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Applied
Geochemistry
Applied Geochemistry 23 (2008) 11861201
www.elsevier.com/locate/apgeochem

Coupled thermo-hydro-chemical models of compacted

bentonite after FEBEX in situ test
Javier Samper a,*, Liange Zheng a,1, Luis Montenegro a, Ana Mara Fernandez b,
Pedro Rivas b
a
E.T.S. Ingenieros de Caminos, Canales y Puertos, Universidad de A Coruna, Campus de Elvina s/n, 15192 A Coruna, Spain
b
Departamento de Medio Ambiente, CIEMAT, Avda. Complutense 22, 28040 Madrid, Spain

Received 9 February 2007; accepted 8 November 2007

Editorial handling by R. Fuge
Available online 26 January 2008

Abstract

FEBEX (Full-scale Engineered Barrier EXperiment) is a demonstration and research project for the engineered barrier
of a high-level radioactive waste (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 drifts and surrounded by a
compacted bentonite clay barrier. The project includes two main large-scale tests which started in February 1997: an
in situ full-scale test performed at Grimsel, Switzerland, and a mock-up test operating at CIEMAT facilities in Madrid,
Spain. Coupled thermal, hydrodynamic and chemical (THC) models for the engineered barrier have been developed from
laboratory experiments and the mock-up test. Dismantling of section 1 of in situ test, which took place in the summer of
2002, provides a unique opportunity to test THC model predictions. Here a numerical THC model of FEBEX in situ test is
presented. Predictions performed with three conceptual geochemical models are compared to measured temperature, water
content and geochemical data obtained from aqueous extract tests of samples collected after dismantling of heater 1. These
data require the use of inverse hydrogeochemical models for their interpretation in order to account for the geochemical
processes suered by bentonite samples during aqueous extraction. Model predictions reproduce temperatures and capture
the trends of water content and most chemical species. However, there are some discrepancies near the heater which are

especially signicant for SO24 and HCO3 . The THC model could be improved by taking into account dierent types of
water in bentonite, bentonite swelling, protonation/deprotonation by surface complexation, and CO2 degassing and
dissolution processes.
2008 Elsevier Ltd. All rights reserved.

1. Introduction

FEBEX (Full-scale Engineered Barrier EXperi-

*
ment) is a demonstration and research project deal-
Corresponding author. Fax: +34 981 167 170.
ing with the bentonite engineered barrier designed
E-mail address: jsamper@udc.es (J. Samper).
1
Present address: Lawrence Berkeley National Lab, 1 Cyclo- for sealing and containment of a high-level radioac-
tron Road, Berkeley, CA 94720, USA. tive waste repository (ENRESA, 2000). FEBEX is

0883-2927/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2007.11.010
 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201
based on the Spanish reference concept for disposal
of radioactive waste in crystalline rock. Canisters
are emplaced in horizontal drifts and surrounded
by a highly-compacted bentonite barrier (ENRESA,
1994). Bentonite has the multiple purpose of provid-
ing canister mechanical stability by absorbing stres-
ses and deformations, sealing discontinuities in the
adjacent rock and retarding radionuclide migration.
FEBEX includes two main large-scale experi-
ments operating since February 1997: an in situ
full-scale test performed at Grimsel (Switzerland),
and a mock-up test in Madrid, Spain (ENRESA,
2000).
One of the objectives of the FEBEX project is the
development and testing of conceptual and numeri-
cal thermal, hydrodynamic and chemical (THC)
models for the engineered bentonite barrier. The
ability of these models to reproduce the observed
THC patterns in a wide range of conditions should
enhance the condence in their predictive capabili-
ties. Conceptual and numerical THC models of
heating and hydration experiments performed on
small-scale lab cells within the FEBEX project pro-
vided excellent results for temperatures, water
inow and nal water content (ENRESA, 2000,
2006d; Samper et al., 2005a,b,c). These models have
been used to simulate the evolution of FEBEX
in situ test. These predictions were compared to
measured and inferred geochemical data collected
after dismantling heater 1 in the summer of 2002.
Geochemical simulations of FEBEX in situ and
mock-up tests are presented by Gens et al. (2004).
Other in situ and mock-up tests include the LOT
experiment at Aspo underground research labora-
tory (URL) in Sweden (Karnland et al., 2000; Arcos
et al., 2003) and Ophelie mock-up test performed at
HADES URL in Belgium (Van Humbeeck et al.,
2006; Verstricht et al., 2007).
Here, a THC numerical model for the FEBEX
in situ test is presented. Model predictions performed
with several conceptual geochemical models are
Sections 7 12
Access Concrete
gallery
Fig. 1. Layout of the FEBEX in situ test. Vertical lines show the location of the dierent sampling sections.
1187
compared to measured geochemical data obtained
from aqueous extract tests. These data require the
use of inverse hydrogeochemical models for their
interpretation in order to account for the geochemi-
cal processes suered by bentonite samples during
aqueous extraction tests. The paper starts by describ-
ing the FEBEX in situ test. Then, THC conceptual
and numerical models are presented. Interpretation
of aqueous extract data with three conceptual geo-
chemical models is described. Inferred chemical data
are compared to model predictions. Finally, main
uncertainties of THC model are discussed.
2. FEBEX in situ test
The FEBEX in situ test is being performed in a
gallery excavated in granite in the northern zone
of the Grimsel underground laboratory operated
by NAGRA in Switzerland. The test includes the
heating system, the clay barrier (bentonite) and
instrumentation, monitoring and control systems.
The drift is 70.4 m long and 2.28 m in diameter.
The test zone is located in the last 17.4 m of the drift
where heaters, bentonite and instrumentation were
installed. The test zone was sealed with a concrete
plug. The main elements of the heating system are
two heaters (1 and 2), separated horizontally by
1 m, which simulate full-sized canisters. Heaters
were placed inside cylindrical steel liners. Heaters
are 4.54 m long, 0.9 m diameter and have a thick-
ness of 0.1 m. Heaters are designed to maintain a
maximum temperature of 100 C at the steel liner/
bentonite interface. The bentonite barrier is made
of blocks of highly-compacted bentonite. A layout
of the in situ test is shown in Fig. 1. Weighted aver-
age values of dry density and water content of ben-
tonite blocks are 1.70 g/cm3 and 14.4%, respectively
(ENRESA, 2000). Mineralogical composition of
FEBEX bentonite is listed in Table 1 (Fernandez
et al., 2004). The main mineral phase (9092 wt.%)
is montmorillonite.
19 28 29
Heater 1 Heater 2 0.9 m 2.28 m
1188 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201
Table 1
Mineralogical composition (in weight %) of FEBEX bentonite (Fernandez et al., 2004)
Main minerals Accessory minerals
Smectite 92 3 Organic Matter (as CO2)
Quartz 21 Carbonates (calcite, dolomite)
Plagioclase 21 Soluble sulfates (gypsum)
Cristobalite 21 Low soluble sulfates (barite, celestite)
K-Feldspars Traces Sulphides (pyrite)
Tridymite Traces Chlorides (halite)
Calcite Traces
The in situ test began on February 27th, 1997.
Heater 1 was switched-o in February 2002. Dis-
mantling of heater 1 was performed from May to
September 2002. A comprehensive post-mortem
bentonite sampling and analysis program was
designed to characterize solid and liquid phases,
measure physical and chemical changes induced by
the combined eect of heating and hydration; and
test THM and THC models (ENRESA,
2006a,b,c,d).
3. THC model
3.1. Conceptual model
The thermo-hydrodynamic (TH) model assumes
that the porous medium contains a liquid phase
consisting of water, aqueous species and dissolved
gases, a gaseous phase which is made of water vapor
and dry air (i.e., a ctitious species which encom-
passes all the gaseous species except water vapor),
and a solid phase which includes several minerals
and the exchange complex.
Water may ow in liquid phase through com-
pacted bentonite in response to a hydraulic gradient
according to Darcys law. It can also ow in gaseous
phase as vapor due to air convection and in
response to a moisture gradient according to Ficks
law. Water vapor ux is several orders of magnitude
smaller than liquid water ux in most cases and
therefore can be neglected. However, near the hea-
ter of the in situ test vapor ux can be important.
Liquid water and water vapor uxes are related
through evaporation and condensation. The energy
transfer due to liquid water/vapor transition is very
important due to the large enthalpy increment of
evaporation/condensation (585 cal/g at 20 C). The
TH conceptual model takes into account the follow-
ing multiphase ow processes: (1) Advective ow
of liquid water, (2) Advective and diusive ow of
water vapor, (3) Advective and diusive ow of
Poorly ordered minerals
0.35 0.05 SiO2 0.038 0.005
0.60 0.13
0.14 0.01 Al2O3 0.035 0.005
0.02 0.00
0.02 0.01 Fe2O3 0.105 0.009
0.13 0.02
dry air, (4) Advective ow of air dissolved in
water, (5) Heat conduction through solid, liquid
and gas phases; and (6) Heat convection through
liquid and gaseous phases. General mass balance
equations for water, air and heat can be found in
Samper et al. (2007c).
Solute transport processes include: advection,
molecular diusion and mechanical dispersion. Sol-
ute transport equations are stated for each chemical
component (primary species) in the system.
Dierent conceptual geochemical models (CGM)
have been proposed for FEBEX bentonite. They
dier depending on the type of test used to obtain
chemical data: squeezing and aqueous extracts tests
(AET). Conceptual model CGM-0 was derived
from a squeezing test performed on a bentonite
sample having a gravimetric water content of
26.5% (ENRESA, 2000). Geochemical models were
used to derive the chemical composition at 14%
water content. Later, Samper et al. (2005b) pre-
sented a model derived from aqueous extract tests
(model CGM-1) which assumes gypsum at equilib-
rium, calcite and dolomite with kinetic mineral dis-
solution, and a prescribed pressure of 103.5 bar for
CO2(g). This model reproduces adequately mea-
sured aqueous extract data performed for dierent
durations and S/L ratios. However, it fails to repro-
duce HCO 3 and pH data, possibly due to changes in
CO2(g) pressure which are not considered in the
model. In general, calculated results with model
CGM-1 could not t SO2 4 squeezing data. Samper
et al. (2005b) presented a modied model (CGM-
2) based on data from both aqueous extract and
squeezing tests. This model does not consider an ini-
tial amount of gypsum in the system but allows for
its precipitation. Models CGM-1 and CGM-2 t
simultaneously both squeezing and aqueous extract
data for most chemical species, although they pres-

