proposed method was verified by the general agreement of the calculated plume
distributions of the three contaminants with concentration data from 66 points in 1982 (linear correlation co­
efficient of about 0.7). In particular, the reproduced peak of 1,4-dioxane corresponding to the large disposal in
1978 was more accurate than the result of preceding minimum relative entropy-based studies. The same peak
also appeared in the tetrahydrofuran and diethyl ether distributions approximately within the range of the
retardation factor derived from the fraction of organic carbon.

1. Introduction underlying physical processes that govern contaminant transport and

Over recent decades, the underground environment in various areas
worldwide has been contaminated by anthropogenic chemical, radio­
logical, and microbiological substances. There are numerous reports of
contamination of groundwater by substances that migrate easily into
groundwater. Examples include contamination by volatile organic
compounds, heavy metals, and radionuclides such as 3H and 90Sr in
nuclear facilities including Hanford (Washington, USA), Sellafield
(United Kingdom), and Chalk River (Canada) (OECD, 2014). To assess
the risk of groundwater contamination and support plans for reme­
diating contaminated sites, the hydrogeological structures and
the contaminant plume distribution must be correctly understood.
There are three main challenges when developing practical methods
to estimate the extent and concentrations of actual contaminant plumes.
First, the amount and location of measured concentration data may be
limited because of temporal and budgetary constraints. If there are
enough data, the plume distribution can be estimated by interpolation or
extrapolation of the data using a spatial estimation method, such as
kriging. To date, several types of kriging, such as ordinary and indicator
kriging, cokriging (for multivariate data), and spatio-temporal kriging
have been applied in various settings (e.g., Saby et al., 2006; Juang et al.,
2008; Iskandar et al., 2012; Antunes and Albuquerque, 2013; Boente

* Corresponding author at: Nuclear Safety Research Center, Japan Atomic Energy Agency, 2-4 Shirakata, Tokai, Ibaraki 319-1195, Japan.
E-mail addresses: takai.shizuka@jaea.go.jp (S. Takai), shimada.taro@jaea.go.jp (T. Shimada), takeda.seiji@jaea.go.jp (S. Takeda), koike.katsuaki.5x@kyoto-u.ac.
jp (K. Koike).

