Chemical Geology 193 (2003) 273 – 293

www.elsevier.com/locate/chemgeo

Argillization processes at the El Berrocal analogue granitic system

(Spain): mineralogy, isotopic study and implications for the
performance assessment of radwaste geological disposal
L. Pérez del Villar a,1, E. Reyes b,*, A. Delgado b, R. Núñez b,
M. Pelayo a, J.S. Cózar a
a
Centro de Investigaciones Energéticas, Medio Ambientales y Tecnológicas (CIEMAT), IDAE,
C.H.E., Avda. Complutense 22, 28040 Madrid, Spain
b
Departamento Ciencias de la Tierra y Quı́mica Ambiental. Estación Experimental del Zaidı́n (CSIC),
Profesor Albareda 1, 18008 Granada, Spain
Received 17 April 2001; accepted 27 September 2002

Abstract

The El Berrocal granite/U-bearing quartz vein (UQV) system has been studied as a natural analogue of a high-level
radioactive waste repository. The main objective was to understand the geochemical behaviour of natural nuclides under
different physicochemical conditions. Within this framework, the argillization processes related to fracturing and formation of
the uranium – quartz vein were studied from a mineralogical and isotopic standpoint in order to establish their temperatures of
formation and thus complete the geothermal history of the system. For this purpose, d18O values were determined for pure
mineral from the unaltered granite and quartz from the uranium – quartz vein, as well as for mixture samples from the
hydrothermally altered granite (sericitised granite) and clayey samples from fracture fillings, including the clayey walls of the
uranium – quartz vein. The isotopic signature of quartz from the uranium – quartz vein and the monophasic nature of its fluid
inclusions led us to conclude that the isotopic signature of water in equilibrium with quartz was approximately in the range
from
8.3xto
5.7xV-SMOV, its temperature of formation being around 85 – 120 jC. The d18O values of pure sericite
from the hydrothermally altered granite, calculated by means of the oxygen fraction molar method, indicate that its
temperature of formation, in equilibrium with the aforementioned waters, is also in the range from 70 jC to approximately
120 jC. Clays from fracture fillings and clayey walls of the uranium – quartz vein are usually mixtures, in different
proportions, of illite, approximately formed between 70 and 125 jC; two generations of kaolinite formed at approximately
90 – 130 jC and at around 25 jC, respectively; smectite, formed at V 25 jC; and occasionally palygorskite, formed either
between 30 and 45 jC or 19 and 32 jC, depending on the fractionation equation used. These data suggest that sericite from
the hydrothermally altered granite, quartz from the uranium – quartz vein, illite and the first generation of kaolinite from the
fracture fillings resulted from the same hydrothermal process affecting the El Berrocal granite in relation to fracturing. Under
certain physicochemical conditions (T c 100 jC, pH c 8 and log [H4SiO4] between
4 and
3), illite and kaolinite can be
paragenetic. As a result of weathering processes, smectite was formed from hydrothermal illite and inherited albite under

* Corresponding author. Fax: +34-958-129600.

E-mail addresses: lpvillar@ciemat.es (L. Pérez del Villar), ereyes@eez.csic.es (E. Reyes).
1
Fax: +34-913-466542.

0009-2541/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 5 4 1 ( 0 2 ) 0 0 3 2 3 - 6
274 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293

alkaline weathering, while the second generation of kaolinite was formed from smectite, under acid conditions and close to
the sulphide-rich uranium – quartz vein. Palygorskite is an occasional mineral formed probably either during the thermal tail
of the above-described hydrothermal process or during weathering processes. In both cases, palygorskite must have formed
from alkaline Si – Mg-rich solutions. Finally, these data and processes are discussed in terms of natural analogue processes,
drawing some implications for the performance assessment of a deep geological radwaste repository (DGRR).
D 2003 Elsevier Science B.V. All rights reserved.