ent discrepancies for SO2
4 and HCO3 data.
Models CGM-0, CGM-1 and CGM-2 account
for aqueous complexation, acidbase, mineral disso-
 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201 1189

Table 2
Chemical species considered in models CGM-0, CGM-1 and CGM-2
Geochemical CGM-0 CGM-1 CGM-2
models

Primary species H2O, H+, Ca2+, Mg2+, Na+, K+, Cl, SO24 ; HCO3 , SiO2(aq),
Aqueous complexes OH, CaSO4(aq), CaCl+, MgCl+, NaCl(aq), MgHCO
3 , NaHCO3(aq), CaHCO3 , MgCO3(aq), CaCO3(aq), CO2(aq),
2   2 
CO3 , KSO4 , MgSO4(aq), NaSO4 ; H2 SiO4 ; HSiO3
Minerals Calcite (equilibrium) Calcite (kinetic) Calcite (kinetic)
Chalcedony (equilibrium) Chalcedony (equilibrium) Chalcedony (equilibrium)
Gypsum/anhydrite (equilibrium, only Gypsum/anhydrite Gypsum/anhydrite
precipitation) (equilibrium) (equilibrium,
only precipitation)
Dis-dolomite (kinetic) Dis-dolomite (kinetic)
Exchangeable Ca2+, Mg2+, Na+, K+ Ca2+, Mg2+, Na+, K+, H+ Ca2+, Mg2+, Na+, K+, H+
cations
Gases No condition on CO2(g) Fixed CO2(g) pressure Fixed CO2(g) pressure

lution/precipitation, gas dissolution/exsolution and which may dissolve or precipitate under kinetic con-
cation exchange. These processes are assumed at ditions in models CGM-1 and CGM-2 (see Table 2).
local equilibrium except for calcite and dolomite Relevant aqueous complexes were identied from
speciation runs performed with EQ3/6 (Wolery,
Table 3
Equilibrium constants for aqueous complexes, minerals and gases 1979). Equilibrium constants at 25 C for aqueous
and selectivity coecients at 25 C (Wolery, 1979) complexes, minerals and gases were taken from
Log K the EQ3/6 database (Wolery, 1979). They are listed
in Table 3. The GainesThomas convention is used
Aqueous complexes
CaCl+ , Ca2+ + Cl 0.6956 for cation exchange. Kinetic laws and rate constants
CaCO3 aq H () Ca2 HCO 3 7.0017 for calcite were taken from Plummer et al. (1979)
CaHCO 3 () Ca
2
HCO 3 1.0467 while those of disordered dolomite were derived
2 2
CaSO4 aq () Ca SO4 2.1111 from Ayora et al. (1994). Values of specic surface
CO2 aq H2 O () H HCO 6.3447

