Physics and Chemistry of the Earth 31 (2006) 640648

www.elsevier.com/locate/pce

Inverse modeling of tracer experiments in FEBEX

compacted Ca-bentonite
a,*
Javier Samper , Zhenxue Dai a,1, Jorge Molinero b, M. Garca-Gutierrez c,
T. Missana c, M. Mingarro c
a
Escuela Tecnica Superior de Ingenieros de Caminos, Canales y Puertos, Campus de Elvina s/n, 15192 La Coruna, Spain
b
Escola Politecnica Superior, Universidad de Santiago de Compostela, 27002 Lugo, Spain
c
Dpto. de Impacto Ambiental de la Energa, Caracterizacion Hidrogeoqumica de Emplazamientos, CIEMAT, Edicio 20-A,
Avda. Complutense, 22, 28040 Madrid, Spain

Received 18 September 2005; received in revised form 28 January 2006

Available online 22 June 2006

Abstract

Solute transport parameters of compacted Ca-bentonite used in the FEBEX Project were derived by Garca-Gutierrez et al. (2001)
from through- and in-diusion experiments using analytical solutions for their interpretation. Here we expand their work and present
the numerical interpretation of diusion and permeation experiments by solving the inverse transport problem which is formulated
as the minimization of a weighted least squares criterion measuring the dierences between computed and measured concentration values.
The inverse problem is solved with INVERSE-CORE2D, a nite element code which accounts for both dissolved and sorbed concentra-
tion data, uses either the Golden section search or GaussNewtonMarquardt methods for minimizing the objective function and allows
the estimation of transport and retardation parameters such as diusion coecient, total and kinematic porosity and distribution coef-
cients. Diusion and permeation experiments performed on FEBEX compacted bentonite using tritium, cesium, selenium, and stron-
tium have been eectively interpreted by inverse modeling. Estimated parameters are within the range of reported values for these
tracers in bentonites. It has been found that failing to account for the role of sinters may lead to erroneous diusion coecients by a factor
of 1.4. Possible ways to improve the design of in-diusion and permeation experiments have been identied. The interpretation of the
tritium permeation experiment requires the use of a double-porosity model with mobile porosity of 0.14 for a dry density of 1.18 g/cm3.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Inverse modeling; Solute transport parameters; FEBEX; Bentonite; Diusion experiments; Sorption

1. Introduction by Minas de Gador, S.A. in Serrata de Njar (Almera,

Predictions of reactive solute transport through com-
pacted bentonites are needed for the performance assess-
ment of the disposal of hazardous wastes such as high-
level nuclear waste (HLW). The FEBEX bentonite was
extracted from the Cortijo de Archidona deposit, exploited
*
Corresponding author. Address: Escuela de Caminos, Campus de
Elvina s/n, Universidad de La Coruna, 15192 La Coruna, Spain. Tel.: +34
981 16 70 00x1433; fax: +34 981 16 71 70.
E-mail address: jsamper@udc.es (J. Samper).
1
Present address: Earth and Environmental Sciences Division,
Los Alamos National Laboratory, New Mexico, USA.
Spain). This bentonite was selected by ENRESA (Empresa
Nacional de Residuos Radioactivos, S.A.) prior to the
FEBEX project (Huertas et al., 2000) as a suitable material
for backlling and sealing of a HLW repository because it
has a very large montmorillonite content, large swelling
pressure and sorption capacity, extremely low permeabil-
ity, acceptable thermal conductivity and ease of compac-
tion for the fabrication of blocks. Bentonite used in the
FEBEX project was homogenized to reduce the uncertain-
ties in parameter variability (Huertas et al., 2000).
The solution of the inverse problem provides a way
whereby measurements of state are used to determine
unknown ow and transport parameters by tting model