Keywords: Clays; Quartz; Fracture fillings; Granite; Oxygen isotopes; Natural analogue

1. Introduction
Over the last 20 years, the international scientific
community has paid particular attention to studying
natural analogues to gain information on the condi-
tions of mobilisation and retention of natural nuclides
and other analogue elements in geological formations,
especially igneous, clayey and salt formations (Chap-
man and Smellie, 1986; Chapman, 1994; Choppin and
Wong, 1996; Smellie et al., 1997; Hidaka and Hol-
liger, 1998; Miller et al., 2000). Granite formations
have been deemed highly favourable for geological
disposal of radioactive wastes (Chapman and Smellie,
1986; Parneix, 1992). In this context, the mineralog-
ical and geochemical analysis of the secondary min-
eral phases from granite formations, particularly of
clay minerals, is informative for charting the history
of the alteration processes of granite rocks and for
determining the role of these minerals in the retention
of natural radionuclides.
The El Berrocal granite/U-bearing quartz vein
(UQV) system has been studied as a natural analogue
of a deep geological radwaste repository (DGRR), the
main objective being to understand the distant past,
recent past and present behaviour of natural nuclides
under real conditions, as well as to interpret it in terms
of rock – water interaction (Rivas et al., 1997). In this
context, the low-temperature hydrothermal alteration
and weathering events in the El Berrocal system have
been comprehensively studied, since they caused the
most important mobilisation, migration and retention
processes that affected the natural radionuclides in the
system (Pérez del Villar et al., 1994, 1995, 1996a,b,
1997; Reyes et al., 1998).
The aim of this work is to study the mineralogical
and isotopic composition of sericite from the hydro-
thermally altered granite, of quartz from the UQV and
the clay minerals from its clayey walls and from the
fracture fillings of the system, in order to:
Establish the approximate temperature of the
hydrothermal processes that affected the El Berro-
cal granite located close to the UQV, and of this
quartz vein itself.
Differentiate the argillization processes in fracture
fillings, according to the formation temperature of
the different clay minerals present in these
fractures.
All these data have been interpreted taking into
account the geological and geochemical background
of the system, emphasizing the relationships between
alteration and migration/retention processes affecting
natural radionuclides. Some implications for the per-
formance assessment of a DGRR in granite forma-
tions have been stated based on the geological
analogies and analogue processes observed at the El
Berrocal natural system.
2. Geological and geochemical background
The El Berrocal system is located some 90 km
southwest of Madrid, near the small town of Nom-
bela, in the province of Toledo (Spain). The system
takes its name from the El Berrocal granite pluton,
which is located in the central part of the Centro-
Iberian Zone, within the Spanish Hercynian Belt
(Julivert et al., 1972). The main granite facies of the
El Berrocal pluton, the so-called El Berrocal facies, is
the host-rock of a U sulphide-bearing quartz vein,
mined in the 1960s and known as ‘‘El Berrocal U
mine’’ (Arribas, 1965) (Fig. 1). Together, the host-
rock and the UQV, make up the so-called El Berrocal
 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293 275

Fig.1. Geographical location and geological scheme of the El Berrocal pluton: (a) biotitic granite of San Vicente type; (b) two mica porphyritic
granite (El Berrocal facies); (c) fine-grained leucogranitic facies; (d) Almorox-Navamorcuende aplitic dyke; (e) uranium quartz vein (UQV); (f)
undifferentiated Tertiary sediments (sands, clays and conglomerates).

system. The geological materials that form the El
Berrocal system are: (i) the El Berrocal facies or
reference granite, (ii) the hydrothermally altered gran-
ite, (iii) the weathered hydrothermally altered granite,
(iv) the weathered reference granite, (v) the UQV,
including its clayey walls, and (vi) the fracture fillings
(Fig. 2).
The reference granite was classified mineralogi-
cally as a weakly altered alkaline-feldspar granite with
two micas, muscovite being dominant over biotite.
Notable among the accessory minerals are ilmenite,
zircon, monazite, xenotime, apatite, uraninite, cassi-
terite and primary sulphides. Muscovite II, fluorite,
sericite, chlorite, rutile, anatase, K-feldspar and albite
II comprise the main secondary minerals, formed
probably during the deuteric and/or early postmag-
matic hydrothermal processes that affected the pluton.
The geochemical features indicate highly evolved
hypocalcic granite, enriched in silica, phosphorus
and alumina. This granite is fertile in U and belongs
276 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293

