Journal of Contaminant Hydrology 98 (2008) 115127

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Journal of Contaminant Hydrology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / j c o n h yd

Inverse modeling of multicomponent reactive transport through single and

dual porosity media
Javier Samper a,, Liange Zheng a, Ana Mara Fernndez b, Luis Montenegro a
a
ETS Ingenieros de Caminos, Canales y Puertos, Universidad de La Corua, Campus de Elvia s/n, 15192, Spain
b
CIEMAT, Avenida Complutense, 22. 28040, Madrid, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep
Received 20 March 2007 geological repositories because it provides hydraulic isolation, chemical stability, and
Received in revised form 13 March 2008 radionuclide sorption. A wide range of laboratory tests were performed within the
Accepted 15 March 2008
framework of FEBEX (Full-scale Engineered Barrier EXperiment) project to characterize buffer
Available online 26 March 2008
properties and develop numerical models for FEBEX bentonite. Here we present inverse single
and dual-continuum multicomponent reactive transport models of a long-term permeation
Keywords:
test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater
Inverse model
was ushed with 5.5 pore volumes of fresh granitic water. Water ux and chemical composition
Multicomponent reactive transport
FEBEX bentonite of efuent waters were monitored during almost 4 years. The model accounts for solute
Single-continuum model advection and diffusion and geochemical reactions such as aqueous complexation, acidbase,
Dual-continuum model cation exchange, protonation/deprotonation by surface complexation and dissolution/
precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local
equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems
which attest the relevance of protonation/deprotonation on buffering pH, our results conrm
that protonation/deprotonation is a key process in maintaining a stable pH under dynamic
transport conditions. Breakthrough curves of reactive species are more sensitive to initial
porewater concentration than to effective diffusion coefcient. Optimum estimates of initial
porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the
inverse problem of multicomponent reactive transport. While the single-continuum model
reproduces the trends of measured data for most chemical species, it fails to match properly the
long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-
continuum reactive transport model.
2008 Elsevier B.V. All rights reserved.

1. Introduction out in fractured granites. FEBEX (Full-scale Engineered Barrier

Underground facilities are being operated by several
countries around the world for performing research and
providing demonstration of the safety of a deep geological
high-level radioactive waste (HLW) repository. The Grimsel
test site at Switzerland is one of such facilities launched and
operated by the Swiss Nuclear Waste Management Company
(NAGRA) where various in situ experiments have been carried
Corresponding author.
E-mail address: jsamper@udc.es (J. Samper).
EXperiment) in situ experiment is part of a larger demonstra-
tion and research project launched by the Spanish Nuclear
Waste Management Company (ENRESA) for the engineered
bentonite barrier of a HLW repository. FEBEX is based on the
Spanish reference concept for radioactive waste disposal in
crystalline rock according to which canisters are emplaced in
horizontal galleries and surrounded by a compacted bento-
nite clay barrier (ENRESA, 1998). This bentonite comes from
the Cortijo de Archidona mine, at Serrata de Njar (Almera,
Spain), has very large montmorillonite content, large swelling
pressure, low hydraulic conductivity, and good retention
properties. Before compaction, bentonite was homogenized

0169-7722/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jconhyd.2008.03.008
116 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127
to reduce uncertainties (ENRESA, 1998). Predictions of water
ow and solute transport in compacted bentonite are
essential for the long-term assessment of a HLW repository
(Alonso and Ledesma, 2005).
Performance assessment of a HLW repository requires
knowing the porewater composition of the clay barrier.
Hydrogeochemical modeling of FEBEX bentonite porewaters
show that main geochemical processes controlling the chem-
istry of the bentonite are: acidbase, aqueous complexation,
cation exchange, protonation/deprotonation by surface com-
plexation and dissolution/precipitation of highly soluble miner-
als, such as calcite, chalcedony, gypsum and possibly dolomite
(Fernndez et al., 2001, 2004; Samper et al., 2005b, 2008).
Compacted bentonite exhibits a complex porosity structure
with interlayer (210 ), intraaggregate (micropores b 50 ) and
interaggregate (macropores: 50200 ) pores (Bradbury and
Baeyens, 2003; Fernndez et al., 2004). There is a clear need for
complex porosity models for bentonites. The term dual
porosity is often used to denote a conceptual model in which
the medium is divided into two or more domains or regions
which are coupled by an interaction term for modeling ow and
solute transport. There can be two mobile domains (Gwo et al.,
1995) or a mobile and an immobile domain. Dual porosity
models were initially introduced by Barenblatt et al. (1960) to
simulate single-phase ow in ssured groundwater reservoirs
by assuming that the medium consists of two connected
continua. A continuum is associated with the network of
fractures while the second one is made of matrix blocks. Dual
porosity models have been also used in soils to account for
macropores (or interaggregate pores) and intraaggregate pores.
Mobileimmobile ow and solute transport has been modeled
by two conceptual models: (1) two ow and transport equations
with mass-transfer coupling terms, or (2) ow and transport in
two regions with coupling boundary conditions. The dual
porosity concept has been commonly used to describe the
preferential movement of water and solutes at the macroscopic
scale (Boudreau, 1997; Schwartz et al., 2000) and variably-
saturated fractured rock formations and structured soils (Gerke
and van Genuchten, 1993a,b, 1996; Ray et al., 1997; Larsson and
Jarvis, 1999; Lichtner, 2000; imunek et al., 2003). Scientists
have used this conceptual model to predict leaching of
pollutants into soils and groundwaters (Hantush et al., 2000,
2002; Hantush and Govindaraju, 2003) and solute transport
through clay soils (Jarvis et al., 1991a,b). Adsorption in dual-
continuum models (DCM) has been considered by van Genuch-
ten and Wagenet (1989), Larsson and Jarvis (1999), Schwartz
et al. (2000) and Hantush and Govindaraju (2003). Lichtner
(2000) considered aqueous complexation and mineral precipi-
tationdissolution in a DCM for a synthetic case of reactive
transport in fractured rocks. Dual-continuum models (DCM)
involve more parameters than single-continuum models (SCM).
Deriving DCM parameters from measurements is difcult.
Recently some researchers have called for the use of inverse
modeling techniques. Schwartz et al. (2000) estimated DCM
parameters of a tropical soil by inverse modeling using steady-
state bromide breakthrough data. They found difculties in
obtaining realistic estimates of dispersion coefcient in micro-
pores. On the other hand, Ktterer et al. (2001) estimated
successfully DCM parameters of undisturbed columns from
breakthrough curves of conservative tracers. Larsbo and Jarvis
(2005) evaluated data requirements for parameter identica-
tion of DCM. They conditioned parameters on water content,
drainow and concentrations of tracers and a pesticide.
However, no experience is available on inverse modeling of
compacted bentonite.
It is difcult to obtain reliable data for porewater chemistry
of compacted bentonite. Squeezing and aqueous extracts tests
alter the system in several ways and introduce sampling artifacts
into the resulting data (Muurinen and Lehikoinen, 1999; Sacchi
et al., 2001). Squeezing at high pressures may produce the
oxidation and dissolution of accessory minerals of bentonite and
CO2(g) outgassing. Furthermore, squeezing does not allow
extracting porewater from bentonites at low water contents.
The aqueous extract method provides a method to quantify the
total content of soluble salts because it works with a low solid-
to-liquid ratio. Since mineral dissolution of various soluble
minerals as well as cation exchange processes takes place during
the extraction, indirect methods based on hydrogeochemical
modeling are needed to infer the porewater chemical composi-
tion (Fernndez et al., 2004; Zheng et al., 2008).
FEBEX porewater chemistry data have been analyzed in
detail by different methods (Fernndez et al., 2001; Zheng et al.,
2008). A permeation test was performed by CIEMAT (Research
Centre for Energy, Environment and Technology) to obtain di-
rectly porewater chemistry of FEBEX bentonite. Porewater solu-
tion of a saturated bentonite sample was ushed with granitic
water. Breakthrough curves of pH and chemical species were
monitored for almost 4 years. Here we present an inverse multi-
component reactive transport model for the interpretation of
CIEMAT permeation test. The paper starts with a description of
the test. Afterwards, details of numerical model are given. Nu-
merical results for inverse single-continuum model (SCM) are
presented. Limitations of SCM are overcome by a DCM model.
The paper ends with a discussion of the main uncertainties and
conclusions.
2. Description of permeation test
The experimental column used for the permeation test
consists on a stainless steel cell in which a sample of FEBEX
compacted bentonite is subjected to water ow (Fig. 1). The cell
has an internal diameter of 5 cm and a length of 2.5 cm. It contains
99.7 g of dry bentonite and 19.09 mL of water. A HPLC pump
injects a solution at a nearly-constant pressure of 4 MPa through a
porous stainless steel lter providing a nearly-constant ow rate
of approximately 2 mL/month. Outow water comes out through
another stainless steel lter and is sampled inside a syringe.
Porous steel lters are needed to ensure a homogeneous
distribution of inow and outow water in contact with bentonite
and prevent swelling and generation of bentonite colloids.
The test started on September 29th 1998 and lasted for
1393 days. Water samples of 2 mL were taken once the cell
delivered enough which were used to perform a complete
chemical analysis. Most samples were taken at regular
monthly intervals, except for the rst one which took a longer
period of 69 days, possibly because the sample of compacted
bentonite was not fully saturated. A total of 44 aliquots were
obtained during the duration of the test. A total volume of
106 mL (which amounts to 5.5 pore volumes) was collected
after 1393 days. Chemical data for all 44 samples are listed in a
table available at the Supplemental information Section of the
journal. Measurement errors of chemical analyses are equal to
 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127 117