1474-7065/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pce.2006.04.013
 J. Samper et al. / Physics and Chemistry of the Earth 31 (2006) 640648
outputs to measurements. A general framework and
description of the coupled inverse problem of water ow
and solute transport is given by Mishra and Parker
(1989) and Sun (1994). More work on inverse ow and sol-
ute and transport in aquifers has been done by Samper
et al. (1990), Gailey et al. (1991), Wagner (1992), Xiang
et al. (1993), Medina and Carrera (1996) and Poeter and
Hill (1997).
However, the ability to fully characterize transport
parameters of compacted bentonite has not kept pace with
the numerical and modeling expertise. Deriving reliable
estimates of transport and sorption parameters of the
FEBEX bentonite is one of the objectives of the FEBEX
Project. Experimental characterization of diusive trans-
port of radionuclides in FEBEX bentonite was carried
out by means of through- and in-diusion experiments
(Garca-Gutierrez et al., 2001). Application of the inverse
approach to estimate various ow and transport parame-
ters of the FEBEX bentonite are presented by Dai and
Samper (1999). Solute transport parameters of compacted
Ca-bentonite used in the FEBEX Project were presented
by Garca-Gutierrez et al. (2001). These parameters were
derived from through- and in-diusion experiments which
were interpreted by means of analytical solutions. Here
we expand on the latter approach and provide results not
only for diusion but also for ow-through or permeation
experiments. Numerical interpretation of laboratory exper-
iments is achieved by solving the inverse problem of solute
transport. The inverse approach overcomes the limitations
of analytical solutions by accounting for: (1) Measurement
errors; (2) The role of the sinters; (3) Time-varying bound-
ary conditions in permeation experiments; and (4) Tran-
sient concentrations in the cell and total concentration
data at the end of in-diusion experiments. The inverse
analysis has been applied to the numerical interpretation
of through-diusion, in-diusion and permeation experi-
ments performed on FEBEX Ca-bentonite using tritium,
strontium, cesium and selenium. The following solute
transport parameters are estimated: molecular diusion
coecient, dispersivity, distribution coecient, Kd, and
kinematic as well total porosities.
2. Direct problem of solute transport and sorption
The equation for the transient transport of a sorbing sol-
ute through a saturated porous medium under steady-state
ow is given by (Bear, 1972):
oC
r  /DrC  qrC rC   C /R 1 3. Inverse problem of solute transport and sorption
ot
where / is porosity, C is solute concentration; q is volumet-
ric water ux; r is a uid sink/source term having a concen-
tration C*, t is time, and R is the retardation coecient
dened as
qK d
R1 2
/ generalized least squares criterion (Sun, 1994; Dai and
641
where Kd is the distribution coecient and q the bulk den-
sity. Tracer concentrations are extremely small. The largest
concentrations are 2.69 109 M for cesium, 5.4 109 M
for selenium and 109 M for strontium. For such low con-
centrations all sorption isotherms are linear. The dispersion
tensor, D, in (1) is given by
D De I Dh 3
and includes the hydrodynamic or mechanical dispersion
tensor, Dh, and the molecular diusion term. Since clay
samples were prepared by compacting powder FEBEX
bentonite which had been previously homogenized, molec-
ular diusion is expected to be isotropic. Therefore, the dif-
fusion term can be written as DeI, where De is the eective
molecular diusion coecient and I is the identity tensor.
In one-dimensional solute transport the mechanical disper-
sion, Dh, is equal to aq where a is dispersivity. The eective
diusion coecient in porous media, De, is usually ex-
pressed as:
De /Dp 4
where Dp is the molecular diusion coecient in the pore
space which in turn is given by
Dp D0 s 5
where D0 is the molecular diusion coecient in pure water
and s is the tortuosity of the medium which is assumed here
to be equal to /1/3 where / is porosity. The apparent diu-
sion coecient, Da, takes into account the combined eect
of diusion and sorption and is dened as
De
Da 6
/ qK d
Solution of Eq. (1) requires appropriate initial conditions:
Cjt0 C 0 7
and boundary conditions:
/DrC  nC1 bC 1  C F 0D 8
where n is a unit vector normal to the boundary C1 point-
ing outwards, C0 is initial concentration, C1 is a prescribed
concentration; b is a parameter controlling the type of
boundary condition. For a Neumann condition, b = 0
and solute ux through the boundary is equal to the disper-
sive ux, F 0D . For a Dirichlet condition, b = 1, F 0D 0 and
the concentration is prescribed to be equal to C1. At water
inow boundaries b = q n and F 0D 0.
The essence of the inverse problem lies on deriving opti-
mum parameter estimates from known concentration data.
Optimum parameters are those which minimize an objec-
tive function measuring the dierence between measured
and computed concentrations.
Our formulation of the inverse problem is based on
642 J. Samper et al. / Physics and Chemistry of the Earth 31 (2006) 640648