https://doi.org/10.1016/j.jconhyd.2022.104097
Received 27 March 2022; Received in revised form 6 October 2022; Accepted 16 October 2022
Available online 19 October 2022
0169-7722/© 2022 Elsevier B.V. All rights reserved.
S. Takai et al.
et al., 2017; Dalla Libera et al., 2017; Liang et al., 2018; Masoudi et al.,
2021). However, these spatial estimation methods may not be suitable
for accurately reproducing the plume distribution in groundwater
because the monitoring wells are not always optimally sited to allow the
delineation of plume structures formed by advection, dispersion, and
sorption along with the groundwater flow (Shlomi and Michalak, 2007).
Therefore, flow and transport modeling is indispensable for reproducing
the plume distribution in a groundwater system. Second, the contami­
nant source (source location or release history) for accidental contami­
nation incidents is usually not identified, and release history records are
particularly rare. For example, when remediating nuclear sites in the
past, source locations have been detected by preliminary surveys or
historical site assessments (U.S. EPA, 2000) in drain lines, sumps, pipes,
and tanks, and the transient release histories have been unknown in all
cases (OECD, 2014). In such a situation, either the plume cannot be
estimated from only the flow and transport simulation or the uncertainty
associated with the estimation will be large. Third, risk assessments
should include a quantitative evaluation of the uncertainty of the plume
estimation. The uncertainty of the estimated plume distribution can aid
in determining the number and location of new measurement points
(Snodgrass and Kitanidis, 1997).
To overcome these issues, a geostatistical approach that incorporated
groundwater flow and transport modeling was proposed to estimate the
distribution of a contaminant plume and the associated uncertainty
(Shlomi and Michalak, 2007). This approach assumes that the source
locations are known but the release history is unknown. The plume
distribution is calculated from the release history estimated by geo­
statistical inversion that accounts for its temporal covariance (e.g.,
Snodgrass and Kitanidis, 1997). If groundwater contamination is a result
of multiple actions of several parties, the reproduced release history can
assist in determining how to divide the remediation cost among the
responsible parties (Skaggs and Kabala, 1994; Michalak, 2002; Michalak
and Kitanidis, 2002; Butera and Tanda, 2003). However, there are three
problems with the preceding geostatistical approaches:
(1) Although actual contamination is three-dimensional, the pre­
ceding geostatistical approaches have so far been applied to es­
timate contamination and release histories in one dimension
along depth profiles (e.g., Michalak and Kitanidis, 2003) or two-
dimensional aquifer modeled with one layer in which a homo­
geneous vertical contaminant distribution is assumed (e.g.,
Butera and Tanda, 2003; Gyzl et al., 2014). This problem is
common to geostatistical and other stochastic approaches such as
minimum relative entropy and backward probability tracking,
because most preceding studies (e.g., Colombo et al., 2020) have
generally been based on two-dimensional aquifer models
(Gomez-Hernandez and Xu, 2022).
(2) The concentrations that are produced from plume estimations
can include negative values and large uncertainties because of a
lack of constraints. Negative values frequently appear in practical
applications where the problem is ill-conditioned and has large
errors. While negative values can be avoided by transforming
data with a power law (Box and Cox, 1964) (e.g., Snodgrass and
Kitanidis, 1997; Gyzl et al., 2014), data transformation can
change linear inversion problems to nonlinear, and can yield
highly asymmetric probability density functions for the estimated
parameter values in the untransformed space that are unrealistic
in some cases (Michalak and Kitanidis, 2003). Alternative ap­
proaches include the Markov chain Monte Carlo (MCMC)
methods, which use Bayes' rule to constrain the posterior prob­
abilistic density function (pdf) (Michalak and Kitanidis, 2002,
2003, 2004a, 2004b, 2005; Michalak, 2008). Michalak (2008)
showed that an application of the non-negativity constraint using
Gibbs sampling, an MCMC method, improved the accuracy and
precision of the estimates of the arsenic release history in the
North Fork of the Humboldt River. The superiority of Gibbs
2
Journal of Contaminant Hydrology 251 (2022) 104097
sampling over power transformation has been verified by a case
study of the atmospheric inverse modeling of trace gas emissions
(Miller et al., 2014). Such study demonstrated the great flexibility
of the Gibbs sampler in determining the shape of the posterior pdf
and its computational efficiency. So far, however, the Gibbs
sampling method has not been applied to estimate plumes in
groundwater flow.
(3) Although contamination is commonly caused by multiple con­
taminants, most studies tackle only one contaminant such as 1,4-
dioxane (14DNE; Michalak and Kitanidis, 2002) and hexa­
chlorocyclohexane (Gyzl et al., 2014). Michalak and Kitanidis
(2003) studies the release histories of two contaminants, tetra­
chloroethene (PCE) and trichloroethene (TCE), but did not
discuss the consistency between the results of the two contami­
nants. Therefore, we are not sure if it is feasible to analyze mul­
tiple components in the same study.
To address these problems, the non-negativity constraint using Gibbs
sampling was incorporated into the geostatistical method with
groundwater flow modeling for estimating the distribution of contami­
nant plume and the associated uncertainty. The method was then tested
on groundwater contamination in the Gloucester landfill in Ontario,
Canada, using three-dimensional contaminant transport model and
multiple concentration data in 1982. The method was applied to three
water soluble organic contaminants: 14DNE, tetrahydrofuran (THF),
and diethyl ether (DEE). The research flows from an estimation of the
release history of a conservative tracer, 14DNE, and its comparison with
the known large disposal in 1978; reproduction of the estimated peak of
14DNE by calculating the retardation factors of THF and DEE and
verifying the factors using fraction of organic carbon; to three-
dimensional plume estimations of the three contaminants and their
verification by comparing the obtained values with concentration data
from 66 points.
2. Methods
2.1. Geostatistical inversion
The contaminant plumes were calculated with the inverse/forward
modeling method of Shlomi and Michalak (2007), which uses a known
source location and a steady groundwater flow for the transport of
contaminant materials. The source intensity is estimated at a time tj (j =
1, ⋯, mt) using the measured concentration data z* ∈ ℝn×1 (n-dimen­
sional real space) at a sample location xi (i = 1, ⋯, n) and time tmes (>tmt).
Assuming steady flow, z* can be related linearly to the release history, s
∈ ℝmt×1, as
z* = H * s + v, (1)
where H* ∈ ℝn×mt is the Jacobian matrix and v ∈ ℝn×1 is the measure­
ment and model error. This linear relationship is illustrated schemati­
cally in Fig. 1(a). Because the Jacobian matrix can be defined in
advance, typically by simulating the groundwater flow, the contaminant
plume distribution can be calculated forward over an area by applying
inverse analysis of the unknown release history s with limited data z*
and the linear system of Eq. (1).
The release history can be estimated by geostatistical inversion
methods, as demonstrated earlier (e.g., Kitanidis and Vomvoris, 1983;
Kitanidis, 1995), where s and v were assumed to be random vectors.
Suppose that s is a multivariate Gaussian distribution with a structural
parameter θ:
s = Xs βs + ε, ε ∼ N (0, Qs (θ) ), (2)
where Xsβs is the drift (i.e., the expected value of s), Xs ∈ ℝmt×ps is a
known matrix of basis functions, βs ∈ ℝps×1 are ps unknown drift co­
efficients, and Qs(θ) ∈ ℝmt×mt is a covariance matrix of s. On the basis of
S. Takai et al. Journal of Contaminant Hydrology 251 (2022) 104097

Fig. 1. Illustration of (a) the linear relationship between the measured concentrations and the source intensity and (b) the steps taken to estimate the release history
(step 1) and the plume distribution (step 2) by geostatistical inversion.

these settings, the unknown release history is estimated using the described as follows:
following two steps. In the first step, the optimal θ is specified . The
̂s = Λs z* , (10)
posterior pdf p(s| z*) can be proportional to the product of the likelihood
p(z*| s) and the prior pdf of p(s) as in Bayes' rule:
V̂s = Qs − Qs H * ΛTs − Xs Ms . (11)
T

* *
p(s|z )∝p(z |s)p(s). (3)
Once ̂s and V̂s are solved, the estimated plume distribution over a
Assuming that v~N (0, R), where R∈ ℝn× is an error covariance
n

study area ̂z ∈ ℝm×1 and its uncertainty V̂z can be solved:

matrix of z*, p(s) and p(z*| s) can be expressed as:
1
[
1
] ̂z = Ĥs , (12)
p(s) = mt /2
|Qs |− 1/2 exp − (s − Xs βs )T Qs − 1 (s − Xs βs ) , (4)
(2π) 2
V̂z = HV̂s H T , (13)
[ ]
1 1 *
p(z* |s) = |R|− 1/2
exp − (z − H * s)T R− 1 (z* − H * s) . (5) where H ∈ ℝn×m is the Jacobian matrix and m is the number of esti­
(2π)n/2 2
mation points. The steps for optimal estimation of the release histories
The optimal structural parameter θ is estimated using a restricted and plume distributions are illustrated in Fig. 1(b).
maximum likelihood approach which maximize the following marginal In most cases, the release history is unknown and the drift shape and/
∫ ( ∫ ⃒ )
likelihood L (θ) = p(z∗ |βs , θ)dβs 　 p(z∗ ) = p(z∗ ⃒s)p(s)ds , in which or the covariance of ̂s are difficult to identify and determine, as in the
the unknown βs is eliminated by integrating. This is equivalent to present case study. Accordingly, the simplest linear trend (Xs = [1 t])
minimizing L(θ) (the negative log of L (θ)): and a cubic generalized covariance (Qs(ti, tj| θ) = θ|ti − tj|3) were used,
following Kitanidis and Lee (2014). This was done by assuming that the
1 1 ⃒ ⃒ 1 T
best ̂s estimate is continuously differentiable and smooth, that is,
L(θ) = ln|Σ| + ln⃒Xs T H * Σ − 1 H * Xs ⃒ + z* Ξ − 1 z* , (6)
T