and Dirichlet ow boundary conditions were tested by

Fig. 1. Schematic design of the permeation test (Samper et al., 2005a).
25% for K+, 20% for HCO3 and 10% for the rest of chemical
species (Muurinen, 2001). Charge balance errors were com-
puted for samples having complete analysis. Data for t = 727
and 785 days have charge balance errors larger than 15% due
to abnormally large Ca2+ concentrations and were not
considered for model calibration. K+ data for t = 377, 450 and
481 days were discarded because they are abnormally large.
Chemical composition of inow granitic water is listed in
Table 1. Given the difculties of deriving reliable data on
bentonite porewater chemistry, we adopted as prior estimate
of initial composition of bentonite porewater that derived by
Samper et al. (2005b) from a squeezing experiment (see Table 1).
The major mineral of FEBEX bentonite is a CaMgNa
montmorillonite (9092 wt.%). Its saturated hydraulic conductiv-
ity is 2.910 14 m/s. FEBEX bentonite has undergone an extensive
laboratory mineralogical, geochemical, thermal, hydrodynamic
and mechanical characterization (ENRESA, 1998, 2006a).
3. Numerical model
3.1. Flow and solute transport model
Samper et al. (2005a) who concluded that a Dirichlet
condition provides a better description of chloride break-
through curve. Therefore, a steady-state ow model was
adopted with pressures of 4 MPa at the inlet and atmospheric
pressure at the downstream end, resulting in a constant Darcy
velocity, q, of 10 10 m/s. Computed cumulative water inows
compare well with measured values (see Fig. 2). Measured
uxes at the beginning of the test are smaller than computed
values probably because the bentonite sample was not fully
saturated at the beginning of the test.
Besides bentonite, the model accounts for upstream and
downstream steel lters. According to manufacturers, poros-
ity of lters is 0.5. There are no measurements of hydraulic
conductivity and effective diffusion coefcients of lters. Their
conductivity was assumed to be several orders of magnitude
larger than that of bentonite. Their effective diffusion
coefcient was taken equal to 1.48 10 10 m2/s. Uncertainties
in lter parameters were studied by means of sensitivity runs.
Their results show that breakthrough curves are not sensitive
to changes in lter parameters.
A mixed-type boundary condition was used for solute
transport at inow and outow boundaries. Solute ux at the
outlet boundary is equal to solute concentration times computed
water ux while solute ux at inlet is equal to water ux times
boundary concentration (van Genuchten and Parker, 1984).
Prior estimates of effective diffusion coefcients, De, for
bentonite were taken from those used by Samper et al.
(2005a) for modeling FEBEX mock-up and in situ experiments.
Even though effective diffusion coefcients are species
dependant, here we assume that all chemical species have
the same De of 5 10 11 m2/s because this assumption provides
acceptable results in other FEBEX experiments (ENRESA,
2006b). Dispersivity of FEBEX bentonite is very small because
it was homogenized during its manufacturing. Molecular
diffusion dominates over dispersion. Peclet number is much
smaller than 1, corroborating that diffusion dominates largely
over advection.
Cl is a species suffering anion exclusion. Its accessible
porosity, a, is smaller than total porosity, . Transport
equation for this species is similar to that of a conservative
species, except for porosity which is replaced by accessible
porosity (see Samper et al., 2003a,b).

The experiment was performed by prescribing a constant

hydraulic gradient with a nearly-constant ow rate. Neuman

Table 1
Chemical composition of inow granitic water and initial bentonite
porewater composition (mol/L) taken from Samper et al. (2005b)

Initial bentonite porewater Inow granitic water

pH 7.94 8.15
Cl 1.12 10 1 3.81 10 4
SO2
4 1.27 10 2 1.46 10 4
HCO3 6.45 10 4 2.37 10 3
Ca 2+
6.34 10 3 9.98 10 4
Mg2+ 8.82 10 3 3.67 10 4
Na+ 1.14 10 1 5.0 10 4
Fig. 2. Comparison of measured (symbols) and computed cumulative water
K+ 1.04 10 3 2.56 10 4
outow using a Dirichlet ow boundary condition.
118 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127