3 for calcite and dolomite were derived by Samper
CO2
3 H () HCO3 10.3288
H2 SiO2 et al. (2005b) from calibration of AET (see Table
4 2H () 2H2 O SiO2 aq 22.9116
HSiO 3 H
( ) H2 O SiO2 aq 9.9525 4). Bentonite chemical composition data at the ini-
KSO
4 () K SO4
2
0.8796 tial water content of bentonite buer (14.4%) for
MgCl+ , Mg2+ + Cl 0.1349 models CGM-0, CGM-1 and CGM-2 are listed in
MgCO3 aq () Mg2 CO2 2.9789
3 Table 5.
MgHCO 3 () Mg
2
HCO 3 1.0357
MgSO4 aq () Mg2 SO2 4 2.4117
NaCl(aq) , Na + Cl+ 
0.7770 3.2. Numerical model
NaHCO3 aq () Na HCO 3 0.1541
NaSO
4 () Na SO4
2
0.8200 The model assumes axial symmetry. Spatial
OH + H+ , H2O 13.9951
domain was discretized with a 1D mesh of rectangu-
Minerals lar nite elements which contains 614 nodes and 307
Calcite H () Ca2 HCO 3 1.8487 elements (Fig. 2). Two material zones were consid-
Dis  dolomite 2H 4.0579
() Ca2 Mg2 2HCO
ered in the mesh: bentonite and granite. The rst
3
Anhydrite () Ca2 SO2 4.3064 two nodes (1 and 2) are located at the heaterben-
4
Gypsum () Ca2 SO2 4 2H2 O 4.4823 tonite interface (r = 0.45 m). Bentonite which lies
Chalcedony , SiO2(aq) 3.7281 at the interval 0.45 m < r < 1.135 m is discretized
Gases with 220 nodes. Granite is simulated with 392 nodes
CO2 g H2 O () H HCO
3 7.8136 and extends from 1.135 m to 50 m. The mesh was
Cation exchange KNa-cation rened near the bentonitegranite interface because
Na+ + X-K ,K+ + X-Na 0.1380 large concentration gradients are expected to take
Na+ + X-H ,H+ + X-Na 8.4  106 place in this zone. The model was run for 1930 days,
Na+ + 0.5 X2-Ca , 0.5 Ca2+ + X-Na 0.2924 which corresponds to the time of dismantling of
Na+ + 0.5 X2-Mg , 0.5 Mg2+ + X-Na 0.2881
heater 1.
1190 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201

Table 4
Kinetic dissolution/precipitation rates, R, for calcite (Plummer et al., 1979) and disordered dolomite (Ayora et al., 1994)
Mineral Kinetic rate R (mol/m2 s) Specic surface (m2/m3)
5 8 11
Calcite 8:91  10  aH 5:01  10  aH2 CO3 6:46  10  aH2 O 0.1
1:86  102  aCa2  aHCO3 1  X
Disordered dolomite 2.20  108 (1-X) 0.5
Specic surfaces derived from calibration of aqueous extract tests (Samper et al., 2005b). Note: a is the activity of chemical species and X is
saturation ratio.

Table 5
Chemical, mineralogical and cation exchange initial composition at 14% water content of FEBEX bentonite and granite for dierent CGM
Conceptual geochemical models for bentonite Granite
CGM-0 CGM-1 CGM-2
T (C) 12 12 12 12
pH 7.86 7.62 7.62 9.25
Na+ (mol/L) 1.88  101 1.28  101 1.28  101 3.76  104
K+ (mol/L) 1.68  103 2.00  103 2.30  103 7.80  106
Ca2+ (mol/L) 1.13  102 2.10  102 2.5  102 2.16  104
Mg2+ (mol/L) 1.44  102 2.20  102 3.2  102 1.32  106
HCO 3 mol=L 5.80  104 3.90  104 4.1  104 3.97  104
SO2
4 mol=L 2.12  102 3.10  102 2.2  102 7.86  105
Cl (mol/L) 1.87  101 1.55  101 1.85  101 1.31  105
SiO2(aq) (mol/L) 1.05  104 2.8  104 2.8  104 6.07  104
Calcite (%) 1 1 1 5
Chalcedony (%) 4.5 4.5 4.5 20
Disordered dolomite (%) n.c.a 2 2 0
Anhydrite (%) 0 n.c.a n.c.a 0
Gypsum (%) n.c.a 5  104 0 0
Na+ (meq/100 g) 31.18 29.35 29.35 n.c.a
K+ (meq/100 g) 1.94 2.56 2.56 n.c.a
H+ (meq/100 g) n.c.a 1 1 n.c.a
Ca2+ (meq/100 g) 34.62 35.71 35.71 n.c.a
Mg2+ (meq/100 g) 34.01 32.29 32.29 n.c.a
a
n.c. means not considered in the model.

Axis Prescribed T = 97 C Prescribed T = 12 C

Water flux = 0 Prescribed liquid pressure = 700 kPa

Bentonite Granite
0 0.45 m 1.135 m 50 m
Heater 1

Fig. 2. Scheme of nite element rectangular grid and thermal and ow boundary conditions used for THC model of FEBEX in situ test.

The initial temperature is uniform and equal to
12 C. A constant temperature of 97 C is prescribed
at the heaterbentonite interface (r = 0.45 m) while
temperature is assumed to remain constant and
equal to its initial value of 12 C at the external
boundary (r = 50 m) because the thermal perturba-
tion induced by heaters does not extend to such a
boundary. Boundary conditions for ow include:
(1) No ow at r = 0.45 m and (2) A prescribed liquid
pressure of 700 kPa at r = 50 m (see Fig. 2).
Since the FEBEX in situ test was not designed to
be air-tight, nothing prevented gas from owing in
 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201 1191

or out of the test section at early stages of the test.
However, it is believed that bentonite swelling
sealed most of buer gaps and voids, making it dif-
cult for gas to ow across the concrete plug. It is
assumed in the model that the system is closed for
gaseous phases. This means that there are neither
gas uxes across external boundaries nor prescribed
gas pressures. Gas in granite and bentonite is simu-
lated as a trapped phase overlapping the liquid
phase.
Table 5 lists initial concentrations of FEBEX
bentonite and granite. Concentrations for the initial
gravimetric water content of bentonite of 14% are
listed for CGM-0, CGM-1 and CGM-2.
Thermal and hydrodynamic parameters for ben-
tonite and granite are summarized in Table 6. The
porewater diusion coecient, D0, is assumed to
be equal to 2  1010 m2/s for all chemical species.
This value was derived from calibration of heating
and hydration laboratory experiments (ENRESA,
2000, 2006d). The eective diusion coecient, De,
is equal to 6.1  1011 m2/s for bentonite and
4.38  1013 m2/s for granite (see Table 6).
There are no dispersivity data for granite. Results
of sensitivity analysis to granite dispersivity indicate
that dispersivity of granite mostly aects solute back
diusion from bentonite into granite (ENRESA,
2000, 2006d). Given the small value of the Peclet
number in bentonite, model results are not sensitive
to bentonite dispersivity. In order to prevent numer-
ical oscillations near the bentonitegranite interface,
a dispersivity of 0.03 m was used for both bentonite
and granite. This ensures that the Peclet number is
much smaller than 2.
3.3. Code description
THC predictions of the in situ test have been per-
formed with INVERSEFADESCORE (Zheng
and Samper, 2004), a code which solves both
forward and inverse multiphase ow and multicom-
ponent reactive transport problems in 1, 2 and 3D