2 2 2 equivalent to cubic spline interpolation (Dubrule, 1984). While R con­

tains measurement and model errors, only the uncorrelated measure­
Σ = H * Qs H * + R, (7)
T
ment error was considered simply as R = σR 2 I, where σ R 2 is the variance
( )− 1 of measurement errors and I ∈ ℝn×n is an identity matrix.
Ξ = Σ − 1 − Σ − 1 H * Xs Xs T H * Σ − 1 H * Xs Xs T H * Σ − 1 . (8)
T T

The optimal θ is calculated iteratively using the Fisher scoring

2.2. Non-negativity constraint using Gibbs sampling
method (Kitanidis, 1995). Then, the unknown release history ̂s is esti­
mated. By maximizing the posterior pdf p(s| z*), the system to be solved
The non-negativity release history can be achieved by constraining
is described as:
p(s| z*) to be non-negative using Gibbs sampling. The sampling can be
( )( T ) ( * ) executed sequentially from the marginal (one-dimensional) conditional
Σ H * Xs Λs H Qs
= , (9) distribution because the unconstrained pdf is explicitly derived by a
(H * Xs )T 0 Ms XsT
product of multidimensional Gaussian distributions, as described in
detail by Michalak (2008). The marginal posterior pdf p(si| z*, s) can be
where Λs ∈ ℝmt×n is a weight matrix and Ms ∈ ℝps×mt is a Lagrange
expressed using Bayes' rule:
multiplier. The form of Eq. (9) is equivalent to that of universal kriging
(or kriging with trend), which is frequently used as a spatial estimator in p(si |z* , s)∝p(z* |si , s)p(si |s)H (si ) (i = 1, ⋯, mt ), (14)
geostatistics. The best estimate and posterior covariance of ̂s are

3
S. Takai et al. Journal of Contaminant Hydrology 251 (2022) 104097

⎧
⎨ 1 si > 0 calculated to be infinite because μ was too low (negative) and τ was
H (si ) = 1/2 si = 0 (15) narrow, the result was set to zero.
⎩
0 si < 0
3. Site description and physical model
where si means s(ti), and H (si ) is the Heaviside function. Based on a
multidimensional Gaussian distribution of the likelihood of the mea­ 3.1. Background information about the Gloucester landfill
surements p(z*| s) in Eq. (5), the marginal likelihood p(z*| si, s) can be
expressed as: The Gloucester landfill in Ottawa, Ontario, Canada, was a municipal
1
(
1 (si − μL )
) and industrial landfill where hazardous wastes containing organic
p(z* |si , s) = √̅̅̅̅̅̅̅̅̅̅exp − , (16) wastes were disposed of from 1969 to 1980 in a special waste compound
2πτL 2 τL
(SWC) along the western edge of the landfill that extended across
aT b σR 2 approximately 3000 m2. The organic wastes were principally organic
μL =
bT b
, τL = T ,
b b solvents (e.g., chloroform, carbon tetrachloride, methanol, acetone,
benzene, and hexane). Soluble organic solvents such as 14DNE caused
∑
mt widespread contamination in the aquifer above the top of the limestone
a j = z* j − Hjk sk , bj = Hji . (17) bedrock at between 25 and 30 m deep (Fig. 2(a)) (e.g., Jackson et al.,
1985; Patterson et al., 1985; Jackson et al., 1989). While there is very
k=1,k∕
=i

Then, the marginal prior pdf p(si| s) is defined as: little information about the release history, records show that approxi­
( ) mately 1 ton of organic solvents (1 ton = 1000 L aqueous solution) was
1 1 (si − μP )2 disposed of in May 1978 (Jackson et al., 1985).
p(si |s) = √̅̅̅̅̅̅̅̅̅̅exp − , (18)
2πτP 2 τP The site sits on top of a complex sequence of Quaternary fluvioglacial
and coastal deposits (Fig. 2(b)) that was classified into five units
where μP and τP are obtained as the solution of the following system for (Jackson et al., 1985). In ascending order, there were a limestone
si: bedrock unit (Unit A); a basal till unit up to 2 m in thickness (Unit B); a
( )( ) ( ) thick confined, outwash aquifer up to 25 m in thickness composed of
Qs k∕=i,k∕=i Xsk∕=i Qs k∕=i,i
Λ
= , (19) interstratified and interfingering silts, sands, and poorly sorted gravels
Xs Tk∕=i 0 − M Xs Ti (Unit C); a clayey silt and silt unit acting as an aquitard or a confining
layer (Unit D); and surface deposits of fine sands to gravels up to 10 m in
∑
m t− 1 ∑
m t− 1 ps
∑ thickness, containing unconfined groundwater at several meters in
μP = Λj sj , τP = Qs ii − Λj Qs ji + Xsil Ml . (20)
j=1 j=1 l=1
depth (Unit E). The contaminants laterally flowed down to the confined
aquifer from the SWC along the topography, approximately from west to
Finally, the marginal posterior pdf p(si| z*) can be expressed by a east (Fig. 2(a)) (MacFarlane et al., 1983; Jackson et al., 1985).
truncated-Gaussian distribution: Of the contaminants in the waste, there was particular concern about
( ) three compounds (14DNE, THF, and DEE) because of their ability to
1 1 (si − μ)2
p(si |z* )∝√̅̅̅̅̅̅̅̅exp − H (si ), (21) migrate rapidly in aquifers (Lessage et al., 1990). 14DNE exhibits the
2πτ 2 τ greatest mobility because of its low KOW and high solubility (Table 1).
( ) Because 14DNE can be regarded as a conservative tracer, two previous
τ=
τP τ L μ μ
,μ = τ P + L . (22) studies estimated its release history three-dimensionally, using the
τP + τL τP τL minimum relative entropy (MRE) approach (Woodbury et al., 1998) and
To summarize the above calculations, the non-negativity- a geostatistical inversion with a non-negativity constraint based on a
constrained release history, contaminant plume, and their uncertainty Metropolis–Hasting algorithm (Michalak and Kitanidis, 2002). Howev­
can be obtained as follows: er, the estimations of plume distribution and the related uncertainty
were out of scope of these studies.
Here, the plume distributions of the three contaminants and the
1. Set initial values as the unconstrained solution ̂s cc 0 =
associated uncertainties were quantified and assessed, with comparing
(̂s uc (t1 ) , ⋯, ̂s uc (tmt ) )T .
the estimated release history of 14DNE with those from previous studies.
2. Draw a conditional realization ̂s cc l+1 from ̂s cc l at each time step by: The estimation comprised three steps. The first step was to estimate the
( ) release history of 14DNE and compare the result with those from pre­
̂s cc l+1 (t1 ) ∼ p ̂s cc l (t1 ) |̂s cc l (t2 ) , ⋯, ̂s cc l (tmt ) ,
l+1 ( l l+1 l ) ceding studies that used the same flow and transport model. Next, the
̂s cc (t2 ) ∼ p ̂s cc (t2 ) |̂s cc (t1 ) , ⋯, ̂s cc (tmt ) , (23) retardation factors of THF and DEE were specified by matching with the
⋮
l+1 ( l l+1
̂s cc (tn ) ∼ p ̂s cc (tn ) |̂s cc (t1 ) , ⋯, ̂s cc (tmt − 1 ) ,l+1 ) release peak of 14DNE. Finally, the three-dimensional plume distribu­
tions and the associated uncertainties for the three contaminants were
estimated.
and calculate ̂z cc l+1 = Ĥs cc l+1 .