Fig. 2. N – S cross-section of the El Berrocal system showing the uranium mine gallery, and sampling points on boreholes.

to the ilmenite granite series or to the S-type granites
(Pérez del Villar et al., 1994).
The Rb – Sr isotopic data, as well as the structural
and textural relationships among the El Berrocal geo-
logical materials and the mineral paragenesis indicate
that the El Berrocal pluton intruded approximately
297 F 1 Ma ago, with an initial 87Sr/86Sr ratio of
0.7175 F 0.0029 (Pérez del Villar et al., 1996a,b). This
strontium ratio is typical of melted granite derived
from the continental crust (Faure and Powell, 1972).
Furthermore, the El Berrocal facies was affected by an
initial set of hydrothermal events at high temperature
 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293
(T>350 jC) defined as deuteric and/or early postmag-
matic alteration processes, which transformed the
original facies into the so-called reference granite.
These processes are weak but pervasive since they
affect the whole granite mass. The internal isochrone
determined from apatite, biotite, albite, K-feldspar and
bulk-rock sample of the El Berrocal facies suggests
that the bulk rock remained as a closed system for the
Rb – Sr pair during late alteration processes, and that
the minerals were closed for Sr isotopes around
289 F 1 my ago (Pérez del Villar et al., 1996a,b).
Consequently, the difference between the intrusion
age and the age estimated from the internal isochrone
(9 my) represents the time during which the first set of
hydrothermal alteration processes took place (Reyes at
al., 1998).
The second hydrothermal event recorded in the
system is related to N80E and N110E fracture fami-
lies. This process transforms the reference granite
close to the fractures into the so-called hydrothermally
altered granite. The alteration is evidenced by the
generalised sericitisation of feldspars, mainly albite,
the presence of secondary ankerite and calcite, which
are scattered in the rock, and the yellow-green colour
of the rock (Pérez del Villar et al., 1994). Based only
on isotopic data, the minimum formation temperature
of secondary carbonates is between 61 and 72 jC for
ankerite, and between 35 and 52 jC for calcite (Reyes
et al., 1998). In both carbonates, the influence of
edaphic carbon is evident, being stronger in the latter
than in the former (Reyes et al., 1998).
In relation to this process, sulphide-bearing quartz
veins and their clayey walls were formed, filling the
aforementioned fractures. The U mineralisation took
place after the fracturing of these veins, mainly in
those oriented N110E. The uraniferous paragenesis is
formed by pitchblende, pyrite, barite and carbonates,
the latter being detected by the presence of dissolution
moulds filled with Fe (Mn) oxyhydroxides (Reyes et
al., 1998). Fracture fillings, composed mainly of clay
minerals, Mn-rich calcite and minor secondary quartz,
result primarily from the interaction between fracture
gouges and hydrothermal solutions.
The intensity and depth of the weathering effects
on the El Berrocal system are related to the degree of
fracturing and hydrothermal alteration of the granite,
as well as the mineralogical composition of the hydro-
thermally altered granite, UQV, its clayey walls, and
277
fracture fillings (see Fig. 2). Geothermometric studies
of Mn-rich calcites, based on d18O values, indicate at
least two generations of carbonates, the first formed
under hydrothermal conditions, at a temperature range
of between 25 and < 100 jC, and the second at
ambient temperature ( < 25 jC) (Reyes et al., 1998).
Almost all the samples analysed were mixtures of the
two types of carbonates. The isotopic signature of
carbon in both generations of carbonates also indi-
cates the influence of edaphic carbon (Reyes et al.,
1998).
As a function of the physicochemical conditions
under which the alteration processes took place in the
system, these processes produced mobilisation, migra-
tion and retention, mainly by precipitation, of U (IV)
and Th (IV), as analogues for Pu (IV) and Np (IV); U
(VI), for Np (V and VI); light rare-earth elements
(LREE), for Am, Cm and Np (III) (Chapman and
Smellie, 1986) and Zr as a fission product (Pérez del
Villar et al., 1994, 1995; Reyes et al., 1998).
During the first set of deuteric and/or hydrothermal
events, uraninite, monazite, xenotime and apatite in
the granite were partially destabilised by F-rich fluids.
Thus, when uraninite crystals were surrounded by
fluorite they were totally or partially pseudomorphised
by complex U silicophosphates. Under the same
circumstances, monazite was totally or partially de-
pleted in REE, xenotime showed U and REE poor al-
tered zones and apatite was partially dissolved. The
presence of U silicophosphates coating chloritized
biotite and filling cleavage planes of distorted musco-
vite and microfissures in quartz implies the migration
of U away from uraninite, as well as its retention in
the rock matrix, respectively. On the contrary, Th from