Table 2 Table 3
Equilibrium constants for aqueous complexes and mineral reactions (Wolery, Initial mineral volume fractions, exchanged cation occupancies and surface
1992), selectivity coefcients for cation exchange reactions (Fernndez et al., site capacities of FEBEX bentonite
2004), and protolysis constants for surface complexation reactions (Bradbury
and Baeyens, 2003) at 25 C dening the geochemical conceptual model Solid property Volume fraction/concentration
Calcite 0.01
Aqueous complexes Log K
Quartz 0.0045
CaCl+ Ca2+ + Cl 0.6956
Gypsum 0.00
CaCO3(aq) + H+ Ca2+ + HCO3 7.0017
Na+ (meq/100 g) 21.16
CaHCO+3 Ca2+ + HCO3 1.0467
K+ (meq/100 g) 2.02
CaSO4(aq) Ca2+ + SO2 4 2.1111
Ca+2 (meq/100 g) 37.15
CO2(aq) + H2O H+ + HCO3 6.3447
2 + Mg2+ (meq/100 g) 35.47
CO3 + H HCO3 10.3288
`SSOH (mol/kg) 2.0 10 3
H2SiO2 +
4 + 2 H 2 H2O + SiO2(aq) 22.9116
`Sw1OH (mol/kg) 4.0 10 2
HSiO3 + H+ H2O + SiO2(aq) 9.9525
`Sw2OH (mol/kg) 4.0 10 2
KSO4 K+ + SO24 0.8796
MgCl+ Mg2+ + Cl 0.1349
MgCO3(aq) Mg2+ + CO3 2 2.9789
MgHCO+3 Ca2+ + HCO3 1.0357 lysis constants (see Table 2) and site concentrations for each
MgSO4(aq) Mg2+ + SO2 2.4117
4
type of sorption site (Table 3). Models with up to three types
NaCl(aq) Na+ + Cl 0.7770
NaHCO3(aq) Na + HCO3
+
0.1541 of protolysis sites (SSOH, Sw1OH and Sw2OH) are con-
NaSO4 Na+ + SO2 4 0.8200 sidered (Bradbury and Baeyens, 1997).
OH + H+ H2O 13.9951 Fluctuations in laboratory ambient temperature have a
Minerals Log K negligible inuence on chemical reactions. Therefore, calcula-
Calcite + H+ Ca2+ + HCO3 1.8487
Chalcedony SiO2(aq) 3.7281
tions were performed at a constant temperature of 25 C.
Gypsum Ca2+ + SO2 4 + 2H2O 4.4823 Table 2 lists chemical reactions and their equilibrium
Exchanged cations KNa-cation constants at 25 C for aqueous complexes and minerals,
+ +
Na + XK K + XNa 0.096 selectivity coefcients for exchangeable cations and protolysis
Na+ + 0.5X2Ca 0.5Ca2+ + XNa 0.237
constants for surface complexation. Initial mineral volume
Na+ + 0.5X2Mg 0.5Mg2+ + XNa 0.269
Surface complexes Log Kint fractions, exchanged cation occupancies and surface site
`SsOH+2 `SsOH + H+ 4.5 capacities of FEBEX bentonite are listed in Table 3.
`SsO + H+ SsOH 7.9
`Sw1 OH+2 `Sw1OH + H+ 4.5 3.3. Inverse model
`Sw1 O + H+ `Sw1OH 7.9
`Sw2 OH+2 `Sw2OH + H+ 6.0
`Sw2 O + H+ `Sw2OH 10.5 Our formulation of the inverse problem is that of Dai and
Samper (2004) which is based on generalized least squares.
Let p = (p1, p2, p3, , pM) be the vector of M unknown
parameters. The objective function, E(p), can be expressed as,
3.2. Geochemical model
X
N N X
X Li
One of the main uncertainties in the interpretation of the E p Ei p w2li rli2 p 1
permeation test is related to the geochemical model. Fernndez i1 i1 l1
et al. (2001, 2004) proposed a geochemical model based on
rli p cil p  Cli
aqueous extract data while Samper et al. (2005b) derived a
geochemical model from squeezing experiments. Their geo- P
where i 1; N denotes different chemical species, cil(p) is
chemical models differ mostly on sulphate and sodium
computed value of the i-th variable at the l-th time; Cil are
concentrations. Here we use the geochemical model of Samper
measured values; Li is the number of observations for the i-th
et al. (2005b) because it is based on experimental conditions
close to those of the permeation test.
The geochemical model accounts for aqueous complexa-
tion, acidbase, mineral disolution/precipitation, surface
protonation/deprotonation and cation exchange. The chemi-
cal system is dened in terms of the following primary
species: H2O, H+, Ca2+, Mg2+, Na+, K+, Cl, SO2
4 , HCO3 and SiO2
(aq). Relevant aqueous complexes were identied from
speciation runs performed with EQ3NR (Wolery, 1992), a
code for geochemical aqueous speciation-solubility calcula-
tions. Calcite, chalcedony and gypsum are assumed at local
equilibrium. Equilibrium constants at 25 C for aqueous
complexes and minerals were taken from EQ3NR database
(see Table 2). The GainesThomas convention is used for
cation exchange (Appelo and Postma, 1993). Surface com-
plexation is modeled with a constant-capacitance double
diffuse layer model (Dzombak and Morel, 1990; Xu et al., Fig. 3. Measured and computed breakthrough curves of pH with 1 and 3
1999). Parameters for surface complexation include: proto- types of sorption sites and without proton sorption for a SCM.
 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127 119

species; rli is the residual or difference between computed

Fig. 4. Measured and computed SCM breakthrough curves of chloride.
and measured concentrations and wli are weights given to
concentration residuals. In a statistical framework such
weights are inverse standard deviations of residuals reecting
the fact that residuals contain errors. If a residual has a small
standard deviation, the algorithm tries to force its computed
value to t the measured value. On the contrary, if the
standard deviation is large, deviations from measured values
are larger. Estimation errors of residuals have an experimental
component associated with measurement, analytical and
interpretation errors. Residuals may contain also computa-
tional as well as conceptual errors arising from inappropriate
or oversimplied conceptualization of processes and spatial
variability. Only the statistical structure of measurement
errors is known a priori (Carrera and Neuman, 1986). This is

Fig. 5. Measured and computed breakthrough curves of SO2 2+ 2+ + +
4 , Mg , Ca , Na , K and HCO3 with direct and inverse SCM (steps 1 and 2).
120 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127

why often modelers use weights equal to the reciprocal of
standard deviations of measurement errors. Since concentra-
tions of different chemical species usually vary within
different logarithmic ranges, weights must contain a spe-
cies-dependant characteristic value to avoid the overwhelm-
ing effect of the most abundant chemical species.
Here we use the weighting scheme proposed by Dai and
Samper (2004) according to which weights are computed as:
e li
w Molinero et al., 2004; Dai and Samper, 2004; Molinero and
wli
ri
where w li is a dimensionless user-specied weight for the l-
th measured value and i is the standard deviation of
measured concentrations of the i-th species,
v
u Li 
u X P 2
ri tLi  11 Cli  Ci
l1
P
where Ci is the average measured concentration of the i-th
species. Dimensionless weights w li take a default value of 1.
Unreliable data are given smaller weights to prevent their
pernicious effect on estimation results. Chemical species such
as K+ and HCO3 having measurement errors larger than those
of other species are given smaller weights.
The GaussNewtonLevenbergMarquardt method is
used to minimize the objective function arising in the
formulation of the inverse problem.
Statistical measures of parameter uncertainty such as
variances of parameter estimation, correlation coefcients
and approximate condence intervals are computed from the
covariance matrix of parameter estimates. Additional details
of the inverse model can be found in Dai and Samper (2004).
Simulations of permeation test were performed with
CORE2D V4 (Samper et al., 2003a), an extended version of
TRANQUI (Xu et al., 1999). Uncertain parameters were esti-
mated by solving the inverse reactive transport problem with
INVERSE-CORE2D (Dai and Samper, 2004). Both CORE2D and
INVERSE-CORE2D are Galerkin nite element codes which solve
for groundwater ow, heat transport and multicomponent
reactive solute transport in saturated/unsaturated steady or
transient groundwater ow under general boundary conditions
in 1-, 2- or 3-D axisymmetric conditions. They account for acid
base, redox, aqueous complexation, surface adsorption via
surface complexation, cation exchange, mineral dissolution/
precipitation, and gas dissolution/ex-solution. Parameters for
surface complexation include protolysis constants and site
concentrations for each type of sorption site. Coupled transport
and chemical equations are solved by the sequential iterative
approach. These codes have been used to model laboratory (Dai
and Samper, 2004) and in situ tests (Samper et al., 2006a, 2006c,
Zhang et al., 2008), eld case studies (Samper et al., 2003b;
4
Samper, 2004, 2006; Dai and Samper, 2006; Dai et al., 2006;
Samper and Yang, 2006), analyze stochastic cation exchange
reactive transport in aquifers (Samper and Yang, 2006) and
evaluate long-term geochemical conditions in radioactive
waste repositories in granite (Yang et al., 2007) and clay (Yang
et al., 2008).
4. Model results
5
4.1. Relevance of surface complexation
Protonation/deprotonation by surface sorption is a key
process controlling pH and bentonite porewater chemistry
(Fernndez et al., 2001, 2004). Previous studies have considered
mostly only one type of proton sorption sites (Wieland et al.,
1994; Samper et al., 2005a). However, Bradbury and Baeyens
(1997) argue that three types of proton adsorption sites are
needed to describe titration data on SWy-1 montmorillonite
and Ni/Zn sorption isotherms. Results for three types of sites are
compared with those of a model with one type of proton sites
having the same total site concentration of 8.2 10 2 mol/kg and
protolysis constants (log K) equal to 5.0 and 8.7, respectively.
These calculations are performed using the initial concentra-
tions listed in Table 1. One can see in Fig. 3 that both models lead
to similar results. Numerical results show also that protonation/
deprotonation by surface sorption is a key process in buffering
pH because a model without proton sorption cannot t
measured pH data (see Fig. 3). Since computed values of pH
with both models are similar, the simplest model with one type
of sorption site was used for the rest of models.
4.2. Inverse Single-continuum model (SMC)
Chloride is a conservative species which exhibits anion
exclusion (Garca-Gutirrez et al., 2006). Its transport para-