3. Repeat step 2 until the calculation is converged (l = ls). 3.2. Contaminant transport in groundwater
4. Calculate the best estimate and 95% confidence interval (difference
(
between the upper and lower limits) of ̂s cc and ̂z cc from ̂s cc lburn +1 , ⋯ Contaminant transport is generally modeled using the advec­
) ( ) tion–dispersion equation. For three-dimensional contaminant transport
, ̂s cc ls and ̂z cc lburn +1 , ⋯, ̂z cc ls . The first lburn steps until the algorithm
in porous media with a steady, uniform groundwater flow along the x-
reaches convergence are discarded as a burn-in period. Convergence
axis, the transport is described as:
is evaluated by tracking the mean values of likelihood and prior
distribution, as in Michalak (2008). ∂c ∂c ∂2 c ∂2 c ∂2 c
Rf + Vx − Dx 2 − Dy 2 − Dz 2 = − λc (24)
∂t ∂x ∂x ∂y ∂z
*
Sampling from p(si| z ), a truncated-Gaussian distribution, was
implemented based on Johnson et al. (1994). If the sampled value was where c is the concentration; t is the time; Vx is the actual groundwater
velocity; Dx, Dy, and Dz are the dispersion coefficients in the x

4
S. Takai et al. Journal of Contaminant Hydrology 251 (2022) 104097

Fig. 2. (a) Plan view of the study area

(Gloucester landfill in Ottawa, Ontario,
Canada) and (b) geological cross-section
showing the distribution of the five
stratigraphic units along the cross-
section (red line) (modified from Jack­
son et al., 1985). The locations of the
contaminant source (special waste
compound), multilevel samplers with
the numbers used in Jackson et al.
(1985), and assumed groundwater flow
direction are indicated. (For interpreta­
tion of the references to colour in this
figure legend, the reader is referred to
the web version of this article.)

z1 and z2 are the top and bottom boundary depths of the source, and y0 is
Table 1
the half-width of the source. For a discretized time of the release history,
Solubilities and octanol-water partition coefficients of 14DNE, THF, and DEE.
t (0 < t < T, T is the measurement time), the analytical solution of the
Contaminant* 14DNE THF DEE Jacobian matrix H is expressed as:
Molecular formula C4H8O2 C4H8O (C2H5)2O [ ]
Solubility+ Miscible (> 8.0 × 105) Miscible (1 × 106) 6.9 × 104 x(z2 − z1 ) 1 (x − Vx (T − t) )2
H(x, y, z, T − t) = √ ̅̅̅̅̅̅̅̅ exp − − λRf (T − t)
logKOW++ − 0.27 0.46 0.89 4B πDx (T − t)1.5 4Dx (T − t)
+
Solubility in water (mg/L) (Yalkowsky et al., 2010; Wishart et al., 2007;
ICSC, 2017). [ ( ) ( )]
y − y0 y + y0
++
Log of octanol-water partition coefficient (Hansch et al., 1995; Brooke • erfc ( )1/2 − erfc ( )1/2
et al., 1998). 2 Dy (T − t) 2 Dy (T − t)
*
14DNE: 1,4-dioxane; THF: tetrahydrofuran; DEE: diethyl ether.
[ ]
x 1 (x − Vx (T − t) )2
+ √ ̅̅̅̅̅̅̅̅ exp − − λR (T − t)
(longitudinal), y (transverse horizontal), and z (vertical) directions, π1.5 4Dx (T − t)1.5 4Dx (T − t)
f