Table 6
Thermal, hydrodynamic and solute transport parameters of FEBEX bentonite in THC model of in situ test
Parameter Bentonite Granite
2 21
Liquid intrinsic permeability K (m ) as a function K0 = 2.75  10 for
of ionic strength I (mol/L) I0=0.2674 mol/L
 1=2
K I
K0 a I0 with a = 1.097 5  1017
p 0:5 2
Liquid relative permeability krl as a function k rl S 3l k rl S l 1  1  S 0:5
l 
of liquid saturation Sl 1:1
19:1107 W
Retention curve: liquid saturation Sl as a function Sl 0:18 Sl = [(1 + 4.76104W)3.33]0.7
15105 W1:22 
of suction W
6 6
Solid density (kg/m3) 2780  e[2  10 (TTref )]
2700  e[2  10 (TTref )]

Thermal conductivity of solids (W/m C) 0.8 1.5

Specic heat of solids (J/kg C) 835.5 1029
Liquid viscosity (kg/m s) as a function of temperature T 0.6612(T  229)1.562
7
Liquid density (kg/m3) as a function of liquid 998.2  e[5  10 (P1  100)2.1  104(T  Tref )]

pressure Pl and temperature T

Intrinsic permeability of gas krg (m2) 5  1010
Gas relative permeability krg krg = (1  Sl)3
Vapor tortuosity 0.5
Gas viscosity (kg/m s) 1.76  105
Liquid thermal conductivity (W/m C) 1.5
Liquid specic heat (J/kg C) 4202
Reference temperature, Tref (C) 12
Air thermal conductivity (W/m C) 2.6  102
Air specic heat (J/kg C) 1000
Vapor thermal conductivity (W/m C) 4.2  102
Vapor specic heat (J/kg C) 1620
Vaporization enthalpy (J/kg) 2.454  106
Porosity 0.41 0.01
Porewater diusion coecient (m2/s) 2  1010
Dispersivity (m) 3  102
Eective diusion coecients (m2/s) 6.1  1011 4.38  1013
1192 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201
axy-symmetric porous and fractured media. This
code is the result of integrating the capabilities of
FADES (Navarro and Alonso, 2000), CORE2D
(Samper et al., 2000) and INVERSECORE (Dai
and Samper, 2004). State variables of the forward
model are liquid pressure, gas pressure, and temper-
ature. They are solved by a NewtonRaphson
method. Reactive transport equations are solved
with a sequential iteration method to obtain concen-
trations of primary species. The inverse problem is
solved by minimizing a generalized least-squares
criterion with a GaussNewtonLevenbergMarqu-
ardt method (Dai and Samper, 2004). Forward rou-
tines of INVERSEFADESCORE have been
widely veried with analytical solutions and used
to simulate THC experiments (Samper et al.,
2005c; ENRESA, 2006d) and THMC problems
(Zheng and Samper, 2004). Codes of the CORE ser-
ies have been extensively used to model laboratory
and in situ experiments including the CERBERUS
experiment in Boom clay in Belgium (Samper
et al., 2006; Zheng et al., 2008), interpretation of
the Redox Zone experiment in a fracture zone of
Aspo site at Sweden (Molinero and Samper, 2004,
2006; Molinero et al., 2004), inverse reactive trans-
port of laboratory experiments and coastal aquifers
(Dai and Samper, 2006; Dai et al., 2006), O2 con-
sumption in a HLW repository in granite (Yang
et al., 2007a), long-term geochemical evolution of
a HLW repository in clay (Yang et al., 2007b),
and stochastic cation exchange and reactive trans-
port in aquifers (Samper and Yang, 2006).
4. Geochemical data after dismantling FEBEX in situ
test
4.1. Bentonite samples
Bentonite samples were taken from vertical sec-
tions normal to the axis of the tunnel. In each sec-
tion several samples were taken along dierent
radii. Bentonite samples were taken for THC analy-
ses from 3 sections in the heater zone (S29, S28 and
S19), a section in the zone between the concrete seal
and the heater 1 (S12) and a section in contact with
the concrete seal (S7) (see Fig. 1). Each sampling
section consisted of an outer, central and inner layer
of bentonite blocks. Fig. 3 shows the location of
bentonite blocks in section 29 collected after dis-
mantling of heater 1. A total of 9 bentonite blocks
were taken (BB29-5 to BB2913). Samples were ana-
lyzed at dierent radial distances. Bentonite blocks
GF
BB29-9
BB29-13
BB29-11
BB29-12 BB29-8
BB29-10
BB29-5 BB29-7
BB29-6
Fig. 3. Location of bentonite blocks BB29-5BB-29-13 used for
chemical analyses after dismantling section 29 of FEBEX in situ
test.
were preserved immediately after their extraction
in plastic lm, two layers of aluminized PET-sheets
and vacuum-sealed plastic bags. The rst PET-sheet
was vacuum-sealed after ushing with N2. Protec-
tion against mechanical actions was used to ensure
the integrity of the material (Fernandez and Rivas,
2003).
4.2. Bentonite porewater chemistry
Obtaining reliable data for clay porewater chem-
istry is a dicult task. A great deal of eort has been
made during recent years to improve water extrac-
tion methods, develop numerical interpretation
methods and achieve consistency of experimental
data and geochemical modelling (Sacchi and Mich-
elot, 2000; Sacchi et al., 2001; Bradbury and Baey-
ens, 2002, 2003; Pearson and Scholtis, 2003;
Fernandez, 2004).
Preserving in situ conditions of core samples is
dicult. A general discussion of perturbations
caused by sampling, storage, preparation and
extraction techniques is given by Sacchi and Miche-
lot (2000), Sacchi et al. (2001) and Pearson and
Scholtis (2003). Aqueous extract tests (AET) have
been used to obtain porewater chemistry for com-
pacted FEBEX bentonite. AET is a method to
quantify the total content of soluble salts in a clay
sample. A 1:R AET consists of adding to a mass
 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201 1193