Table 4
Effective diffusion coefcients, De (m2/s), initial concentrations, ci, (mol/L) and pH for base run of direct SCM and estimated in steps 1 and 2 of inverse SCM

Parameters Base run Estimates for Estimates for 95% condence intervals for Estimates for inverse SCM step 2
inverse SCM step 1 inverse SCM step 2 inverse SCM estimates step 2 (smaller weights for K+ and HCO3)
De 5.70 10 11 9.51 10 12 (3.02 10 12, 1.62 10 11) 8.43 10 12
ci of Ca2+ 6.34 10 3 1.34 10 2 1.24 10 2 (8.48 10 3, 1.43 10 2) 1.22 10 2
ci of Mg2+ 8.82 10 3 20 10 2 1.60 10 2 (1.16 10 2, 1.74 10 2) 1.56 10 2
ci of Na+ 1.14 10 1 1.14 10 1 1.18 10 1 (9.79 10 2, 1.31 10 1) 1.13 10 1
ci of K+ 1.04 10 3 5.74 10 4 5.94 10 4 (2.16 10 4, 9.46 10 4) 5.61 10 4
ci of SO2
4 1.27 10 2 3.84 10 2 3.50 10 2 (3.04 10 2, 3.77 10 2) 3.60 10 2
ci of HCO3 6.45 10 4 4.02 10 4 4.24 10 4 3.60 10 4
Initial pH 7.94 7.92 7.92 (7.69, 8.10) 7.92

Initial concentrations of HCO3 in steps 1 and 2 are computed from equilibrium with calcite. Last column corresponds to the case when K+ and HCO3 data are given
smaller weights.
 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127 121

Table 5
Objective function and partial contributions of each chemical species for direct and inverse SCM and DCM

Models Objective Partial contributions

function
pH Ca2+ Mg2+ Na+ K+ SO2
4 HCO3
Direct SCM 662.3 0.158 50.10 68.40 19.90 231.00 242.00 50.4
Inverse SCM step 1 123.4 0.160 3.90 7.39 22.00 17.80 7.44 64.7
Inverse SCM step 2 121.5 0.163 3.76 1.88 24.50 15.80 9.41 66.0
Inverse SCM step 2 (smaller weights for K+ and HCO3) 38.0 0.163 4.10 1.80 19.10 0.44 8.44 4.1
Inverse DCM 82.6 0.158 3.07 4.29 7.41 15.60 3.57 48.5

The last column corresponds to the case when K+ and HCO3 data are given smaller weights. Unless specied, all chemical species are given the same weight.

meters are estimated separately from those of the rest of
chemical species. The direct model without exclusion and an
efcient diffusion, De, of 5 10 11 m2/s fails to reproduce Cl
breakthrough curve (Fig. 4) which depends on De, initial
concentration and accessible porosity, a. Initial concentra-
tion affects computed concentrations mostly during the rst
pore volume. Fig. 1 in the Supplemental information shows
that computed concentrations for t N 400 days are much
smaller than measured data even if the initial concentration is
increased from 0.112 mol/L (reference value) to 0.18 mol/L.
The sensitivity analysis of chloride breakthrough curve to
changes in De shows that the model cannot t measured data
by changing De (see Fig. 2 in the Supplemental information).
Computed chloride breakthrough curve is very sensitive to
accessible porosity (see Fig. 3 in the Supplemental informa-
tion). However, there is no accessible porosity for which
model matches measured data.
The best t to measured breakthrough curve is achieved
by inverse estimation of a and De while initial concentration
is xed to its reference value of 0.112 mol/L. The best
estimates are a = 0.219 and De = 6.33 10 12 m2/s. The latter
is an order of magnitude larger than that obtained by Garca-
Gutirrez et al. (2006) of 9.3 10 13 m2/s for FEBEX bentonite
from through-diffusion experiments. These values lead to a
good t to measured breakthrough curve for t b 400 days.
However, model results underestimate noticeably measured
concentrations for t N 400 days (Fig. 4). Simultaneous estima-
tion of a and De fails to t measured data even if larger
weights are given to late concentration data. In other words,
the mist of SCM model to late-time Cl data cannot be
attributed to inappropriate choice of inverse weights, wli, in
Eq. (1). Given the limitations of SCM, a dual-continuum model
is postulated for the long tail of Cl breakthrough curve.
Breakthrough curves of reactive species computed with a
single-continuum model (SCM) reproduce the general trends
of measured data, but show discrepancies at early times and
fail to t the long tails of measured data (see Fig. 5). These
deviations are overcome by inverse estimation of initial
porewater concentrations and effective diffusion coefcient.
Estimation is performed in two steps. Initial concentrations of
Ca2+, Mg2+, Na+, K+, SO2
4 and pH are estimated in step 1 while
step 2 is devoted to the simultaneous estimation of effective
diffusion coefcient and initial concentrations and pH.
Estimates of initial concentrations and effective diffusion
coefcient obtained in steps 1 and 2 are listed in Table 4. It
should be noticed that initial HCO3 concentrations in steps 1
and 2 are not estimated, but computed from chemical
equilibrium with respect to calcite. Results of direct and
inverse models of steps 1 and 2 are compared to measured
breakthrough curves in Fig. 5. Estimation of initial concentra-
tions leads to a signicant improvement in the t to measured
breakthrough curves of almost all species. In fact, the
objective function in Eq. (1) decreases from 662.3 to 123.4
by estimating initial concentrations. Estimates of initial Na+
concentration and pH coincide with reference values (those of
the direct or base run). Estimates of initial concentrations of
Ca2+, Mg2+ and SO2 4 are larger than reference concentrations
by a factor of 2 to 3 while optimum estimates of initial K+ and
HCO3 concentrations are smaller than reference values.
The improvement achieved by estimating effective diffu-
sion coefcient, De, besides initial concentrations, is less
signicant and the objective function experiences a mild
reduction from 123.4 to 121.5 (see Table 5). Estimates of initial
concentrations in step 2 are almost similar to estimates of
step 1. Optimum estimate of De is equal to 9.51 10 12 m2/s.
Bicarbonate and sodium contribute the most to the objective
function. On the other hand, contribution of pH is extremely
small (see Table 5). Breakthrough curves of pH computed with
inverse SCM in steps 1 and 2 (not shown here) are similar to
that of the direct SCM shown in Fig. 3.
Weights w li in Eq. (4) are all equal to 1 except for Ca2+ data
at t = 727 days and K+ data at t = 69 and 727 days which are
unreliable and are given a smaller weight of 0.1 to prevent
their insidious effect on estimation results. The effect of larger
measurement errors for K+ and HCO3 was evaluated by
performing and additional run of inverse SCM of step 2 with
weights for K+ and HCO3 data which are smaller than the
weights of other species. Since HCO3 measurement errors are
2 times larger than those of other species, weights for HCO3
are 4 times smaller than others. In a similar manner, weights
for K+ are 6.25 smaller than those of other species. Although
the objective function lessens signicantly due to the
decrease of K+ and HCO3 contributions (see Table 5),
Table 6
Correlation matrix of parameter estimates for SCM inverse model (step 2)
De ci of Ca+2 ci of Mg+2 ci of Na+ ci of K+ ci of SO2 Initial
4
pH
De 1
ci of Ca+2 0.06 1
ci of Mg+2 0.05 0.98 1
ci of Na+ 0.07 0.98 0.99 1
ci of K+ 0.05 0.53 0.53 0.54 1
ci of SO2
4 0.01 0.99 0.99 0.99 0.54 1
Initial pH 0.02 0.98 0.99 0.99 0.53 0.23 1
122 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127