monazite remains immobile, and no secondary REE-
bearing minerals have been found. These textural
features suggest that F is responsible for the alteration
of U, Th and REE-bearing minerals, as well as for the
transport of U and REE, probably as fluoride com-
plexes. This hypothesis was confirmed by the pres-
ence of secondary fluorite and U silicate compounds
filling dissolution voids in albite (Pérez del Villar et
al., 1995).
The second hydrothermal process, responsible for
the hydrothermally altered granite and quartz veins,
mobilised and also precipitated U, Th, REE and Zr.
The mineralogical evidence for these processes are: (i)
the appearance of U silicophosphates lining and filling
278 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293
microfissures of secondary pyrite; (ii) precipitation of
botryoidal mineraloids with a variable chemical com-
position from U>Th to Th>U silicophosphates; (iii)
presence of Th and Zr silicates filling microfissures in
quartz; (iv) neoformation of florencite and (v) the
general increase of U, Th, Ce, Y, and Zr contents in
the hydrothermally altered granite. In this case, the
chemical agent that mobilised U, Th, REE and Zr is
not as clearly defined as in the former case. However,
the presence of secondary carbonates in this hydro-
thermally altered granite implies that carbonate sol-
utions were at work in the system (Pérez del Villar et
al., 1995).
In relation to this second hydrothermal event, U
mineralised the main quartz vein. Its mineral para-
genesis (pitchblende, carbonates, pyrite and minor
barite) suggests that U from uraninite scattered in
the granite was oxidised, mobilised and transported,
as uranyl –carbonate complexes, downwards through
the fractures. These solutions, reheated at depth by
tectonic events, moved upwards, probably by con-
vective flow. After destabilisation of uranyl – carbo-
nate complexes, caused by rock – water interaction
processes and a drop in temperature and pressure,
uranyl cations were probably reduced by H2S, pre-
cipitating pitchblende, carbonates and pyrite. The
coexistence of pyrite and barite suggests that the
precipitation occurred between
200 and
300 mV
(Krivovichev, 1979). The same process also affected
the hydrothermally altered granite close to the UQV
and, to a less extent, the intragranitic fractures.
The effects of weathering on the uranium minerals
of each part of the system may be summarised as
follows:
On the uraninite from the reference granite, the
effects vary depending on the nature and fracturing
degree of the host minerals. When uraninite is
included in feldspars, the former is usually dissolved
and only the outlines of the crystals remain, with
residual Th – Ca silicophosphates inside. Uranium
from uraninite, forming U silicophosphates, usually
fills adjacent microfissures or is adsorbed, togeth-
er with P, onto Fe oxyhydroxides.
On the hydrothermally altered granite, weathering
mainly redistributed the U that forms large autunite
crystals and/or is adsorbed onto secondary sericite
and Fe oxyhydroxides.
On the U ore body, the effects of weathering are
represented by strong oxidation of pitchblende and
sulphides, dissolution of carbonates and neoforma-
tion of secondary U minerals such as uranotyle,
autunite, in secular equilibrium, torbernite and ura-
nocircite. Furthermore, U is also adsorbed onto Fe
oxyhydroxides.
On fracture-filling materials, similar weathering
effects have been found. Uranium forms uranyl
silicates and phosphates, such as uranotyle, autunite
and phosphuranylite, and occasionally it is ad-
sorbed onto Fe oxyhydroxides. Currently, uranyl –
carbonate complexes are the predominant uranium
species in oxidising groundwaters of the system
(Pérez del Villar et al., 1995; Reyes et al., 1998).
3. Sample collection and experimental methods
3.1. Sampling
Twelve samples from the reference granite (M)
were taken along the core of borehole 16, between
6.27 and 590.15 m in depth (Table 1, see Fig. 2) for
the separation of pure quartz, albite and muscovite, as
well as mixtures of chlorite and biotite, since both
phyllosilicates were closely associated in the samples.
Ten samples from the hydrothermally altered granite
(DTG) were taken along borehole S-13, between
84.93 and 100.65 m in depth, on both sides of the
UQV (Table 1, see Fig. 2). For reference granite, the
average sample size was cylinder-shaped, 20 cm long
and 8.6 cm in diameter, while for hydrothermally
altered granite, the average size was cylinder-shaped,
1 cm long and 8.6 cm in diameter.
Nine samples from the weathered hydrothermally
altered granite (LAR), six samples from the UQV
(DQ) and four from its clayey walls (DAR) were
taken from the U mine gallery (Table 1, Fig. 3).
Fracture fillings (RF) were sampled on the hole-cores
of S-13, S-14, S-15, S-16 and S-17 (Table 1, see
Fig. 2).
3.2. Analytical methods
For mineral separation from samples of the refer-
ence granite, 125 – 60 Am fractions were subjected to
electromagnetic methods and dense liquids. The pow-
 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293 279