Ms of powdered clay sample a mass of distilled
water equal to R times Ms. Clay sample and water
are stirred during a period of time usually of two
days during which equilibration of water and clay
sample is allowed. Chemical analyses are performed
on the supernatant solution after phase separation
by centrifugation (Sacchi et al., 2001). The solid-
to-liquid ratio, S/L, is related to the aqueous extract
ratio R through
S 1
1 of relevant aqueous complexes, (2) relevant mineral
L wi R1 wi
where wi is the gravimetric water content of the clay
sample. It should be noted that S/L coincides with
1/R only when the clay sample is dry (wi = 0).
In addition to dilution, several chemical pro-
cesses take place during porewater extraction from
clay samples, including dissolution of soluble miner-
als (halite, sulfates and carbonates mostly), dissolu-
tion and ex-solution of gases and cation exchange.
All these processes change the concentrations of dis-
solved species in a complex nonlinear manner which
makes it dicult to derive the chemical composition
of the original (before aqueous extraction) clay
porewater from aqueous extract data (Bradbury
and Baeyens, 1998; Sacchi and Michelot, 2000; Sac-
chi et al., 2001). The inference of dissolved concen-
tration for reactive species requires geochemical
modelling based on mineralogical data (Baeyens
and Bradbury, 1991; Pearson and Scholtis, 1995;
Baeyens and Bradbury, 1997, 1998, 2003; Pearson
and Scholtis, 2003; Fernandez and Rivas, 2005a;
Zheng et al., 2008).
4.3. Inference of porewater chemistry by inverse
geochemical modelling
The methodology to infer bentonite porewater
chemical composition from AET data is based on
the denition of a conceptual geochemical model
(CGM) for the claywater system. A CGM for a clay
sample is dened in terms of relevant chemical pro-
cesses taking place during aqueous extraction. Iden-
tication of the CGM requires knowing: (1) The list
phases, their initial volume fractions and equilibrium
constants, (3) cation exchange reactions, CEC and
cation selectivities, and (4) relevant gas phases, pres-
sures and conditions (open or closed). The method
starts from an initial CGM and a guess of sample
porewater concentrations, ci. Inverse modelling
accounts for perturbations caused by aqueous
extraction and computes concentrations of aqueous
extracts. Optimum estimates of ci are those which
minimize the dierences between measured and cal-
culated aqueous extract concentrations. Large devi-
ations of model results from measured data may
indicate the need to modify or update the CGM.
Estimated parameters include pH and concentra-
tions of major anions and cations of the original clay
sample. Additional details of inverse AET interpre-
tation can be found in Zheng et al. (2008).
4.4. Inferred chemical compositions
Table 7 shows measured water content and AET
data for bentonite samples at dierent radial dis-

Table 7
Chemical composition (in mg/L) of bentonite aqueous extracts samples (1:4 solid-to-liquid ratio) at dierent radial distances
Sample Radial distance (cm) Water content (w. %) pH Cl SO2
4 HCO
3 SiO2 Na+ K+ Ca2+ Mg2+
BB29-7/2-5 106.0 26.8 8.4 22 77 207 24.0 155 31 42 144
BB29-7/2-6 106.0 27.4 8.9 21 70 216 56.4 168 44 65 35
BB29-7/2-7 101.5 26.6 8.3 26 132 176 31.4 143 8.1 10 49
BB29-7/2-8 101.5 25.5 8.4 27 118 184 37.6 148 16 21 70
BB29-7/1-9 97.5 26.5 8.1 24 259 136 23.2 185 2.9 <1 1.1
BB29-7/1-10 97.5 26.5 8.2 29 156 162 28.2 148 3.2 1.1 2
BB29-7/1-11 93.5 25.8 8.0 38 260 141 26.1 185 2.9 <1 1.1
BB29-7/1-12 93.5 26.0 8.1 33 264 136 25.7 185 3.0 <1 1.1
BB29-12/2-1 87.5 21.0 8.1 59 270 143 26.3 215 3.1 1.1 1.6
BB29-12/2-2 82.5 22.0 8.1 76 293 139 27.6 219 3.6 1.9 2.1
BB29-12/2-3 77.5 20.3 8.0 164 255 121 27.1 250 4.1 2.8 2.6
BB29-12/2-4 72.5 19.9 8.0 280 207 108 26.8 280 5.4 6.2 4.3
BB29-11/2-1 66.0 16.3 8.1 348 137 119 31.5 300 6.4 7.9 5.1
BB29-11/2-2 61.0 15.2 7.9 370 171 111 32.4 310 6.9 9.1 5.6
BB29-11/2-3 56.0 14.2 8.1 348 192 123 34.6 310 7.0 8.1 5.4
BB29-11/2-4 51.0 14.2 8.2 315 209 153 35.7 280 6.7 5.1 3.4
1194 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201

Table 8
Inferred, calculated and measured 1:4 aqueous extract data for bentonite sample BB29-7/1-12 having a gravimetric water content of 26%
(concentrations in mol/L)
CGM-0 CGM-1 CGM-2 Measured
Inferred Calculated Inferred Calculated Inferred Calculated
Ca2+ 8.3  103 2.5  105 1.3  103 2.7  105 6.3  103 2.4  105 2.5  105
Cl 1.9  102 9.2  104 1.9  102 9.7  104 1.9  102 9.2  104 9.3  104
HCO 3 4.6  102 2.2  103 1.5  104 7.2  104 1.7  104 1.2  103 2.2  103
K+ 1.1  103 7.6  105 5.3  104 8.0  105 1.0  103 7.6  105 7.6  105
Mg 2+
1.5  102 4.4  105 2.4  103 4.9  105 1.3  102 4.6  105 4.5  105
Na+ 1.2  101 8.0  103 5.5  102 8.4  103 1.0  101 8.1  103 8.0  103
SO2
4 5.7  102 2.7  103 9.6  103 2.9  103 5.7  102 2.7  103 2.7  103

Table 9
Inferred, calculated and measured 1:4 aqueous extract data for bentonite sample BB29-11/2-3 having a gravimetric water content of 14.2%
(concentrations in mol/L)
CGM-0 CGM-1 CGM-2 Measured
Inferred Calculated Inferred Calculated Inferred Calculated
Ca2+ 6.2  102 1.9  104 4.3  102 2.0  104 6.2  102 2.1  104 2.0  104
Cl 3.2  101 9.8  103 3.2  101 9.8  103 3.2  101 9.8  103 9.8  103
HCO 3 6.7  102 2.1  103 1.4  104 8.2  104 1.5  104 9.1  104 2.0  103
K+ 2.8  103 1.8  104 2.4  103 1.8  104 2.8  103 1.8  104 1.8  104
Mg2+ 6.5  102 2.1  104 4.0  102 2.2  104 6.0  102 2.1  104 2.2  104
Na+ 1.9  101 1.3  102 1.6  101 1.3  102 1.9  101 1.3  102 1.3  102
SO2
4 6.7  102 1.9  103 2.0  102 2.0  103 6.7  102 1.9  103 2.0  103

tances of section 29 (Fernandez and Rivas, 2003).
Inverse geochemical modeling was performed for
all AET data of section 29. Detailed results for sam-
ples BB29-7/1-12 and BB29-11/2-3 which have
gravimetric water contents of 26% and 14.2%,
respectively, are listed in Tables 8 and 9. These
tables include measured AET data as well as
inferred and calculated compositions with CGM-0,
CGM-1 and CGM-2. Inferred concentrations are
much smaller than calculated concentrations due
to dilution caused by aqueous extraction. It can be
seen by comparing calculated and measured col-
umns in Tables 8 and 9 that models generally repro-
duce measured data. Models CGM-1 and CGM-2,
however, do not reproduce HCO 3 concentrations
accurately. This is an indication of their limitation
to represent adequately the chemistry of FEBEX
bentonite.
It should be noted that all models lead to similar
inferred results for all chemical species except for