Fig. 6. Finite element grid used for DCM with a detailed zoom of porous lter (material 3), mobile zone (material 1) and immobile zone (material 2). Top and bottom
sides of the domain are assumed impervious.

parameter estimates are not affected signicantly by weights
of K+ and HCO3 data (Table 4).
Although inverse modeling improves the t to measured
breakthrough curves, computed concentrations of SO2 2+
4 , Mg ,
+
Na and HCO3 deviate from measured values at large times.
Such deviations could be caused by uncertainties in selectiv-
ity coefcients, cation exchange capacity, CEC, mineral phases
other than those listed in Table 2 and dual porosity behaviour
of bentonite.
To evaluate the uncertainty in selectivity coefcients and
its effect on Na+ breakthrough curve, an inverse run of SCM
was performed by estimating the 3 cation selectivity
coefcients. Upper (lower) bounds for selectivities were set
equal to an order of magnitude larger (smaller) than ref-
erence values. This inverse run improves slightly the t to
Na+ and HCO3 data, but leads to worse t for Ca2+ and Mg2+
(not shown here). Cation selectivities are much smaller than
those reported by Fernndez et al. (2004). On the other
hand, changes in CEC of 5% around its reference value of
95.8 meq/100 g do not affect cation breakthrough curves.
Therefore, it can be concluded that model deviations are not
caused by uncertainties in cation selectivities and CEC.
Another source of model uncertainty is related to mineral
phases such as dolomite and gypsum which are not considered
in the model. An additional inverse run was performed by
assuming that the sample contains an initial volume fraction of
gypsum of 0.08%. This run leads to results much worse than
those of a model without initial gypsum because gypsum
dissolution results in excessively large initial sulphate and
calcium concentrations which in turn lead to large concentra-
tions of other cations due to cation exchange. A model with an
initial volume fraction of dolomite of 0.6% improves the t to
measured Na+, but gets worse for most other species. In fact, the
objective function increases from 121 to 240.
Statistical measures of parameter uncertainty such as
variances of parameter estimation, correlation coefcients
and approximate 95% condence intervals have been derived
from the covariance matrix of parameter estimates for inverse
SCM step 2. Correlation coefcients of parameter estimates are
listed in Table 6. The estimate of De is clearly uncorrelated with
other parameter estimates. The rest of parameter estimates
have correlation coefcients of 1 except for initial K+
concentration which has coefcients of 0.5. Initial concen-
trations are positively correlated among themselves and
negatively correlated with initial pH. Such negative correla-
tion is caused by equilibrium with calcite which requires pH to
decrease (increase) when dissolved Ca2+ increases (decreases).
Positive correlations among initial concentrations of cations
are caused by cation exchange reactions which depend on the
ratios of cation concentrations.
Large correlations among parameter estimates do not lead
in our case to large estimation errors because estimation
variances are generally small. Approximate 95% condence
intervals are narrow except for effective diffusion and initial
K+ concentration (see Table 4). The large scatter in K+ data
causes uncertainties in initial K+ concentration (see Fig. 5).
On the other hand, the condence interval of De is large due to
the limitations of SCM which cannot capture concentrations at

Table 7
Sensitivity analysis of chloride breakthrough curve to effective diffusion coefcients and accessible porosities, a, of mobile and immobile domains

Parameters De mobile domain (m2/s) De immobile domain (m2/s) a mobile domain a immobile domain
13 12 16 15
6.76 10 2.70 10 4.88 10 1.96 10 0.154 0.616 0.090 0.226
Relative change (%) 50 100 50 100 50 100 50 25
Relative sensitivity 1.71 1.63 52.6 33.8 21.3 48.1 87.8 193
P
n
Csi Cbi
Parameter relative changes (P) are computed as 100 PsPPb
b
while relative changes in concentration (C) are equal to 100 C where Ps and Pb are parameter
i
b
i
values for sensitivity and base runs, respectively, Cs and Cb are computed chloride concentrations in sensitivity and base runs, respectively, and n is the total
number of time increments. Relative sensitivities are equal to DC
DP .
 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127
the tails of breakthrough curves of SO24, Na+ and HCO3. Adding
prior information into the objective overcomes correlations
among parameters. According to Dai and Samper (2004), prior
information improves the structure of the objective function,
reduces estimation variances and correlations among trouble-
some parameters and improves stability and avoids ill-posed
parameters.
4.3. Inverse Dual-continuum model (DCM)
Dual continua are simulated as two non-overlapping
materials for mobile and immobile domains. Fig. 6 illustrates
the geometry adopted for DCM which considers a material
zone #1 for mobile domain, a material zone #2 for immobile
domain and a material zone #3 for stainless steel lters
located upstream and downstream the clay sample. Bulk or
global porosity, , is related to local porosities, m and im of
mobile and immobile zones, respectively through (Gerke and
van Genuchten, 1993a):
/ /m wm /im 1  wm
where wm is the volumetric weighting factor which is equal
to the volume of mobile zone divided by the total volume of
medium. In a similar manner, bulk hydraulic conductivity, K,
is related to local mobile and immobile hydraulic conductiv-
ities, Km, and Kim, through:
K Km wm Kim 1  wm
Samper et al. (2006b) report a value of 0.2 for wm in
modeling a tritium permeation test in FEBEX bentonite. All
possible attempts to model our permeation test with wm = 0.2
led to unfeasible values of m larger than 1. Such unrealistic
values of m are avoided when mobile domain occupies 30%
of the total volume of the sample. The solution of the inverse
problem for wm = 0.3 leads to m = 0.7 and a global porosity of
mobile domain of mwm = 0.7 0.3 = 0.21.
DCM is solved by using a 2-D rectangular nite element
grid 2.7 10 2 m long and 10 3 m width. Thickness is such that
the cross-sectional area is equal to that of bentonite sample
(1.963 10 3 m2). Fig. 6 shows the nite element grid used for
DCM which includes the mobile zone (material 1), the
Fig. 7. Sensitivity of computed breakthrough curve of chloride to effective
diffusion coefcient of immobile zone for a DCM.
123
Fig. 8. Sensitivity of computed breakthrough curve of chloride to local
porosity of immobile zone for a DCM.
immobile zone (material 2) and porous sinters (material 3).
6
Since mobile domain occupies 30% of the total volume of the
sample (wm = 0.3), transverse width of mobile zone is 30% of
total width.
Our model assumes that there is no water ow through the
immobile zone. Therefore, Kim is assigned an extremely low
value. Since the bulk conductivity is equal to 2.93 10 14 m/s, it
follows from Eq. (7) that Km is approximately equal to K/wm =
7 9.76 10 14 m/s.
The dual porosity behavior of chloride is studied rst.
Since chloride exhibits anion exclusion, its global accessible
porosity, a, is given by an expression similar to Eq. (6):
/a /am wm /aim 1  wm 8
where am and aim are local accessible porosities of mobile
and immobile zones, respectively.
Normalized sensitivities of chloride concentrations to
changes in effective diffusion coefcients and accessible
porosities of mobile and immobile zones were computed.
Relative changes of parameters (P) are dened as 100 PsPP b
b
while
P
relative changes in concentrations (C) are computed as
n
C C
i i
100 s
C , where Ps and Pb are parameter values for sensitivity
i
b
b
Fig. 9. Measured and computed breakthrough curves of chloride with SCM
and DCM.
124 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127