Samper, 2004). Let P = (p1,p2,p3, . . . ,pM) be the vector of
M unknown parameters. The least squares criterion, E(p),
can be expressed as,
X
NE
Ep W i Ei p 9 been developed. The code can estimate any ow and trans-
i1
where i 1; NE denotes dierent types of data, i = 1 for
dissolved concentration; i = 2 for total concentration;
i = 3 for prior information on model parameters, Wi is
the weighting coecient of the ith generalized least-squares
criterion Ei(p) which is dened as:
X
Li
Ei p w2li r2li p
l1
rli p uil p  F il
where uil p is the computed value of the ith variable at the
lth observation point; F il are measured values; Li is the
number of observations, either in space or in time, for
the ith type of data; and rli is the residual or dierence be-
tween model outcome and measurement; wli is the weight-
ing coecient for the lth measurement of the ith type of
data. Its values depend on the accuracy of observations.
If some data are judged to be unreliable, they are assigned
small weights in order to prevent their pernicious eect on
the optimization process.
Eq. (9) is a weighted multiobjective optimization crite-
rion. Weighting coecients Wi are computed from (Car-
rera and Neuman, 1986; Dai and Samper, 2004):
W 0i
Wi i 1; NE 10
Ei p
Li
where W0i are user-dened dimensionless initial weighting
coecients for dierent types of observation data. While
coecients W0i are dimensionless, Wi have dimensions
which are reciprocal of those of Ei(p). Generally Ei(p) has
been used to solve the inverse problem. Combining these
two inverse methods with the forward modeling code
CORE2D (Samper et al., 2000; Xu et al., 1999), an inverse
code INVERSE-CORE2D (Dai and Samper, 1999) has
port parameter in the code CORE2D and provides the sta-
tistical measures of goodness-of-t as well as parameter
uncertainty by computing the covariance and correlation
matrices, eigenvalues and approximate condence intervals
(see Dai and Samper, 2004).
4. Description of transport experiments
Several types of diusion experiments (Fig. 1) were car-
ried out by Garca-Gutierrez et al. (2001) to estimate trans-
port and sorption parameters of FEBEX bentonite,
including total and kinematic porosity, diusion coe-
cients (eective and apparent) and distribution coecient.
These experiments were interpreted by means of available
analytical solutions by Garca-Gutierrez et al. (2001). The
conditions of some experiments are not taken into account
by such solutions. The use of numerical models for exper-
iment interpretation overcomes these limitations of analyt-
ical solutions.
4.1. Through-diusion experiments
Through-diusion experiments were performed using
tritium (experiments TD-HTO1, TD-HTO2 and TD-
HTO3) and strontium (experiments TD-Sr5, TD-Sr6,
TD-Sr7 and TD-Sr8).
Experiments were performed on bentonite plugs of
50 mm of diameter, with lengths ranging from 5.3 mm for
PERMEATION
Pressure