respectively; Rf is the retardation factor; and λ is the first-order

biochemical decay constant. To facilitate comparison, the contaminant [ ( ) ( )]
y − y0 y + y0
transport model with a three-dimensional analytical solution used in this • erfc ( )1/2 − erfc ( )1/2
study was the same as those used in the previous studies discussed 2 Dy (T − t) 2 Dy (T − t)
earlier. We assume that a contaminant is sourced in a rectangular area in [ ( ) ( )] ( ) [ 2 2 ]
∑∞
the yz plane and transported from there in an aquifer. The extent of •
1
sin
lπz2
− sin
lπz1
cos
lπz
exp −
l π Dz (T − t)
. (26)
aquifer is semi-infinite, infinite, and finite with thickness B in the x-, y-, l=1
l B B B B2
and z-directions, respectively. The initial and boundary conditions of the
The values of the parameters in Eq. (26) used in the two previous
solution are as follows:
studies discussed earlier, derived from the analysis of reported data by
c(x, y, z, 0) = 0, Jackson et al. (1985), were used in this study (Table 2). The top
{
s(t) ( − y0 ≤ y ≤ y0 z1 ≤ z ≤ z2 ) boundary of the calculation domain was set to the ground surface
c(0, y, z, t) = ,
0 (otherwise) because the water table, the aquitard, and the top of the bedrock were
approximately parallel. The top and bottom depths of the confined
c(∞, y, z, t) = 0, c(x, ±∞,z, t) = 0, outwash aquifer were assigned to z1 and z2, respectively. Woodbury
∂c ∂c⃒
⃒ (25) et al. (1998) calculated the transport velocity Vx on the basis of an
= 0, ⃒⃒ =0
∂zx,y,B,t ∂z x,y,0,t analysis of the center of mass of the plume, which was generally
consistent with the reported values: A borehole dilution survey in a
where z is the depth from the ground surface, s(t) is the release history, single piezometer showed that the mean groundwater velocity in the

5
S. Takai et al.
Table 2
Parameter values used for the contaminant transport model using the advection–dispersion equation.
Parameter Vx (m/d) αx (m) αy (m) αz (m)
Value 0.127 2.6 0.5 0.1
target area was 0.07 m/day, while a pumping test showed it was 0.15 m/
day (Jackson et al., 1985, 1989). The dispersivity coefficients can be
expressed as (Dx, Dy, Dz) = (Dm + Vxαx, Dm + Vxαy, Dm + Vxαz), where Dm
is the molecular diffusion coefficient and αx, αy, and αz are the longitu­
dinal, transverse and, vertical dispersivities, respectively. The values of
the dispersivity coefficients were defined from the plume moments and
by referring to classic theory (Domenico and Schwartz, 1990), and
corresponded to the estimated values of (αx, αy) = (2.0, 1.5) (m) by
calibrating with the hydraulic head and concentration data (Gailey
et al., 1991). The λ value was set to 0. The start date of the special waste
activities, May 1, 1969, was set to t = 0. The release history was
recovered until the beginning of the measurement period, September
1982, or t = 4870 days.
The following empirical relationship can be used to define Rf:
/ 5000 realizations and the first 100 realizations were regarded as the
Rf = 1 + ρb • Kp ε, Kp = fOC • KOC , (27)
where ρb is the soil bulk density, ε is the porosity (0–1), Kp is the par­
titioning coefficient, fOC is the fraction of organic carbon, and KOC is the
organic carbon partitioning coefficient related to the octanol–water
partitioning coefficient, KOW, derived from the study of the sorption of
chlorinated benzenes for sediments with an fOC > 0.001 (Schwarzenbach
and Westall, 1981):
logKOC = 0.72logKOW + 0.49.
The Rf values were derived as shown in Table 3 by setting ρb = 2000
kg/m3, and ε = 0.35 based on the values of 0.3 to 0.35 for the outwash
aquifer (Jackson et al., 1985), and using the KOW values of each
contaminant (Table 2). The resulting values were the same as those of
Jackson et al. (1985). Because the Rf of 14DNE was close to 1 regardless
of fOC, the sorption of 14DNE was not considered as in earlier studies
(Woodbury et al., 1998; Michalak and Kitanidis, 2002). In contrast, the
Rf values of THF and DEE depended on fOC. Therefore, we calculated the
value of Rf, by reproducing the estimated peak of 14DNE and verified it
against a value range derived from the fOC.
3.3. Measurement and estimation of the contaminant plume
We used the concentration data collected by Jackson et al. (1985). At
that time, the organic compounds in the groundwater were measured
using bundle-type multilevel samplers (Cherry et al., 1983) with screens
set at depth intervals of approximately 1 m (Nos. 14, 17, 21, 34, 37, 38,
39, 47, and 54; Fig. 2) or 4 m (Nos. 12, 18, 33, 40, 52, and 56) along 15
observation wells. The organic compounds in the groundwater samples
were analyzed using gas chromatography/mass spectrometry (Finnigan
4000 GC/MS system). From all the data, 176 points measured from
September to December 1982 were selected (the blank was treated as
zero, as in Jackson et al., 1985). Then, the 1-m interval data were
adjusted to the 4-m interval data by averaging the original data over
each 4-m depth range, to account for the variation in the sample location
distributions and measurement time intervals. The distributions of the
66 data points that resulted are shown in Fig. 3. The averaging did not
Table 3
Definitions of the retardation factor (Rf) values of the three contaminants using
the two fractions of organic carbon (fOC).
Contaminant 14DNE THF
Rf (fOC = 0.0035) 1.0 1.1
Rf (fOC = 0.01) 1.1 1.4
Journal of Contaminant Hydrology 251 (2022) 104097
Dm (m2/d) λ (/d) y0 (m) z1 (m) z2 (m) B (m)
0.0 0.0 25.0 6.0 24.0 24.0
significantly change the original depth–profile trend (Fig. 4).
The measured concentration data were shown by the least significant
digit of 0.1 (μg/L), but Jackson et al. (1985) did not provide information
about data precision. Assuming that this digit included uncertainty and
the measurement errors were normally distributed, the error variance
was assigned by σR 2 = 0.25 (μg/L)2, to correspond with the 95% confi­
dence interval of ±1 (μg/L) (Michalak, 2008). Meanwhile, the detection
limit of 14DNE using the conventional purge-and-trap coupled with GC/
MS was reported to range from 3 to 20 (μg/L) because of the poor purge
efficiency (Issacson et al., 2006; Mohr, 2001; Draper et al., 2000).
Therefore, we have also considered the large measurement error for
14DNE in our discussion, i.e., σR= 3.0 (μg/L), assuming the detection
limit was 10 (μg/L) and this limit was equal to three times σR (Loconto,
2001). The time interval was one day. The Gibbs sampling was set to
burn-in period. The release histories and plume distributions were
calculated for the rectangular area covering x = [0,300] (m) × y =
[− 150, 150] (m) as shown in Fig. 2(a).
4. Results
4.1. Release history of 14DNE
(28) For the recovered release history of 14DNE, the value of θ used in the
cubic covariance was 1.3 × 10− 3 (mg2/L2/day3). The resulting release
histories without a non-negativity constraint and those constrained
using the Gibbs sampling are compared in Fig. 5(a) and (b). It is worth
noting that the peak corresponding to the large disposal in May 1978
was clearly reproduced by the non-negativity constraint. The peak
concentration was much lower than the solubility limit >8 × 105 mg/L
(Yalkowsky et al., 2010). It is also worth noting that the 95% confidence
interval was almost equivalent to the best estimate, and supports the
accuracy of the inversion result. In contrast, the best estimate without
the non-negativity constraint contained unrealistic negative concentra­
tions. In addition, the 95% confidence interval was much larger than the
best estimate by a factor of two orders (e.g., the peak concentration of
the best estimate was 0.4 mg/L and had a confidential interval of
approximately 206 mg/L), which meant that the uncertainty was very
large and the accuracy of estimates was low.
Comparison of the recovered release histories showed that the pro­
posed method was superior to the MRE approach of Woodbury et al.
(1998) that assumed Gaussian or uniform prior distributions (Fig. 5(c)).
When assuming the Gaussian prior, the latter peak in the two estimated
peaks corresponded to the large disposal in 1978 (Woodbury et al.,
1998). However, the resulting release histories were strongly dependent
on the prior distribution. In contrast, we were able to reproduce the
large spill without any prior information, which is an advantage of
geostatistical inversion (Michalak and Kitanidis, 2002).
The results presented in this paper differed from those presented by
Michalak and Kitanidis (2002), even though the geostatistical inversion
approach was used. This is mainly because they also used the data from
1983 onwards; the difference in measurement data results in a different
setting of the covariance structure (θ) and the error (σR). The ground­
water flow and contaminant conditions may be changed after 1983 by
the GTC purge well test in October 1983 (Jackson et al., 1985), soil
remediation from 1987 to 1989, and contaminant removals from the
deep and shallow groundwater plume after April 1992 (Franz Environ­
DEE
mental Inc., 2007). Therefore, calculations using the data after 1983
1.3 under steady-flow conditions can be considered misleading. In addition,
1.8
Michalak and Kitanidis (2002) constrained the non-negativity with the
6
S. Takai et al. Journal of Contaminant Hydrology 251 (2022) 104097