and base runs, respectively, Cs and Cb are computed chloride
concentrations in sensitivity and base runs, respectively, and n
is the total number of time increments. Relative sensitivities are
equal to DC
DP . Values of relative sensitivities are listed in Table 7. It
should be noticed that an increase in De of immobile zone leads
to an increase in concentrations before 400 days but a decrease
in concentrations after 400 days (Fig. 7). Therefore, relative
changes in concentrations in response to changes in De of
Pn
C C
i i
Estimates of local accessible porosities for chloride are
am = 0.308 (mobile zone) and aim = 0.181 (immobile zone).
According to Eq. (8), global accessible porosity for chloride a
is equal to 0.219 which is smaller than global porosity which is
0.39. Our estimate of global accessible porosity for chloride is an
order of magnitude larger than that obtained by Garca-
Gutirrez et al. (2004) from tracer experiments. Local effective
diffusion coefcients for chloride are 1.35 10 12 (mobile) and

immobile zone are calculated as 100 j C j. Chloride con-

s
i
b
b
9.76 10 16 m2/s (immobile). The effective diffusion coefcient
i
centrations are most sensitive to the local porosity of immobile for chloride in the mobile zone is more similar to the values
zone (see Table 7 and Fig. 8). The smallest relative sensitivity of reported by Garca-Gutirrez et al. (2004, 2006) than the value
chloride concentration is for De of mobile zone. This result obtained with a SCM. The DCM leads to an excellent t to the
shows that chloride breakthrough curve is mostly determined measured Cl breakthrough curve (see Fig. 9) which improves
by properties of the immobile zone. greatly that of SCM.

Fig. 10. Measured and computed breakthrough curves of SO2 2+ 2+ + +
4 , Mg , Ca , Na , K and HCO3 with inverse SCM and DCM.
 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127 125