units equal to the square of the unit used for each type
of data (i.e., (mol/l)2 for dissolved concentrations). Weights TRACER CLAY C
Wi are updated automatically during the iterative optimiza-
tion process according to Eq. (10) whenever NE > 1.
Weights wli for dierent observation points in (6) must
be specied in advance. In a statistical framework, these THROUGH DIFFUSION
coecients are inverse standard deviations expressing the
uncertainty of measured data. Such standard deviations TRACER
can be derived from measurement or analytical errors, TRACER CLAY
IN OUT
rm, or in the case of time series from random uctuations
about a trend. For a given type of data (i.e., for a xed
i), wli for all l = 1, 2, . . . , Li are all equal to r1
m whenever
IN DIFFUSION
all data values are equally reliable.
Minimization of the expression in Eq. (9) can achieved
by dierent methods such as: golden section search (Sun, TRACER CLAY TRACER
1994), Newton, GaussNewton, GaussNewtonLeven- IN IN
bergMarquardt (Yeh, 1986; Sun, 1994), conjugate gradi-
ent (Carrera and Neuman, 1986), quasi-Newton, and
simulated annealing. In this paper, golden section search Fig. 1. Methods used for determining sorption and diusion parameters
and GaussNewtonLevenbergMarquardt methods have (from Garca-Gutierrez et al., 2001).
 J. Samper et al. / Physics and Chemistry of the Earth 31 (2006) 640648
tritium to 8.3 mm for strontium (Fig. 1). They were
immersed in water for 4 weeks achieving a nal density
of 1.18 g/cm3. The clay plug was located in contact with
two cells. To ensure a uniform diusion through the whole
cross-section of the plug, porous stainless-steel sinters man-
ufactured by Mott were located at both sides of the plug.
According to technical specications sinters are 3.35 mm
long and have a porosity of 0.5. A known mass of tracer
was added initially to one of the cells. The evolution of tra-
cer activity was measured in both cells at regular intervals.
Experiments lasted around 54 days for tritium and nearly
200 days for strontium.
The model domain of through-diusion experiments
includes the following subdomains: the upstream and
downstream cells, two sinters and the clay plug. Finite ele-
ments representing the cells were assigned a porosity of 1
and a large-enough diusion coecient in order to ensure
that all nodes within the cell have the same activity. For
the sinters the eective diusion was computed using Eqs.
(4) and (5) with a porosity of 0.5.
The initial activity in the upstream cell was taken equal
to the initial prescribed tracer activity. Initial activity is
equal to zero in the rest of the subdomains.
Two nite element grids were used for the numerical sim-
ulation of through diusion experiments. That of tritium
(TD-HTO1, TD-HTO2 and TD-HTO3) includes 200 trian-
gular elements and 202 nodes. The grid for strontium exper-
iments (TD-Sr5, TD-Sr6, TD-Sr7 and TD-Sr8) has 114
triangular elements and 116 nodes. The simulation time
horizon covers the expected duration of the experiments.
For TD-HTO1, TD-HTO2 and TD-HTO3 the total time
is 54 days, which was discretized with 800 time increments.
For strontium experiments the total experiment time of 193
days was divided into 1800 time increments. Before running
the inverse model, some forward runs were made to test and
ensure the numerical stability of the solutions.
4.2. In-diusion experiments
In-diusion (ID) experiments consist on the immersion
of a clay sample of 38 mm of diameter and 25 or 50 mm
of length into a cell containing granite synthetic groundwa-
ter until saturation. Then a tracer, which is initially not
present either on the clay or on the sinters, is added to
the solution and allowed to diuse into clay samples from
both sides. The gradient in tracer activities induces a diu-
sive ux from the cell into clay samples (Fig. 1). The
decrease in tracer activity in the immersion cell was moni-
tored continuously. At the end of the experiment clay plugs
were sliced to obtain the activity prole along clay samples.
In-diusion experiments were carried using cesium and
selenium. Se(IV) was added as a sodium selenite SeO3Na2.
Tests were performed under oxic conditions.
The model domain for in-diusion experiments contains
ve parts: two cells, two sinters and a clay plug. Initial activ-
ities in the two cells are equal to the initial tracer activity
while in the sinters and the clay plug they are equal to zero.
643
Two kinds of numerical models were used in these
experiments, one for cesium (In-Cs-9 and In-Cs-10) with
600 triangular elements and 602 nodes, and the other for
selenium (In-Se-17, In-Se-18) with 200 triangular elements
and 202 nodes. The simulation time for both tracers
(cesium and selenium) is 439 days and it is discretized with
630 time increments.
4.3. Permeation experiments
A high-pressure stainless steel cell was used for perme-
ation experiments. The clay plug, 5.3 mm in length and
50 mm of diameter was sealed between two 3.35 mm thick
stainless steel sinters (Fig. 1). The granite synthetic ground-
water was injected into the sample with a low driving pres-
sure (6 bar) ensured by a HPLC pump with pressure and
ow regulation (the ow rate in the cells ranged from 2.7
to 4.0 ml/day). The nal density is 1.18 g/cm3. All the
experiments were performed under oxic conditions. After
4 weeks of sample saturation, a small pulse of tritium tracer
(500 ll or 183,000 counts) was injected into the uid path-
way. The breakthrough curve of the tracer at the outlet was
monitored continuously by a fraction collector.
Single and double porosity models were used to model
permeation experiments. The former is simulated with a 1-
D grid while the latter requires a 2-D nite element grid con-
taining a mobile part where water can ow and an immobile
part where only molecular diusion can take place.
Since the tracer was injected as a non-instantaneous
pulse, the duration and distribution of the pulse is uncer-
tain. Only the ow rate and the total tracer mass injected
are known. Tracer injection was modeled by using a
time-dependent pulse function. A trial and error method
was used to estimate such pulse function (Fig. 2) by keep-
ing constant the total mass of tracer injected. Initial activ-
ities in all of the nodes are zero.
1000
Permeation 1 (P-1d)
800 (Double-porosity)
Time function 1 Obj.=185.6
Activity (Mcount/l)
Time function 2 Obj.=72.0
Time function 3 Obj.=12.2
600
400
200
0
0.0 0.5 1.0 1.5 2.0
Time (days)
Fig. 2. Time functions used to dene the tracer pulse of the inow water.
Also shown are the values of the objective function for each time function.
One can see the large sensitivity of the t to the selected time function.
644 J. Samper et al. / Physics and Chemistry of the Earth 31 (2006) 640648

per, 1999). Results of the numerical interpretation of TD,

IN and P experiments are shown in Table 1. This table con-
tains also the parameters obtained by Garca-Gutierrez
et al. (2001) by using analytical methods. It should be
noticed that not all experiments could be interpreted
analytically.

Fig. 3. Finite element mesh for the double-porosity model.