Fig. 3. Distribution of groundwater concentration data from 1982 for the three contaminants: (a) 14DNE, (b) THF, (c) DEE.

Fig. 4. Examples of the measured and averaged concentration data for the three contaminants at depth intervals of 4 m at the three wells. The solid and dashed lines
denote the original 1 m interval data and the averaged concentrations, respectively (Jackson et al., 1985).

Fig. 5. The release histories of 14DNE recovered using geostatistical inversion (a) with no constraint and (b) with a non-negativity constraint. The red and dashed
black lines denote the best estimate (BE) and the 95% confidential interval (95% CI), respectively. (c) Comparison of the best estimates with those of two previous
studies using a minimum relative entropy approach (Woodbury et al., 1998) and geostatistical inversion using the Metropolis–Hasting algorithm (Michalak and
Kitanidis, 2002). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Metropolis–Hasting algorithm, an MCMC method. The Gibbs sampling is
considered superior to the Metoropolis–Hasting algorithm (the random
walk procedure containing the acceptance test) because of its compu­
tational efficiency and shorter computation time. If the posterior pdf for
each time can be calculated using Eq. (21) in advance, as in this study,
the constrained solution can be obtained efficiently using the Gibbs
sampling. Previously, residual variance values of 22.5 (μg/L)2 (Wood­
bury et al., 1998) and 12.3 (μg/L)2 (Michalak and Kitanidis, 2002) were
reported. Only a rough comparison is possible because of the difference
in the used data; however, the residual variance of our result was 1.07