SO2 2
4 and especially for HCO3 . Inferred SO4 con-
centrations with CGM-1 are smaller by a factor of
36 than those inferred with CGM-0 and CGM-2
because in model CGM-1 part of the measured
SO24 in aqueous extract tests is assumed to be
released by gypsum dissolution.
Bicarbonate inferred concentrations obtained
with model CGM-0 are almost two orders of magni-
tude greater than those of models CGM-1 and
CGM-2. This large dierence is caused by the
hypothesis of constant CO2(g) pressure of models
CGM-1 and CGM-2. These two models assume that
most of the measured HCO 3 in aqueous extract
tests is supplied by a constant CO2(g) pressure. In
other words, the assumption of constant CO2(g)
pressure provides the main source of dissolved
HCO 3 . Then, inferred concentrations are much
smaller than they would otherwise be.
5. Testing THC model predictions
THC model reproduces properly the radial distri-
bution of computed temperatures in bentonite and
granite just when heater 1 was switched o at
t = 1827 days (Fig. 4). The t to measured temper-
atures at dismantling time (t = 1930 days) is worse
because dismantling of concrete plug and bentonite
buer induced a 3-dimensional heat re-distribution
which is not taken into account in the 2D axy-sym-
metric THC model (Fig. 5).
The model captures the general trend of mea-
sured gravimetric water contents at the bentonite
 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201 1195

100 0.6

0.5 Bentonite
Granite
80

heater
1827 days
Temperature (C)

measured data 0.4 recalculated data CGM0

model results

Cl- (mol/L)
60 recalculated data CGM1
recalculated data CGM2
0.3 model results CGM0
model results CGM1
40 model results CGM2
0.2

20
0.1

0 0.0
0 4 8 12 16 0.30 0.45 0.60 0.75 0.90 1.05 1.20 1.35 1.50

Radial distance (m) Radial distance (m)

Fig. 4. Radial distribution of computed (line) and measured Fig. 7. Comparison of predicted Cl concentrations with models
temperatures after 1827 days of heating, just the day in which CGM-0, CGM-1 and CGM-2 (lines) with inferred aqueous
heater 1 was switched-o. extract data (symbols) at section 29 after 1930 days of heating.

40 0.16

1930 DAYS HEATER1 0.14 Bentonite

35 Granite
measured data

heater
0.12
model results
Temperature (C)

30 recalculated data CGM0

Ca2+ (mol/L)

0.1 recalculated data CGM1

recalculated data CGM2
0.08 model results CGM0
25
model results CGM1
model results CGM2
0.06
20
0.04

15
0.02

10 0
0 4 8 12 16 0.30 0.45 0.60 0.75 0.90 1.05 1.20 1.35 1.50
Radial distance (m) Radial distance (m)

Fig. 5. Radial distribution of computed (line) and measured Fig. 8. Comparison of predicted Ca2+ concentrations with
temperatures after 1930 days of heating. models CGM-0, CGM-1 and CGM-2 (lines) with inferred
aqueous extract data (symbols) at section 29 after 1930 days of
heating.

28

bentonite granite
gravimetric water content (%)

heater (Fig. 6). It should be noted that measured water

24 contents near the granitebentonite interface are
larger than the water contents corresponding to full
20
saturation at the original dry density of the buer
(w = 25%) due to bentonite swelling, a process not
taken into account in the model.
16 data Overprediction of measured water contents near
model results the heater is partly due to the fact that the model
12
considers a xed temperature of 97 C at the heater
0.3 0.45 0.6 0.75 0.9 1.05 1.2 1.35 1.5 which is equal to the average of measured tempera-
Radial distance (m)
tures at the heater surface which range from 75 to
Fig. 6. Radial distribution of computed and measured gravimet- 100 C. Model t to measured water contents near
ric water content after 1930 days of heating. the heater would improve if a temperature larger
than 97 C had been prescribed at the heaterben-
barrier after 1930 days. However, it underpredicts tonite interface. Another reason for overpredicting
measured water contents near the granitebentonite measured water contents near the heater is benton-
interface and overpredicts them near the heater ite shrinkage which is not considered in the model.
1196 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201

0.12 0.08
Bentonite Granite
recalculated data CGM0
0.10 Bentonite
Granite recalculated data CGM1

heater
recalculated data CGM2
heater

0.06 model results CGM0

recalculated data CGM0
0.08 recalculated data CGM1 model results CGM1

SO4 2- (mol/L)
Mg2+ (mol/L)

recalculated data CGM2 model results CGM2

model results CGM0

0.06 model results CGM1 0.04
model results CGM2

0.04

0.02
0.02

0.00
0.30 0.45 0.60 0.75 0.90 1.05 1.20 1.35 1.50 0.00
0.30 0.45 0.60 0.75 0.90 1.05 1.20 1.35 1.50
Radial distance (m)
Radial distance (m)
Fig. 9. Comparison of predicted concentrations of Mg2+ (lines)
Fig. 12. Comparison of predicted concentrations of SO24 (lines)
with inferred aqueous extract data (symbols) at section 29 after
with inferred aqueous extract data (symbols) at section 29 after
1930 days of heating using models CGM-0, CGM-1 and CGM-2.
1930 days of heating using models CGM-0, CGM-1 and CGM-2.

0.5
Bentonite Granite
1x10-1
0.4 recalculated data CGM0
heater

recalculated data CGM1

Granite
recalculated data CGM2 1x10-2

heater
model results CGM0
Na+ (mol/L)

0.3 model results CGM1

HCO3- (mol/L)

model results CGM2

1x10-3

0.2

1x10-4
recalculated data CGM0
0.1
recalculated data CGM1
-5 recalculated data CGM1
1x10
model results CGM0
model results CGM1
0.0
model results CGM2
0.30 0.45 0.60 0.75 0.90 1.05 1.20 1.35 1.50 Bentonite
1x10-6
Radial distance (m) 0.30 0.45 0.60 0.75 0.90 1.05 1.20 1.35 1.50
Radial distance (m)
+
Fig. 10. Comparison of predicted concentrations of Na (lines)
with inferred aqueous extract data (symbols) at section 29 after Fig. 13. Comparison of predicted concentrations of HCO 3
1930 days of heating using models CGM-0, CGM-1 and CGM-2. (lines) with inferred aqueous extract data (symbols) at section
29 after 1930 days of heating using models CGM-0, CGM-1 and
CGM-2.
0.006
Bentonite Granite
0.005
at t = 1930 days (see Figs. 713). Such a comparison
heater

recalculated data CGM0

0.004
recalculated data CGM1
recalculated data CGM2
provides a unique opportunity to test the THC
K+ (mol/L)