5.1. Through-diusion experiments

The 1-D single porosity model (P-1) has 200 triangular
elements and 202 nodes. This model proved to be unable
to match observed data and then a 2-D double porosity
model (P-1d) was used which was discretized with 560 tri-
angular elements and 324 nodes. Fig. 3 illustrates the nite
element mesh used for the double-porosity model. The
total length of the system is 1.2 cm, including two sinters
at both sides (2 0.335 cm long) and the bentonite sample
in the middle (0.53 cm long). The width is 0.2 cm. Based on
a prior estimate of mobile porosity of about 20%, the width
of the mobile part (bottom row) is 0.04 cm while that of the
immobile part (the upper seven rows) is 0.16 cm.
The simulation time is 3.78 days. It is discretized with 88
time periods with gradually increasing time increments.
5. Interpretation by inverse modeling
Diusion experiments were interpreted numerically
using the inverse code INVERSE-CORE2D (Dai and Sam-
Several sets of through-diusion (TD) experiments were
performed on clay samples at dry densities ranging from
1.18 to 1.65 g/cm3 using tritiated water (tritium) and stron-
tium. Tritium was used in three TD experiments which
lasted about 50 days, a time long enough for the experi-
ment to attain steady activities along the samples.
Tritium experiments were used to test the estimation
algorithms and to explore the role of the sinters. Our
results indicate that the sinters should be taken into
account for a proper interpretation of the experiments.
The results in Table 1 clearly demonstrate that bentonite
diusion coecients obtained from analytical solutions
underestimate the true diusion coecient by a factor of
1.4. To demonstrate the accuracy of the numerical results,
experimental data were interpreted numerically with a
model without sinters. In this case, inverse estimates of dif-
fusion coecients coincide with those obtained with ana-
lytical methods. Therefore, failing to account for the
sinters can lead to the underestimation of diusion coe-

Table 1
Summary of interpretation of CIEMAT diusion experiments performed on samples of compacted FEBEX bentonitea
Tracer Experiments and Numerical Analytical
bentonite density (g/ 2 2
/ De (m /s) Da (m /s) Kd (ml/g) De (m2/s) Da (m2/s) Kd (ml/g)
cm3)
Tritium TD-HTO1 1.18 0.56b 1.41 1010 1.03 1010
0.5 1.41 1010
TD-HTO2 1.18 0.56b 1.24 1010 8.89 1011
0.45 1.24 1010
TD-HTO3 1.18 0.56b 1.18 1010 9.80 1011
0.44 1.17 1010
P-1 1.18 0.52/0.14 3.5 109
Strontium TD-Sr5 1.39 0.48b 1.10 109 6.74 1013 1176 8.81 1012 1410
TD-Sr6 1.39 0.48b 1.81 109 7.13 1013 1823 3.44 1012 1200
TD-Sr7 1.65 0.38b 1.25 109 5.47 1013 1383 3.99 1012 1550
TD-Sr8 1.65 0.38b 9.70 1010 5.28 1013 1114 5.61 1012 1300
Cesium ID-Cs-9 1.65 0.42b 8.03 1010 3.34 1013 925.1 3.07 1013 823 121
0.49 8.05 1010 3.32 1013 931.8
ID-Cs-10A 1.57 0.42b 3.3 1010 1.37 1013 924.1 2.51 1013
0.49 3.44 1010 1.43 1013 924.4
ID-Cs-10B 1.57 0.42b 7.57 1010 3.21 1013 907.9 3.51 1013
0.45 8.81 1010 3.39 1013 999.6
Selenium ID-Se-17 1.57 0.42b 4.35 1013 6.51 1014 2.41 6.25 1014 3.35 1.5
0.21 1.73 1013 3.4 1014 1.87
ID-Se-18 1.57 0.42b 1.39 1013 2.29 1014 2.17
0.25 1.23 1013 2.23 1014 2.02
a
Analytical results were obtained by Garca-Gutierrez et al. (2001). Here / denotes diusion-accessible porosity; De is eective diusion coecient; Da is
apparent diusion coecient and Kd is distribution coecient in ml/g.
b
Parameter is xed and therefore not estimated.
 J. Samper et al. / Physics and Chemistry of the Earth 31 (2006) 640648 645