Our model assumes that chemical species and reactions in Table 8

Table 2 are the same for both domains. Initial concentrations
are also identical in both domains and are taken equal to
those obtained with inverse SCM in step 1. Since chloride
concentrations are more sensitive to im than to m (as
attested by relative sensitivities in Table 7), im was estimated
from some exploratory runs. Its optimum value is equal
to 0.257. Since the global porosity is 0.39, it follows from
Eq. (6) that m is equal to 0.7.
All reactive species are assumed to have the same local
effective diffusion coefcients. The estimate of effective diffusion
coefcient for reactive species is equal to 8.3410 11 m2/s in the
mobile zone and 4.5810 17 m2/s in the immobile domain. The
global effective diffusion coefcient is equal to 5.8410 11 m2/s.
Inverse DCM results are compared to those of inverse SCM in
Figs. 10 and 11. It should be noticed that effective diffusion
coefcients of immobile domain are several orders of magni-
tude smaller than those of the mobile domain. We recall here
that molecular diffusion dominates over dispersion. Therefore,
the disparity in the diffusion/dispersion coefcients between
mobile and immobile zones is not caused by a large dispersion
coefcient in the mobile zone. Instead, such disparity in
diffusion coefcients is probably due to differences in diffusion
tortuosities and constrictivities of the two domains. The need
for a dual porosity model here arises from the large contrast in
diffusive properties of mobile and immobile domains.
Table 5 shows the values of the objective function for
direct SCM, inverse SCM of steps 1 and 2 and inverse DCM as
well as contributions, Ei(p) in Eq. (1), of each reactive species.
Compared to inverse SCM, inverse DCM improves the t to all
breakthrough curves except that of Mg2+. Bicarbonate
accounts for a large proportion of total objective function. It
can be seen in Fig. 10 that model results almost catch the
steady bicarbonate concentration, but miss the initial trend of
measurements, possibly due to changes in CO2(g) which are
not taken into account in our model or to differences in
chemical system in mobile and immobile domains.
Flushing of initial bentonite porewater by inow granitic
water causes calcite dissolution which takes place mostly in
the mobile domain. Dissolved Ca2+ released by calcite is
exchanged with XNa. This source of dissolved Na+ in turn
causes the release of exchanged magnesium. The immobile
zone is much less affected by dilution and therefore by
Fig.11. Measured and computed breakthrough curves of pH with SCM and DCM.
Charge balance errors (%) at a node located at the outow boundary for
different times
Time (days) 0 20 100 500 1000 1400
Direct SCM 5.3 5.2 4.7 5.9 26.0 23.1
Inverse SCM step 1 6.3 6.4 7.1 4.3 7.4 12.6
Inverse SCM step 2 4.8 4.8 5.0 2.6 7.8 11.6
Inverse DCM 6.3 6.4 7.3 4.2 2.1 5.6
Negative values when anions dominate over cations.
calcite dissolution. Diffusive mass transfer from/into mobile
zone causes dissolved bicarbonate to be affected by the
dual nature of the porous medium (Fig. 10). Dissolved
calcium is less affected than dissolved bicarbonate by dual
behaviour because calcium is buffered by cation exchange
(see Fig. 10).
4.4. Charge and mass balance
Charge and mass balance have been checked for SCM and
DCM. Mass balance errors are generally smaller than 0.1% for
all models.
Relative charge balance errors are computed from 2  AC
AC
where A (C) is total charge of aqueous anions (cations) at a
given node. Charge balance errors at the node located at the
outlet of the column are listed in Table 8. Errors are negative for
SCM at all times meaning that there is decit of anions. It
should be noticed that Cl is the dominant anion in bentonite
porewater (see Table 1). Since measured data have small charge
balance errors, they can be used as a reference to check charge
balance errors of SCM and DCM. SCM results t measured Cl
data for the rst 400 days (Fig. 9). After this time SCM
computed breakthrough deviates from measured data and
charge errors increase reaching a value of 26% after 1000 days.
Therefore, large SCM charge errors are caused by the fact that
the model signicantly underestimates measured Cl data. It
should be noticed that the DCM ts Cl data measured after
400 days much better than SCM and consequently DCM charge
balance errors are smaller than those of SCM.
5. Model uncertainties
There are minor uncertainties related to the fact that the
model overpredicts water inows (see Fig. 2). This discrepancy
could be attributed to the fact that the bentonite sample was
not fully saturated at the beginning of the test. A variably-
saturated ow model would be useful to test this hypothesis.
Results of previous models of FEBEX experiments show that
changes in CO2(g) pressures affect bicarbonate concentrations
(Samper et al., 2005b). The mist of bicarbonate data could
therefore be related to the fact that our model of the permeation
test assumes a closed-system and does not account for possible
changes in CO2(g) pressure.
Our DCM assumes that the mobile domain occupies 30% of
the total volume and has a local porosity of 0.7. Therefore, the
global porosity of the mobile domain, mwm, is equal to 0.21.
Estimates of such porosity from experimental data should be
derived to reduce this uncertainty. Another assumption of our
DCM is that chemical processes are the same in both domains.
There may be differences in the chemical system between
126 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127
domains such as cation exchange reactions which mostly take
place in the micro-porous domain. Future DCM models
should account for different conceptual geochemical models
in each domain and explore other possible ways to describe
interactions between the mobile and immobile domains.
Our DCM is based on an arbitrary choice of transverse
dimensions which affects the estimates of diffusion coef-
cients in the immobile zone. The more conventional DCM of
overlapping continua which relies on a physically-based
geometric denition of mobile and immobile zones should
be used in future dual-continuum models of FEBEX bentonite.
It could be argued that the DCM ts experimental data better
than SCM simply because DCM has a larger number of estimated
parameters. Model over-parameterization and identication of
the right conceptual model can be assessed by resorting to
identication criteria similar to those successfully used among
others by Carrera and Neuman (1986) to identify ow models
and Samper and Neuman (1989) to infer covariance functions.
These identication criteria, which were developed within the
context of maximum likelihood theory, include those of Akaike,
Hannan and Kashyap. Dai et al. (2006) report the use of such
information criteria to select the best model among a set of
alternative reactive transport models for Aquia aquifer. These
criteria, however, are very sensitive to the choice of weights wli in
Eq. (1) which in our case can only be estimated in an approximate
manner.
6. Conclusions
Inverse single and dual-continuum multicomponent reac-
tive transport models of a long-term permeation test performed
on a sample of FEBEX bentonite have been presented. Models
account simultaneously for solute advection and diffusion and a
comprehensive suite of geochemical reactions. Model results
conrm that protonation/deprotonation is a key process in
maintaining a stable pH during the experiment. Breakthrough
curves of reactive species are more dependent dependant on
initial porewater concentration than to effective diffusion
coefcient. Optimum estimates of initial porewater chemistry
of saturated compacted FEBEX bentonite have been obtained by
solving the inverse problem of multicomponent reactive
transport. While a single-continuum model (SCM) reproduces
the trends of measured data for most chemical species, it fails to
match properly the long tails of most breakthrough curves. A
dual-continuum reactive transport model (DCM) overcomes
most limitations of SCM.
Anion exclusion is a relevant process for chloride trans-
port. Models without exclusion fail to reproduce the break-
through curve of chloride. While our estimate of effective
diffusion coefcient for Cl is similar to that measured by
Garca-Gutirrez et al. (2006) from tracer diffusion tests, our
estimate of accessible porosity is an order of magnitude larger
than that of Garca-Gutirrez et al. (2004). This discrepancy
could be attributed to differences in hydrochemical condi-
tions between our permeation experiment and their diffusion
tests.
Acknowledgments
This research was performed within the framework of
FEBEX project funded by ENRESA and European Union through
contracts FI4W-CT95-0006 and FIKW-CT-2000-00016 of the
Nuclear Fission Program. Partial funding was provided also by
Spanish Ministry of Science and Technology (CICYT, HID98-282)
and University of La Corua through a research scholarship
awarded to the second author. We thank A. J. Valochi, Editor in
Chief of this publication and two anonymous reviewers for
comments, suggestions and recommendations which have
contributed to signicantly improve the paper.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.jconhyd.2008.03.008.
References
Alonso, E., Ledesma, A. (Eds.), 2005. Advances in Understanding Engineered
Clay Barriers. A. Balkema Pub., Leiden. 583 pp.
Appelo, C.A.J., Postma, D., 1993. Geochemistry, Groundwater and Pollution.
Balkema, Rotterdam.
Barenblatt, G.I., Zheltov, I., Kochina, I., 1960. Basic concepts in the theory of
seepage of homogeneous liquids in ssured rocks. J. Appl. Math. Mech.
24, 852864.
Boudreau, B.P., 1997. Diagenetic Models and Their Implementation: Modeling
Transport and Reactions in Aquatic Sediments. Springer-Verlag. 414 pp.
Bradbury, M.H., Baeyens, B., 1997. A mechanistic description of Ni and Zn
sorption on Na-montmorillonite. Part II: modelling. J. Contam. Hydrol. 27,
223248.
Bradbury, B., Baeyens, B., 2003. Porewater chemistry in compacted
resaturated MX-80 bentonite. J. Contam. Hydrol. 61, 329338.