Table 1
Sampling from the El Berrocal site for mineralogical and isotopic purposes
Reference granite Hydrothermally altered granite U mine Fracture filling
(S-16) Depths (S-13) Depths gallery Samples Depths
Samples (m) Samples (m) (m)
M-2 6.27 – 6.45 DTG.10554 84.93 LAR-1 Hydrothermally RF.13-6 87.30
M-3 8.59 – 8.79 DTG.10555 85.40 LAR-2 altered granite, RF.13-7 87.86
M-4 13.53 – 13.73 DTG.10556 86.10 LAR-3 affected by RF.13-14 108.02
M-5 17.62 – 17.82 DTG.10557 86.24 LAR-4 weathering RF.13-17 113.07
M-6 21.60 – 21.90 DTG.10558 87.47 LAR-5 RF.14-10 106.85
M-10 48.70 – 40.90 DTG.10559 88.96 LAR-6 RF.15-17 129.50
M-16 115.00 – 115.19 DTG.10560 90.15 LAR-7 RF.15-18 132.29
M-26 185.09 – 185.20 DTG.10561 91.60 LAR-8 RF.15-29 143.72
M-39 300.16 – 300.36 DTG.10562 96.30 LAR-9 RF.16-54 220.31
M-49 399.90 – 400.10 DTG.10563 100.65 DQ-1 Uranium RF.16-55 221.31
M-59 500.34 – 500.54 DQ-2 quartz vein RF.16-8 238.16
M-69 589.95 – 590.15 DQ-3 RF.16-10 413.58
DQ-4 RF.16-21 471.04
DQ-5 RF.16-23 473.15
DQ-6 RF.16-40 569.15
DAR-1 Clayey Walls RF.16-45 596.65
DAR-2 RF.17-12 70.85
DAR-3 RF.17-15 76.83
DAR-4 RF.17-27 156.05
Types of samples and location.