cients. Based on this nding, the sinters were considered for
the interpretation of all the diusion experiments.
In general, the numerical solution matches observed tra-
cer data in both cells (Fig. 4). Eective diusion coecients
for tritium range from 1.17 to 1.41 1010 m2/s which are
within the range of published values for this tracer in bent-
onites (Yu and Neretnieks, 1996). The 95% condence
interval of the estimated eective diusion coecient of
TD-HTO1 is rather small: (1.34 1010, 1.48 1010) m2/
s. The best t to TD tritium data is obtained with diusive
porosities ranging from 0.44 to 0.5 (see Table 1) which are
slightly smaller than the total porosity. Tortuosity factor
ranges from 0.76 to 0.79.
Estimates of porosity and diusion (D0), however, are
strongly correlated as attested by their large computed cor-
relation coecients which are greater than 0.95. Given the
large uncertainties in porosity and diusion coecient, the
value of porosity was xed. Several runs were performed
using porosities ranging from 0.45 to 0.56. These runs led
to similar ts but dierent estimates of D0. Estimates of
4.0
Through-Diffusion 1 (TD-HTO1)
3.5 Observations (IN)
Numerical results (IN)
3.0 Observations (OUT)
Numerical results (OUT)
Activity (Mcount/L)
porosity and D0 always provide a similar values of the
eective diusion coecient. This means that tritium TD
experiments only allow the unambiguous estimation of
the eective diusion coecient.
Four TD experiments were performed using strontium:
TD-Sr5 and TD-Sr6 with a dry density of 1.18 and TD-
Sr7 and TD-Sr8 with a density of 1.39 g/cm3. This tracer
has a large distribution coecient. In fact, the tracer does
not reach the downstream cell after almost 200 days while
it has been fully ushed from the upstream cell after that
time. These experiments were interpreted in two groups.
For TD-Sr5 and TD-Sr6 porosity was xed to a value of
0.48 that corresponds to a dry density of 1.39 g/cm3. For
the second group (TD-Sr7 and TD-Sr8) porosity was xed
to 0.38 that corresponds to a dry density of 1.65 g/cm3. Kd
and D0 were estimated in all four experiments. The best t
is shown in Fig. 4. Eective diusion coecients De range
from 9.7 1010 to 1.81 109 m2/s with a mean value of
1.28 109 m2/s. Estimated values of Kd show also a
wide range (from 1114 to 1823 cm3/g) with a mean of
1374 cm3/g. Estimated results of the apparent diusion
Da show much less scatter (from 5.28 1013 to
7.13 1013 m2/s) with a mean value of 6.15 1013 m2/s.
Estimation errors and condence intervals are similar for
all four experiments. For experiment TD-Sr5, the 95%
condence intervals for the estimates of eective diusion
and Kd are (5.47 1010, 1.65 109) m2/s and (786.6,

2.5
1566) cm3/g, respectively. These values are within the range
2.0 of published values for this tracer in bentonites. It should
be noticed that in this case the estimates of eective diu-
1.5
sion and Kd show consistently a signicant negative corre-
1.0 lation of about 0.5. The inverse analysis indicates that Kd
is the parameter having the largest uncertainty (estimation
0.5
error).
0.0
5.2. In-diusion experiments
0 10 20 30 40 50 60
Time (days)
Several sets of ID experiments were performed on clay
samples having a total porosity of 0.42 which amounts to
25 a dry density of 1.57 g/cm3 using radioactive cesium
Through-Diffusion 5 (TD-Sr5)
Observations (IN)
(137Cs) and selenium SeO2 3 . Tracer activity in the cell
20 Numerical results (IN) was monitored for full duration of the experiment. At the
Observations (OUT) end of the experiment, clay samples were sliced and total
Activity (Mcount/L)

15
Numerical results (OUT) tracer activity was measured in each slice. This activity
includes the activity in the liquid and solid phases, in
Mcount/per gram of sample (clay + water).
10
In order to t the transient liquid activity in the cell and
the nal total activity (including the liquid and solid
5
phases) in the clay at the end of experiments, it is necessary
to translate modeling results from liquid activity to total
0 activity by means of
0 50 100 150 200
/ qd K d
CT CL 11
Time (days) /qw qd

Fig. 4. Numerical interpretation of through diusion experiments: tritium where CT = total activity (Mcount/g), CL = liquid activity
TD-HTO1 (top) and strontium TD-Sr5 (bottom). Upstream (IN cell) and (Mcount/cm3), qd = bulk dry density of the porous med-
downstream (OUT cell) cell activities are shown. ium (g/cm3), and qw = density of water (g/cm3). Therefore,
646 J. Samper et al. / Physics and Chemistry of the Earth 31 (2006) 640648