Carrera, J., Neuman, S.P., 1986. Estimation of aquifer parameters under steady
state and transient condition: 2. Uniqueness, stability, and solution
algorithms. Water Resour. Res. 22 (2), 211227.
Dai, Z., Samper, J., 2004. Inverse problem of multicomponent reactive
chemical transport in porous media: formulation and applications. Water
Resour. Res. 40, W07407. doi:10.1029/2004WR003248.
Dai, Z., Samper, J., 2006. Inverse modeling of water ow and multicomponent
reactive transport in coastal aquifer systems. J. Hydrol. 327 (34), 447461.
Dai, Z., Samper, J., Ritzi, R., 2006. Identifying geochemical processes by
inverse modeling of multicomponent reactive transport in Aquia aquifer.
Geosphere 4 (4), 210219.
Dzombak, D.A., Morel, F.M.M., 1990. Surface Complexation Modelling:
Hydrous Ferric Oxide. John Wiley & Sons, New York. 393 pp.
ENRESA, 1998. FEBEX Full-scale Engineered Barriers Experiment in Crystalline
Rock: Pre-operational Stage Summary Report. ENRESA Tech. Pub. 1/98.
ENRESA, 2006a. Full-scale Engineered Barriers Experiment: Updated Final
Report 19942004. ENRESA Tech. Pub. 05-0/2006.
ENRESA, 2006b. FEBEX Project Final Report: Final THG modelling report.
ENRESA Tech. Pub. 05-3/2006.
Fernndez, A.M., Cuevas, J., Rivas, P., 2001. Pore water chemistry of the FEBEX
bentonite. Mater. Res. Soc. Symp. Proc. 663, 573588.
Fernndez, A.M., Baeyens, B., Bradbury, M., Rivas, P., 2004. Analysis of the
pore water chemical composition of a Spanish compacted bentonite used
in an engineered barrier. Phys. Chem. Earth 29, 105118.
Garca-Gutirrez, M., Cormenzana, J.L., Missana, T., Mingarro, M., 2004. Diffusion
coefcients and accessible porosity for HTO and 36Cl in compacted FEBEX
bentonite. Appl. Clay Sci. 26, 6573.
Garca-Gutirrez, M., Cormenzana, J.L., Missana, T., Mingarro, M., Molinero, J.,
2006. Overview of laboratory methods employed for obtaining diffusion
coefcients in FEBEX compacted bentonite. J. Iber. Geol. 32 (1), 3753.
Gerke, H.H., van Genuchten, M.Th., 1993a. A dual porosity model for
simulating the preferential movement of water and solutes in structured
porous media. Water Resour. Res. 29, 305319.
Gerke, H.H., van Genuchten, M.Th., 1993b. Evaluation of a rst order water
transfer term for variably saturated dual porosity ow models. Water
Resour. Res. 29, 12251238.
Gerke, H.H., van Genuchten, M.Th., 1996. Macroscopic representation of
structural geometry of simulating water and solute movement in dual-
porosity media. Adv. Water Resour. 19, 343357.
Gwo, J.P., Jardine, P.M., Wilson, G.V., Yeh, G.T., 1995. A multiple-pore-region
concept to modeling mass transfer in subsurface media. J. Hydrol. 164,
217237.
Hantush, M.M., Govindaraju, R.S., 2003. Theoretical development and
analytical solutions for transport of volatile organic compounds in
dual-porosity soils. J. Hydrol. 279, 1842.
 J. Samper et al. / Journal of Contaminant Hydrology 98 (2008) 115127
Hantush, M.M., Mario, M.A., Islam, M.R., 2000. Models for leaching of
pesticides in soils and groundwater. J. Hydrol. 227, 6683.
Hantush, M.M., Govindaraju, R.S., Mario, M.A., Zhang, Z., 2002. Screening
mode for volatile pollutants in dual porosity soils. J. Hydrol. 260, 5874.
Jarvis, N.J., Jansson, P.E., Dik, P.E., Messing, I., 1991a. Modelling water and
solute transport in macroporous soil. 1. Model description and sensitivity
analysis. J. Soil Sci. 42, 5970.
Jarvis, N.J., Bergstrom, L., Dik, P.E., 1991b. Modelling water and solute
transport in macroporous soil. 2. Chloride breakthrough under non-
steady ow. J. Soil Sci. 42, 7181.
Ktterer, T., Schmied, B., Abbaspour, K.C., Schulin, R., 2001. Single- and dual-
porosity modelling of multiple tracer transport through soil columns:
effects of initial moisture and mode of application. Eur. J. Soil Sci. 52 (1),
2536.
Larsbo, M., Jarvis, N., 2005. Simulating solute transport in a structured eld
soil: uncertainty in parameter identication and predictions. J. Environ.
Qual. 34, 621634.
Larsson, M.H., Jarvis, N.J., 1999. Evaluation of a dual-porosity model to predict
eld scale solute transport in a macroporous soil. J. Hydrol. 215, 153171.
Lichtner, P.C., 2000. Critique of dual continuum formulation of multi-
component reactive transport in fractrued porous media. Geophys.
Monogr. 122, 281298.
Molinero, J., Samper, J., 2004. Groundwater ow and solute transport in
fracture zones: an improved model for a large-scale eld experiment at
sp (Sweden). J. Hydraul. Res. 42, 157172 Extra Issue.
Molinero, J., Samper, J., 2006. Modeling of reactive solute transport in fracture
zones of granitic bedrocks. J. Contam. Hydrol. 82, 293318.
Molinero, J., Samper, J., Yang, C., Zhang, G., 2004. Biogeochemical reactive
transport model of the Redox zone experiment of the sp hard rock
laboratory (Sweden). Nucl. Technol. 48 (2), 151165.
Muurinen, A., 2001. Development and Testing of Analysis Methods for
Bentonite Porewaters. POSIVA Oy, Technical Working Report 2001-07.
Helsinki. 37 pp.
Muurinen, A., Lehikoinen, J., 1999. Porewater chemistry in compacted
bentonite. Eng. Geol. 54 (1), 207214.
Ray, C., Ellsworth, T.R., Valocchi, A.J., Boast, C.W., 1997. An improved dual
porosity model for chemical transport in macroporous soils. J. Hydrol.
193, 270292.
Sacchi, E., Michelot, J.L., Pitsch, H., Lalieux, P., Aranyossy, J.F., 2001. Extraction
of water and solutes from argillaceous rocks for geochemical character-
ization: methods, processes, and current understanding. Hydrogeol. J. 9,
1733.
Samper, F.J., Neuman, S.P., 1989. Estimation of spatial covariance structures by
adjoint state maximum likelihood cross-validation: 2. Synthetic experi-
ments. Water Resour. Res. 25 (3), 363372.
Samper, J., Yang, C., 2006. Stochastic analysis of transport and multicomponent
competitive monovalent cation exchange in aquifers. Geosphere 2,102112.
Samper, J., Yang, C., Montenegro, L., 2003a. Users Manual of CORE2D Version
4: a Code for Groundwater Flow and Reactive Solute Transport.
University of A Corua, Spain. 105 pp.
Samper, J., Molinero, J., Yang, C., Zhang, G., 2003b. Redox Zone II. Coupled
Modeling of Groundwater Flow, Solute Transport, Chemical Reactions
and Microbial Processes in the sp Island. SKB Technical Report, TR-03-
16, Stockholm, Sweden.
Samper, J., Zheng, L., Montenegro, L., Fernndez, A.M., Rivas, P., Dai, Z., 2005a.
Direct and inverse modelling of multicomponent reactive transport in
single and dual porosity media. In: Alonso, E.E., Ledesma, A. (Eds.),
127
Advances in Understanding Engineered Clay Barriers. A.A. Balkema
Publishers, Leiden, The Netherlands, pp. 493503.
Samper, J., Vzquez, A., Montenegro, L., 2005b. Inverse hydrochemical
modelling of aqueous extracts experiments for the estimation of FEBEX
bentonite pore water chemistry. In: Alonso, E.E., Ledesma, A. (Eds.),
Advances in Understanding Engineered Clay Barriers. A.A. Balkema
Publishers, Leiden, The Netherlands, pp. 553563.
Samper, J., Zheng, L., Montenegro, L., Fernndez, A.M., Rivas, P., 2008. Testing
coupled thermo-hydro-chemical models of compacted bentonite after
dismantling the FEBEX in situ test. Appl. Geochem. 23 (5), 11861201.
doi:10.1016/j.apgeochem.2007.11.010.
Samper, J., Zhang, G., Montenegro, L., 2006a. Coupled microbial and geochemical
reactive transport models in porous media: formulation and application to
synthetic and in situ experiments. J. Iber. Geol. 32 (2), 211217.
Samper, J., Dai, Z., Molinero, J., Garca-Gutirrez, M., Missana, T., Mingarro, M.,
2006b. Interpretation of solute transport experiments in compacted Ca-
bentonites using inverse modelling. Phys. Chem. Earth 31, 640648.
Samper, J., Yang, C., Naves, A., Yllera, A., Hernndez, A., Molinero, J., Soler, J.M.,
Hernn, P., Mayor, J.C., Astudillo, J., 2006c. A fully 3-D anisotropic model
of DI-B in situ diffusion experiment in the Opalinus clay formation. Phys.
Chem. Earth 31, 531540.
Schwartz, R.C., Juo, A.S.R., McInnes, K.J., 2000. Estimating parameters for a
dual-porosity model to describe non-equilibrium, reactive transport in a
ne-textured soil. J. Hydrol. 229, 149167.
imunek, J., Jarvis, N.J., Van Genuchten, M.T., Grdens, A., 2003. Review and
comparison of models for describing non-equilibrium and preferential
ow and transport in the vadose zone. J. Hydrol. 272, 1435.
van Genuchten, M.T., Parker, J.C., 1984. Boundary conditions for displacement
experiments through short laboratory soil columns. Soil Sci. Soc. Am. J.
48, 703708.
van Genuchten, M.T., Wagenet, R.J., 1989. Two-site/two-region models for
pesticide transport and degradation: theoretical development and
analytical solutions. Soil Sci. Soc. Am. 53 (5), 13031310.
Wieland, E., Wanner, H., Albinsson, Y., Wersin, P., Karland, O., 1994. A Surface
Chemical Model of the BentoniteWater Interface and its Implications for
Modelling the Near Field Chemistry in a Repository for Spent Fuel. SKB
Technical Report 94-26. 64 pp.
Wolery, T.J., 1992. EQ3/6, a Software Package for Geochemical Modeling of
Aqueous Systems: Package Overview and Installation Guide (version 7.0).
Technical Report UCRL-MA-110662-Pt 1. Lawrence Livermore National
Laboratory, CA, USA.
Xu, T., Samper, J., Ayora, C., Manzano, M., Custodio, E., 1999. Modeling of non-
isothermal multi-component reactive transport in eld scale porous
media ow system. J. Hydrol. 214 (14), 144164.
Yang, C., Samper, J., Molinero, J., Bonilla, M., 2007. Modeling geochemical and
microbial consumption of dissolved oxygen after backlling a high level
radioactive waste repository. J. Contam. Hydrol. 93, 130148.
Yang, C., Samper, J., Montenegro, L., 2008. A coupled non-isothermal
reactive transport model for long-term geochemical evolution of a
HLW repository in clay. Environ. Geol. 53, 16271638. doi:10.1007/
s00254-007-0770-2.
Zhang, G., Samper, J., Montenegro, L., 2008. Coupled thermo-hydro-bio-
geochemical reactive transport model of the CERBERUS heating and
radiation experiment in Boom clay. Appl. Geochem. 23 (4), 932949.
doi:10.1016/j.apgeochem.2007.09.010.
Zheng, L., Samper, J. and Montenegro, L., in press. Inverse hydrochemical
models of aqueous extract experiments. Phys. Chem. Earth.