model results CGM0

model results CGM1
model of the engineered barrier system.
0.003 model results CGM2
Spatial distribution of the concentration of a
0.002
conservative species such as Cl is the result of the
combined eect of the following processes: (1) Ben-
0.001 tonite porewater evaporation near the heater, (2)
Water condensation some distance away from hea-
0
0.30 0.45 0.60 0.75 0.90 1.05 1.20 1.35 1.50 ter, (3) Dilution due to inow of granitic groundwa-
Radial distance (m) ter, (4) Advective displacement of the hydration
Fig. 11. Comparison of predicted concentrations of K+ (lines) front, and (5) Solute diusion which tends to dissi-
with inferred aqueous extract data (symbols) at section 29 after pate solute gradients. All of these processes lead to
1930 days of heating using models CGM-0, CGM-1 and CGM-2. a pattern of decreasing Cl concentration with
increasing radial distance (Fig. 7). THC predictions
THC predictions of the in situ test performed for CGM-0 and CGM-2 are slightly larger than
with CGM-0, CGM-1 and CGM-2 are compared those of CGM-1 because initial Cl concentration
to inferred AET geochemical data from section 29 of CGM-0 and CGM-2 (0.187 M) was derived from
 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201
squeezing tests while initial Cl concentration for
CGM-1 was derived from AET and is equal to
0.155 M (Table 5). The THC model overpredicts
Cl concentrations near the granitebentonite inter-
face (0.75 < r < 1.1 m) while it underpredicts them
for r < 0.75 m. While computed concentrations
decrease monotonically with distance in a convex
manner, measured values show a maximum at
r = 0.6 m.
Inferred aqueous extract Ca concentrations
from section 29 are largest near the heater and
decrease with increasing radial distance. Near the
bentonitegranite interface they increase again
due to a sampling artefact caused by colloidal par-
ticles (Fernandez and Rivas, 2003). Similar to Cl,
inferred Ca data show a maximum at r = 0.6 m.
Calcium inferred with CGM-0 and CGM-2 are
similar and generally larger than those inferred
with CGM-1. Such a discrepancy in Ca data is
related to the fact that CGM-1 assumes that ben-
tonite contains gypsum which may dissolve/precip-
itate at local equilibrium (see Table 2). THC
predictions with CGM-0 and CGM-1 are similar
and deviate from the cloud of inferred data. The
best t to inferred Ca data is achieved with
CGM-2 (Fig. 8).
Inferred Mg concentrations show a maximum at
r = 0.5 m. CGM-0 and CGM-2 lead to similar
inferred Mg concentrations which are generally lar-
ger than those inferred with CGM-1. The three
models lead to dierent predictions for Mg. The
best t for this cation is obtained with CGM-1
(Fig. 9).
In contrast to dissolved Ca and Mg, inferred Na
and K concentrations do not show a maximum at
r = 0.6 m. Sodium data inferred with CGM-0 and
CGM-2 are similar and generally larger than those
inferred with CGM-1. Predictions, however, are
similar for CGM-1 and CGM-2 which are smaller
than those obtained with CGM-0. Computed Na
concentrations reproduce the overall trend of
inferred data, but largely overpredict them near
the heater (Fig. 10). The best t to inferred Na data
is achieved with CGM-0 (Fig. 10).
Inferred K concentrations are similar for all
models. Predictions, however, are similar for
CGM-1 and CGM-2 and are larger than those
obtained with CGM-0. The best t to inferred K
data is obtained with CGM-2 (Fig. 11).
Inferred SO24 concentrations with CGM-0 and
CGM-2 are similar and generally larger by a factor
of 23 than those inferred with CGM-1. Inferred
1197
concentrations generally decrease with increasing
radial distance and show local minima at
r = 0.66 m. The best t to inferred SO2 4 data is
achieved with CGM-1 (Fig. 12).
CGM-1 and CGM-2 lead to similar inferred
HCO 3 concentrations. They are more than two
orders of magnitude smaller than those inferred
with CGM-0. Such a discrepancy in HCO 3 data is
related to the dierence in CO2(g) conditions (see
Table 2). THC predictions with CGM-0 deviate lar-
gely from the cloud of inferred data (Fig. 13). Pre-
dictions of CGM-1 and CGM-2 capture the trend
of inferred data, although such data are highly
uncertain.
Calcite which in model CGM-0 is assumed at
equilibrium (Table 2) precipitates at the node closest
to the heater and dissolves everywhere in the buer
(Fig. 14). The maximum cumulative precipitation at
the heater interface is 1.6 103 mol/L. Cumulative
calcite dissolution/precipitation computed with
models CGM-1 and CGM-2 is extremely small
due to the slow kinetic rate adopted for calcite
(see Table 4).
Dolomite is only considered in models CGM-1
and CGM-2. This mineral dissolves at the benton-
itegranite interface with cumulative values of
about 103 mol/L and precipitates in the rest of
the buer (not shown here).
All models have in common that anhydrite pre-
cipitates only at the node closest to heater. Cumula-
tive precipitation is about 0.1 mol/L. In model
CGM-1 anhydrite dissolves everywhere in the
0.0002
Bentonite Granite
heater
0.0001
Calcite (mol/L)
0.0000
-0.0001 model results CGM0
model results CGM1
model results CGM2
-0.0002
0.30 0.45 0.60 0.75 0.90 1.05 1.20 1.35 1.50
Radial distance (m)
Fig. 14. Spatial distribution of computed cumulative calcite
dissolution/precipitation (negative values for dissolution and
positive for precipitation) with model CGM-0 after 1930 days of
heating. Precipitation at the heater interface is much larger than
dissolution at other places and is not shown here.
1198 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201

40
Bentonite
Concentration of exchanged Ca, X2-Ca,
decreases about 6 meq/L near the heater and
Exchangeable Ca2+ (meq/100 g)

36
Granite increases slightly at the bentoniteconcrete inter-
heater

32 face due to calcite dissolution (Fig. 15). Exchanged

model results CGM0 Mg shows a pattern similar to that of X2-Ca
model results CGM1
28
model results CGM2 (Fig. 16). Exchanged Na, on the other hand,
increases 9 meq/L near the heater and decreases
24
slightly (1 meq/L) at the bentoniteconcrete
20 interface (Fig. 17). Exchanged K does not change
signicantly.
16
0.30 0.45 0.60 0.75 0.90 1.05 1.20 1.35 1.50
Patterns of reactive species show some similari-
Radial distance (m) ties with those of Cl, although their data show
more scatter. Reactive species are aected by ther-
Fig. 15. Spatial distribution of computed concentrations of
interlayer Ca with models CGM-0, CGM-1 and CGM-2 after
mohydrodynamic processes as well as by chemical
1930 days of heating. reactions. Aqueous concentrations increase near
the heater due to evaporation. This leads to precip-
40
itation of carbonate and sulphate minerals. Precipi-
tation of calcite causes a depletion of dissolved Ca
Exchangeable Mg2+ (meq/100 g)

Granite
which is compensated by a release of exchanged
heater

Bentonite Ca, X2-Ca. To ll the sites left by the release of

36
exchanged Ca, dissolved Na gets into the exchanger
and consequently X-Na increases. Since total cation
exchange concentration, CEC, is constant, an
32 increase in X-Na induces also a decrease in X2-Mg.
Mixing of bentonite and granite porewaters at
model results CGM0
model results CGM1 the bentonitegranite interface induces calcite disso-
model results CGM2