inverse modeling of ID experiments uses two types of data: cial care should be taken in measuring the activities of the
transient liquid activity in the cell and nal total activity in slices located near the faces of the clay samples.
the clay. The best t is obtained with diusive porosities slightly
Two cesium experiments were available (ID-Cs-9 and larger (0.49) than total porosity (0.42). This result could
ID-Cs-10). In one of them, the behavior of the sample is be caused by Cs diusion through clay interlayers. Diusive
not symmetric, i.e., the tracer diuses on one side faster porosities range from 0.45 to 0.49. Eective diusion coef-
than on the other. In this case, data from each side of cients De range from 3.44 1010 to 8.81 1010 m2/s.
the sample were interpreted separately (tests ID-Cs-10A Estimated values of Kd range from 924.4 to 999.6 cm3/g.
and ID-Cs-10B). The experiments were interpreted in two Apparent diusion coecients range from 1.43 1013 to
stages. First, the porosity was xed to a value of 0.42 while 3.39 1013 m2/s. These values are within the range of pub-
Kd and D0 were estimated. In the second stage, porosity lished values for this tracer in bentonites. Numerical solu-
was also estimated, resulting in an excellent t to measured tions t perfectly measured data (Fig. 5).
nal concentration data. Some discrepancies are observed Two selenium (in the form of SeO2 3 ) experiments were
in the time evolution of tracer activity in the cell which performed on clay samples of 2.5 cm, half the length of
are attributed to uncertainties in the initial activity and the cesium cells. Again, the experiments were interpreted
the lack of well-mixed conditions in the cell. A detailed sen- in two stages. First, the porosity was xed to a value of
sitivity analysis was performed to evaluate the eects of 0.42 while Kd and D0 were estimated. In the second stage,
several sources of uncertainty including: (1) the initial con- porosity was also estimated, resulting in an excellent t
centration in the sinters, (2) the appropriate boundary con- to both nal concentration data and time evolution of
dition for the cell, (3) the initial concentration in the cell, tracer activity in the cell. The best t is obtained with
and (4) the eective volume of the cell. The results of this diusive porosities smaller than total porosity (Fig. 5).
analysis indicate that estimated parameters are very sensi- Diusive porosities are equal to 0.21 and 0.25. Eective
tive to the properties and conditions prevailing at the cell. diusion coecients De range from 1.23 1010 to 1.72
Therefore, for the proper interpretation of this type of 1010 m2/s. Estimated values of Kd range from 1.87 to
experiment we suggest that: (1) only one clay sample 2.02 cm3/g. Apparent diusion coecients range from
should be located in each cell, (2) the initial concentration 2.23 1013 to 3.40 1013 m2/s. Garca-Gutierrez et al.
should be measured as accurately as possible, and (3) spe- (2001) reported diculties in obtaining a unique t to sele-

15

0.25
In-Diffusion-Cs-9
Measurements In-Diffusion-Cs-9
0.20 Model fit 10 Measurements
Activity (Mcount/l)
Activity (Mcount/g)

Model fit
0.15

5
0.10

0.05
0
0.00

0.0 0.1 0.2 0.3 0.4 0.5 0 100 200 300 400 500
Distance (dm) Time (days)
30
0.004
In-Diffusion-Se-18
Measurements 25 In-Diffusion-Se-18
Model fit Measurements
Activity (Mcount/g)

0.003
Activity (Mcount/g)

20 Model fit

15
0.002

10
0.001
5

0.000 0

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0 100 200 300 400 500
Distance (dm) Time (days)

Fig. 5. Numerical interpretation of in diusion cesium ID-Cs-9 (top) and selenium ID-Se-18 (bottom) experiments. (Left gures show the nal total
activities in the clay sample and gures on the right show the concentration evolution in the cell.)
 J. Samper et al. / Physics and Chemistry of the Earth 31 (2006) 640648 647

nium IN diusion experiments that were attributed to
chemical reactions. Selenium could be present in several
oxidation states and form dierent complexes with dierent
properties. Although Se(IV) oxidation into Se(VI) seems
unlikely, Se(IV) could be reduced by Fe (II) or organic mat-
ter inside the clay sample.
5.3. Permeation experiments
Contrary to in- and through-diusion experiments, per-
meation experiments involve advective and dispersive
transport. These experiments are intended to provide infor-
mation on kinematic porosity which measures the volume
of well-interconnected water-owing pores. Permeation
experiments were performed using tritiated water. Follow-
ing the parsimony principle, the classic single-porosity
model was tested rst. For the permeation experiment a
convergent but suboptimal solution is obtained with a
porosity of 0.35 (Fig. 6). Given the limitations of the sin-
gle-porosity model, a more complex double-porosity model
was considered.
In our double-porosity model the domain is divided into
two domains. Let fm and fim be the fractions of the total
25
PERMEATION 1 (P-1)
Measurements
20 Model fit
Activity (Mcount/l)
volume of the sample occupied by the mobile and immobile
domains, respectively. From prior information we set
fm = 0.2 and fim = 0.8. In our formulation of double poros-
ity, model porosities for mobile and immobile zones are not
global porosities, but relative porosities. Let /m and /im be
the relative porosities of the mobile and immobile zones
which are dened as the ratio of void volume to total vol-
ume of each domain. The total porosity of the sample is
given by / = /mfm + /im fim where /mfm is the overall
porosity of the mobile domain and /imfim represents the
overall porosity of the immobile domain. According to
our experience, this way of parameterizing double porosity
is not aected by the geometry adopted in the model.
Therefore, the values /mfm and /imfim are independent of
the model geometry.
The inverse double-porosity model leads to an excellent
t of the activity breakthrough curves (Fig. 6) with relative
porosities /m = 0.73 and /im = 0.65 for which the overall
porosity of the mobile domain is 0.14 and that of the
immobile domain is 0.52. It should be noticed that the esti-
mated total porosity (0.66) is slightly greater than total vol-
umetric porosity (0.56). This could be caused by tritium
accumulation in clay minerals which according to Kalini-
chenko et al. (2002) takes place under room conditions
by a two-stage isotope exchange. Tritium ions rst migrate
from the solution to the bound layers and then substitute
the protons of the structural hydroxyls.
The eective diusion coecient in the mobile phase is
3.5 109 m2/s while that of the immobile phase is almost

15 three orders of magnitude smaller. The longitudinal disper-

sivity for the mobile phase was set equal to one-tenth of the
10 length of the clay sample and was not estimated.