7
S. Takai et al. Journal of Contaminant Hydrology 251 (2022) 104097

(μg/L)2, which was approximately on the same scale as that of the error at around 1 × 10− 3 (mg/L) for THF and DEE (Fig. 7(b)). These data were
setting σ R 2 = 0.25 (μg/L)2. collected from shallow depth (z = 4 to 12 m) at sampling point No. 34
(Fig. 2(a)), which is located in the stratified low permeability zone of the
confined aquifer (Unit C, shown in Fig. 2(b)). Such unit-dependent dif­
4.2. Verification of the retardation factors of THF and DEE
ferences in permeability were not considered in the analytical solution,
and so may have caused the overestimation. This is considered in more
The retardation factors of THF and DEE estimated by accounting for
detail in the discussion.
the fraction of organic carbon (Table 2) were verified using the repro­
duced release peak of 14DNE. The release histories of THF and DEE
5. Discussion
(Fig. 6) were reproduced using the optimal θ of 1.8 × 10− 3 and 2.5 ×
10− 3 (mg2/L2/day3). The peaks of THF (25 mg/L) and DEE (77 mg/L)
5.1. Effect of averaging the measurement concentrations
are much lower than solubility limits of THF (1.0 × 106 mg/L) (Wishart
et al., 2007) and DEE (6.9 × 104 mg/L) (ICSC, 2017). The retardation
As described earlier, the original concentration data at the 176 points
factors were determined as 1.75 for THF and 1.8 for DEE to reproduce
were averaged over a 4-m depth range to calculate the release history
the peak of 14DNE caused by the large disposal in 1978 (Fig. 5(b)) under
using the measured concentrations at 66 points. To examine whether the
the following settings: from 1.1 to 1.4 for THF and from 1.3 to 1.8 for
averaging affected the calculation accuracy, the release history of
DEE (Table 3). This comparison supports the suitability of the parameter
14DNE was calculated using the original data with the nonnegativity
set for DEE but indicates that the retardation factor of THF was slightly
constraint. The value of θ in the cubic covariance was 1.2 × 10− 3 (mg2/
overestimated. This may reflect insufficient measurement locations,
L2/day3). Two release histories were estimated using the original and
which might have decreased the accuracy of the inversion result, or co-
averaged data (Fig. 8). While the release history based on the original
metabolic biodegradation of 14DNE with THF (Kohlweyer et al., 2000;
data had a slightly larger peak and more uncertainty than the one based
Vainberg et al., 2006; Sun et al., 2011), which may have affected the
on the averaged data, the distributions of the release histories were
shapes and concentrations of the 14DNE and THF plumes.
similar. The residual variance of the result was 1.55 (μg/L)2, which is
similar to that using averaged data (1.07 (μg/L)2). Consequently, this
4.3. Contaminant plume distributions of the three contaminants confirmed that the averaging had little effect on the release history and
plume distribution estimations.
The plume distributions of the three contaminants were calculated
(Fig. 7(a)) from the release histories estimated using the non-negativity
5.2. Effect of the large measurement error
constraint. The accuracy of the estimations was checked using scatter­
plots of the absolute error between the calculated and measured con­
The effect of the measurement error caused by the poor purge effi­
centrations (Fig. 7(b)), the mean absolute error (MAE), and the linear
ciency was examined using a σR value of 3.0 (μg/L) for 14DNE. The value
correlation coefficient (r) values of these concentrations (Table 4). With
of θ in the cubic covariance was 4.9 × 10− 2 (mg2/L2/day3). The esti­
the non-negativity constraint, the MAEs of all the contaminants
mated release history with a large measurement error showed a wider
decreased considerably, with decreases of 46%, 67%, and 59% for
peak concentration than the release history with a small measurement
14DNE, THF, and DEE, respectively, and the r values increased to be­
error (Fig. 9(a)), but the plume distributions were similar regardless of
tween 0.60 and 0.77. These results indicate a high reproduction accu­
the measurement error (Fig. 9(b)), in which MAE was 2.0 × 10− 2 (μg/L)
racy and demonstrate the effectiveness of the non-negativity constraint.
and r was 0.76. The maximum uncertainty of the estimated plume dis­
In addition, the low uncertainties of these distributions can be confirmed
tribution with the large measurement error was up to 1.9 times greater
from the 95% confidence intervals, which were one or more orders
than that with the small measurement error. However, the high uncer­
lower than the best estimates common to the three contaminants (Fig. 7
tainty area (the middle of the study area) was the same regardless of the
(a)). The uncertainties for the three contaminants were relatively high
measurement error, and corresponding to a large release peak and a lack
around the middle of the study area, probably because of the relatively
of measurement points.
high concentrations in that area associated with the large peak after
1978 and the sparse density of the measurement points. The uncertainty
distribution can be used to determine the number and location of 5.3. Verification of the release histories and plume distributions
additional measurements.
The disagreement in the measurements was probably caused by The release histories and plume distributions of the three contami­
using the analytical solution for contaminant transport. The absolute nants are examined in detail below. A vertical cross-section at y = 0 m in
errors between the calculated and measured concentrations were large the E–W direction (along the x-axis) was drawn for the three

Fig. 6. Comparison of the release histories of (a) THF and (b) DEE recovered using geostatistical inversion with a non-negativity constraint. The thick and dashed
lines denote the best estimate (BE) and the 95% confidential interval (95% CI), respectively.

8
S. Takai et al. Journal of Contaminant Hydrology 251 (2022) 104097

Fig. 7. (a) Perspective views of the plume distributions of the three contaminants (the top row shows the best estimates, the bottom row shows the 95% confidential
intervals). The top surface (z = 24 m) corresponds to the bottom of the aquifer. (b) Scatterplots showing the relationship between the absolute error and the measured
concentrations of the three contaminants using the non-negativity constraint (red circle) and without any constraint (black circle) with each mean absolute error
(dashed line). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

contaminants and overlain with the original (not averaged) measured

Table 4
concentrations (Fig. 10). The calculated plume distributions were
Comparison of the mean absolute error (MAE) and the linear correlation coef­
generally consistent with the measured concentrations. Any disagree­
ficient (r) of the relationships between the calculated and measured concen­
trations with and without the non-negativity constraint. ments between the calculated and measured concentrations may have
been caused by heterogeneity of the aquifer permeability. The geolog­
Contaminant 14DNE THF DEE
ical columnar section had more geological units and suggested inter­
2 1 1
No constraint MAE (mg/L) 3.4 × 10− 2.7 × 10− 4.0 × 10− stratified low permeability zones in the aquifer (Unit C; Jackson et al.,
r 0.60 0.39 0.56
2 2 1 1985). Because of this low permeability, the measured concentrations
Nonnegativity MAE (mg/L) 1.8 × 10− 9.0 × 10− 1.6 × 10−
r 0.77 0.60 0.71 were remarkably low in the area (e.g., low THF and DEE zones extended
through the aquifer at an elevation of around 85 m). In addition, the
groundwater flow direction was presumed to be heterogenous,
depending on the geological structure. However, a simple transport
model with a one-direction flow was adopted in this study to compare
our results with those from the studies of Woodbury et al. (1998) and
Michalak and Kitanidis (2002). The Jacobian matrix in Eqs. (1) or (12)
expresses the sensitivity of the concentration at each point and each
time. This can be calculated numerically by running a flow and transport
model with a release of a unit concentration pulse. Therefore, accurate
three-dimensional groundwater flow models that account for detailed
geological structures are needed to improve the estimation accuracy
instead of the analytical solution.
Differences may also occur by simplifying the contaminant transport
from the source (SWC) to the aquifer (Unit C). Although the SWC was at
a depth of about 10 m, we assumed that the source was uniformly
distributed at the edge of the aquifer in the analytical solution. This
Fig. 8. Comparison of the release history of 14DNE with the non-negativity assumption originated from the fact that the aquitard (Unit D) under the
constraint using all the original data (solid lines) and the data averaged over SWC was locally discontinuous because of heterogenous lithofacies or
each 4-m depth range (translucent lines). The thick and dashed lines denote the excavation for waste disposal (Jackson et al., 1985). This implies that
best estimate (BE) and the 95% confidential interval (95% CI), respectively. most contaminants may have moved rapidly through the discontinuities
in the aquitard, thereby causing the peak after the large disposal in