28
lution (Fig. 14) and cation exchange. Divalent cat-
0.30 0.45 0.60 0.75 0.90 1.05 1.20 1.35 1.50 ions have larger selectivities than those of
Radial distance (m)
monovalent cations and therefore both exchanged
Fig. 16. Spatial distribution of computed concentrations of Ca and Mg increase while X-Na decreases slightly
interlayer Mg with models CGM-0, CGM-1 and CGM-2 after (see Figs. 1517).
1930 days of heating.
6. Conclusions and uncertainties
50
model results CGM0
model results CGM1
THC predictions of the in situ test performed
Exchangeable Na+ (meq/100 g)

Bentonite
model results CGM2
with three conceptual geochemical models have
heater

40 been compared to measured temperature, water

content and chemical data collected after disman-
tling section 29.
Granite
30
Raw aqueous extract data for section 29 have
been interpreted with an inverse geochemical model
which accounts for geochemical processes taking
place in bentonite samples during aqueous extrac-
20
0.30 0.45 0.60 0.75 0.90 1.05 1.20 1.35 1.50 tion. To ensure consistency between inferred data
Radial distance (m) and model predictions, aqueous extract chemical
Fig. 17. Spatial distribution of computed concentrations of data have been inferred using the same conceptual
interlayer Na with models CGM-0, CGM-1 and CGM-2 at geochemical model used to perform THC
section 29 after 1930 days of heating. predictions.
Estimation errors for inferred chemical data are
buer, but its cumulative dissolution is four orders much smaller than errors associated with the identi-
of magnitude smaller than the amount precipitated cation of the conceptual geochemical model for
at the heater. FEBEX bentonite. For this reason, three dierent
 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201
conceptual models have been used to interpret AET.
Models reproduce measured aqueous extract data
except for CGM-1 and CGM-2 which cannot t
HCO 3 data accurately. They lead to similar inferred
results for all chemical species except for HCO3 and
SO2
4 . Inferred aqueous extract concentrations of
most species near the heater are larger than at the
granitebentonite interface where dilution is much
more pronounced.
Model predictions reproduce temperatures and
capture the trends of water content. The model
underestimates measured water contents near the
bentonitegranite interface and overestimates mea-
sured values near the heater. These discrepancies
are caused by the clay swelling/shrinking phenom-
ena which are not taken into account in the current
THC model.
Predicted Cl concentrations near the granite
bentonite interface overestimate measured values.
This discrepancy could be caused by changes in
porosity induced by the swelling/shrinking phenom-
ena and uncertainties in eective diusion coecient
of Cl and vapor tortousity.
Computed results of Mg, Na and K with the
three models reproduce the general trends of aque-
ous extract data. Models CGM-0 and CGM-1 t
Ca data better than model CGM-2. Predicted
SO2
4 concentrations underestimate systematically
inferred aqueous extract data. Such a discrepancy
could be related to the role of gypsum/anhydrite.
Bicarbonate inferred concentrations obtained with
model CGM-0 are greater than those from models
CGM-1 and CGM-2. This discrepancy is related
to the assumption on CO2(g).
Models CGM-1 and CGM-2 are less likely to
represent FEBEX bentonite porewater due to their
limitations in reproducing aqueous extract HCO 3 As indicated by an anonymous reviewer, high
data. On the other hand, models CGM-1 and espe-
cially CGM-2 lead to the best t to inferred chemi-
cal data of section 29. Therefore, since there is no
single model which performs well for inferring aque-
ous extract data and reproduces in situ test data, it
cannot be clearly concluded which conceptual geo-
chemical model is the best. Future studies should
improve CGM by identifying the role of sulfate
minerals and ascertaining the role of gaseous
phases.
THC model predictions have been tested with
aqueous extract data which in turn must be previ-
ously inferred with a hydrochemical model. This is
one of the main sources of uncertainty in the THC
model for bentonite. Another source of uncertainty
1199
is related to the fact that the model assumes that all
water content is accessible to solutes for transport
and geochemical reactions. Compacted bentonite,
however, contains dierent types of water such as
interlayer water located at the interlayer space
between montmorillonite units, double layer and
free water (Bradbury and Baeyens, 2002, 2003;
Fernandez et al., 2004; and Fernandez and Rivas,
2005b). Dual porosity models based on the dual
continuum approach of Zheng and Samper (2005)
provide a framework for considering free water,
interlayer and double layer water.
THC predicted concentrations systematically
overestimate measured values near the heater and
show gradients sharper than those of measured
data. This discrepancy could be overcome by con-
sidering bentonite swelling/shrinking and improving
the estimate of water evaporation at heaterbenton-
ite interface.
Laboratory experiments and model results
performed on FEBEX bentonite have provided rm
evidence for the relevance of proton surface
complexation for buering pH and controlling
HCO 3 concentrations (Fernandez, 2004; Samper
et al., 2007b). Future THC models should account
also for surface complexation protonation/
deprotonation.
THC models could be improved by incorporating
mechanical and geochemical couplings to account
for porosity changes caused by swelling phenomena.
This leads to fully coupled THMC models (Zheng,
2006). Preliminary results from a coupled THMC
model of a heating and hydration experiment on
FEBEX bentonite indicate that geochemical results
improve when changes in porosity caused by swell-
ing are considered (Zheng, 2006).
temperatures close to the heater may cause CO2
degassing from liquid water. Such CO2 will trans-
port through the gas phase and eventually redissolve
in liquid water again when it reaches the condensa-
tion zone. Future models should account for CO2
degassing and dissolution processes which aect
pH, dissolved HCO 3 and calcite dissolution and
precipitation.
The THC model has been tested with data from
section 29 of the FEBEX in situ test. Available data
indicate that there are chemical heterogeneities
along the buer which remain to be analyzed (Fern-
andez and Rivas, 2003).
It should be pointed out that the THC model
presented here was aimed at evaluating the geo-
1200 J. Samper et al. / Applied Geochemistry 23 (2008) 11861201
chemical evolution of the clay barrier during the
transient thermal and hydration stage. Performance
assessment of the long-term geochemical evolution
of a HLW repository requires models which
account for processes not considered here such as
redox reactions and interactions of canister corro-
sion products with bentonite (see Samper et al.,
2008).
Acknowledgements
This research was performed within the frame-
work of FEBEX project funded by ENRESA and
European Union through Contracts FI4W-CT95-
0006 and FIKW-CT-2000-00016 of the Nuclear Fis-
sion Program. We acknowledge contributions of
UDC researchers who participated throughout the
various stages of the FEBEX project. We thank
Wilfried Pngstein and a second anonymous re-
viewer for comments, suggestions and recommenda-
tions which have contributed to greatly improve the
paper.
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