5 5.4. Comparison of numerical estimations with analytical

solutions
0
Standard analytical methods (see Garca-Gutierrez et al.,
0 1 2 3 4 2001) for the interpretation of TD and ID experiments do
Time (days) not take into account the sinters. Such a limitation of analyt-
ical methods can lead to erroneous estimates of diusion
25
coecients. Inverse modeling of tritium TD experiments
Permeation 1 (P-1d)
(Double-porosity) has revealed that for the experimental conditions of FEBEX
20
Measurements bentonite failing to account for the sinters can lead to under-
Model fit
estimation of eective diusion coecients by a factor of 1.4.
Activity (Mcount/l)

15 Analytical methods for the interpretation of ID experi-

ments rely entirely on activity data measured at the end
10 of the experiment. They make no use of data measured
at the immersion cell and allow only the estimation of
5 apparent diusion coecient and /R (see Eq. (2)). Inverse
modeling, on the contrary, allows the estimation of trans-
0 port and sorption parameters by using simultaneously both
nal total activities and time evolution of activities in the
0 1 2 3 4 immersion cells.
Time (days) Numerical methods are better suited than analytical
Fig. 6. Numerical interpretation of tritium permeation experiment. methods especially for the interpretation of permeation
Computed activities (lines) and measured data (symbols) are shown for experiments which may require time-varying pulse func-
single-porosity (top) and double-porosity (bottom) models. tions and double porosity models for bentonite.
648 J. Samper et al. / Physics and Chemistry of the Earth 31 (2006) 640648
Limitations of analytical methods may lead to biased
estimates of diusion coecients. According to the com-
parison shown in Table 1, such a bias is about a factor
of 1.4 for the eective diusion coecient of tritium and
an order of magnitude for the apparent diusion coecient
of strontium. However, the biasness is rather small for the
apparent diusion and the distribution coecient of Cs
and Se (Table 1).
6. Conclusions
Diusion and permeation experiments performed on
FEBEX compacted bentonite using tritium, cesium, sele-
nium, and strontium have been eectively interpreted by
inverse modeling. Contrary to standard analytical meth-
ods, numerical inverse modeling allows an ecient, fast
and optimum interpretation of these experiments. It has
been found that failing to account for some experimental
conditions may lead to erroneous diusion coecients
which for the experimental conditions of FEBEX bentonite
could deviate from true values by a factor of 1.4.
Inverse modeling of permeation experiments allows the
use of time-varying pulse functions and double porosity
models for bentonite. Numerical methods have proved use-
ful for indicating identiability problems and suggesting
possible improvements in experimental conditions such as
measuring directly the eective diusion coecient of por-
ous sinters.
Possible improvements for in-diusion experiments
include: (1) Determining accurately the initial tracer con-
centration and the eective volume of the cells; and (2)
Obtaining detailed and accurate concentration proles,
especially near the faces of the clay samples, and using only
one clay sample in each cell.
In our work the porosity and the eective diusion of
the sinters were taken from manufacturer technical speci-
cations. However, it is recommended to determine these
parameters experimentally by means of diusion experi-
ments to reduce unneeded uncertainties.
The duration of the tracer pulse should be much smaller
than the duration of the permeation experiment. Other-
wise, the concentration of the inow water should be care-
fully measured. Similar to other clays, FEBEX bentonite
exhibits a complex porosity structure. Two types of poros-
ities can be distinguished: a mobile porosity along which
porewater ows and an immobile porosity where water
does not ow while only molecular diusion takes place.
The results of the tritium permeation experiment per-
formed on FEBEX bentonite indicate that mobile porosity
is 0.14 for a dry density of 1.18 g/cm3.
Acknowledgement
This work was supported by the Spanish Nuclear Waste
Company (ENRESA) within the framework of the FEBEX
Research Project through Research Grants signed with the
University of La Coruna (Contracts 70323 and 770045).
The FEBEX Project as a whole is funded by the EC (Pro-
jects FI4W-CT95-0008 and FIKW-CT-2000-0016) within
the Nuclear Fission Safety Programme. We gratefully
acknowledge the assistance of John Apps of LBNL. We
thank the two anonymous reviewers for their thoughtful re-
views of the paper which contributed to improve it.
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