9
S. Takai et al. Journal of Contaminant Hydrology 251 (2022) 104097

Fig. 9. Estimated (a) release history and (b) plume distribution of 14DNE using a large measurement error setting. The thick and dashed lines denote the best
estimate (BE) and the 95% confidential interval (95% CI), respectively.

Fig. 10. E–W cross-sections showing the calculated concentrations of the three organic compounds along the x-axis at y = 0 m (Fig. 2(a)). Five hydrogeologic units
(A-E), measured concentrations at sampling locations along the observation wells (colored circles), a heterogeneous silt distribution in the confined aquifer (Unit C),
and the assumed groundwater flow direction in the confined and unconfined aquifer are overlapped.

1978. Meanwhile, the estimated release histories of THF and DEE
showed second peaks in 1981 (Fig. 6) because of the high concentrations
measured in the upper part of the aquifer at around E.L. = 100 m near
the SWC. Although other large spills may have occurred in 1980, the
estimated second peak may be considered a result of the slow transport
of contaminants through the aquitard. Assuming that the hydraulic
gradient (ih) was 0.002, the hydraulic conductivity of the aquitard (KD)
was 7.9 × 10− 6 (m/s) and the porosity (ρD) was 0.4, following Jackson
et al. (1985), and the thickness of the aquitard (h) was 1.5 m, the
transport time calculated as h • Rf/(ih • KD/ρD), in the aquitard was
estimated as 769 days for THF and 791 days for DEE. The transport time
in the aquitard was approximately consistent with the time lags between
the first and second peaks of the estimated release history, which was
880 days for THF and 890 days for DEE. To improve the accuracy of the
estimations, the contaminant release from the SWC needs to be modeled.
Differences may also occur because of seasonal change in rainfall.
After the large disposal in May 1978, rainy seasons with rainfall
amounting to approximately 100 mm/month were recorded almost
every year. Our steady flow assumption may be valid for long-term
contaminant transport. Therefore, the effects of rainfall infiltration
and seasonal changes in groundwater flow fields on the release condi­
tion settings (amount and flow direction) of contaminants from a source
needs to be confirmed.
6. Conclusions
The aim of this study was to demonstrate the applicability and
effectiveness of a geostatistical approach that incorporated groundwater
flow modeling to estimate the contaminant plume when the release
history is unknown. The approach was tested on groundwater contam­
ination in the Gloucester landfill. The approach was effective, as the
accuracy of the estimation was improved by applying a non-negativity

10
S. Takai et al.
constraint using Gibbs sampling. With the geostatistical approach and a
non-negativity constraint, the three-dimensional plume distributions
were produced with adequate accuracy for the three organic solvents
(14DNE, THF, and DEE) with linear correlation coefficients between the
estimation and measurement of 0.60 to 0.77 for the concentration data
from multiple depths. In addition, the reconstructed release peak for
14DNE that corresponded to the large disposal in 1978 was more correct
than for the preceding studies, without any prior information of the
release history. The reconstructed release histories for THF and DEE also
indicated the same peaks with retardation factors that were generally
consistent with the estimation using fraction of organic carbon. This
study may be the first application to estimate three-dimensional plume
distributions and the associated uncertainties when the release history is
unknown, targeting multiple contaminants. The proposed method can
be applied widely to contaminated groundwater fields.
To increase the accuracy of the estimation, the modeling of the
groundwater flow and the hydrogeologic structure should be improved.
The accuracy of the predictions of future plume transport could be
improved with precise estimation of the hydrogeological structure,
which would be useful when planning for remediation. The hydro­
geological structure could be estimated from transient measurements of
groundwater concentrations. For example, the hydraulic parameters
used in the analytical solution could be calibrated by sensitivity analysis
with an objective function, such as the reproducibility of measurement.
The Ensemble Kalman filter is one of the potential methods, which can
be also applied to a joint estimation of contaminant source and hydraulic
conductivity (e.g., Chen et al., 2021). Geostatistic-based hydraulic to­
mography using well hydraulic test data could be used to help account
for heterogeneity of hydraulic conductivity from limited data (e.g., Lee
and Kitanidis, 2014). The estimations in this study could also be
improved by considering spatial correlation of measurement data
(Shlomi and Michalak, 2007), in addition to the temporal correlation of
release history. However, the steady-flow assumptions may not be valid
if the transient change of groundwater flow increases (e.g., by pumping
wells). In this case, our method should be repeated with temporal
measurement data to estimate the plume distributions.
CRediT authorship contribution statement
Shizuka Takai: Conceptualization, Data curation, Formal analysis,
Investigation, Methodology, Validation, Visualization, Writing – orig­
inal draft. Taro Shimada: Funding acquisition, Supervision, Writing –
review & editing. Seiji Takeda: Funding acquisition, Supervision,
Writing – review & editing. Katsuaki Koike: Supervision, Methodology,
Validation, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
The data that has been used is confidential.
Acknowledgments
This study was funded by the Secretariat of Nuclear Regulation Au­
thority, Nuclear Regulation Authority, Japan.
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