der X-ray diffraction (XRD) method was used for
checking the purity of minerals. Mineralogical com-
position of the hydrothermally altered granite was
determined by combining optical microscopy with
the powder XRD method, by using a plane-rotating
sample holder, and by scanning as well as transmi-
ssion electron microscopy (SEM and TEM) coupled
to an energy dispersive X-ray analysis system (EDX).
The mineralogical composition of < 2 Am fractions
from this type of granite was also determined.
For preparation and study of clayey materials from
the walls of the UQV and fracture fillings, the fol-
lowing method was used. After being dried at 30 jC,
the samples were smoothly ground in a porcelain mor-
tar to obtain a concentrate of the neoformed mine-
rals and another of the inherited minerals, under the
assumption that the former were preferentially con-
centrated in the soft fraction, while the second were
concentrated in the hard one. A 150-mesh (104 Am)
sieve was used to separate the two fractions. Only
soft fractions ( < 104 Am) were studied, after groun-
ding and sieving to a grain size of < 60 Am. Then,
the carbonates were eliminated to clean the silicate
fraction. An aliquot of the < 60 Am fraction was used
to determine the mineralogical composition, and ano-
ther to separate the < 2 Am fraction, according to the
Stoke’s law.
The < 60 and < 2 Am fractions were characterised
by XRD, combining the powder and oriented ag-
gregate methods. The former was applied to both
fractions, while the second, with ethylene glycol,
sulphoxide dimethyl and thermal treatments, was
applied only to the < 2 Am fractions. For semi-
quantification of the different clay minerals in the
samples, the Bradley and Grim (1961) method was
used. The percentage of apatite was calculated by
stoichiometry, under the assumption that the P2O5/
CaO ratio is 0.73 in the apatite of the reference granite
(Pérez del Villar et al., 1992). The clay minerals in the
< 2 Am fractions were more accurately identified using
TEM + EDX, thus facilitating the calculation of their
respective structural formulae.
For isotopic measurements, 12 samples from the
reference granite were used for determining 43 d18O
values on pure quartz (12), albite (10), muscovite (12)
and biotite – chlorite mixtures (9). Similarly, 10 ser-
280 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293

Fig. 3. Bird’s eye and side views of the inner part of uranium mine gallery (from 36 m to the end) showing fractures, quartz veins, including the
UQV and its clayey walls, and sampling points on weathered hydrothermally altered granite (LAR series), quartz veins (DQ series) and clayey
walls (DAR series).

icite-rich samples from the hydrothermally altered clayey mixtures from fracture fillings, more or less
granite, 9 samples from the weathered hydrothermally enriched in illite, smectite, kaolinite or palygorskite,
altered granite, 6 quartz samples from the UQV, 4 were also analysed. The d18O values of all the
clayey samples from its walls, and 19 samples of samples were determined using a Finnigan-MAT

Table 2
Oxygen isotope composition of pure minerals from the reference Table 3
granite (borehole S-16) (d values as xvs. V-SMOW) Mineralogical composition and d18OT of samples from the hydro-
Samples Q-d18O Ab-d18O Mus-d18O (B + Chl)-d18O thermally altered granite intersected by borehole S-13 (d values as
xvs. V-SMOW)
M.2 11.4 – 8.4 10.3
M.3 11.6 9.7 9.0 9.2* Samples Seric Q Ab K-Fd Chl Cc d18OT
M.4 11.7 8.9 9.9 9.0 DTG.10554 67 24 9 0 0 0 12.2
M.5 12.0 7.9 9.5 – DTG.10555 62 31 7 0 0 0 8.1
M.6 12.4 9.7 7.9 5.6 DTG.10556 81 16 3 0 0 0 8.5
M.10 11.5 11.1 8.7 – DTG.10557 65 31 4 0 0 0 7.5
M.16 11.5 9.1 10.1 – DTG.10558 34 31 23 10 2 0 10.4
M.26 11.3 10.8 8.0 4.6 DTG.10559 75 15 0 10 0 0 12.8
M.39 11.4 9.5 8.3 8.0 DTG.10560 39 26 0 8 0 27 12.4
M.49 11.6 – 9.2 5.2 DTG.10561 34 22 11 8 0 25 12.9
M.59 11.0 10.0 8.4 7.1* DTG.10562 40 9 20 12 7 12 13.5
M.68 10.8 8.1 8.0 7.1** DTG.10563 52 7 15 7 19 0 13.0
Q: quartz; Ab: albite; Mus: muscovite; B: biotite; Chl: chlorite; Seric: sericite; Q: quartz; Ab: albite; K-Fd: K-feldspar; Chl: chlorite;
* 100% biotite; ** 100% chlorite. Cc: calcite; d18OT: isotopic composition of the bulk sample (x ).
 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293 281

Table 4
Mineralogical composition of granite, quartz and clayey samples taken from the El Berrocal uranium mine gallery
Min Hydrothermally altered granite affected by weathering Quartz from UQV Clayey walls
(%) LAR- LAR- LAR- LAR- LAR- LAR- LAR- LAR- LAR- DQ- DQ- DQ- DQ- DQ- DQ- DAR- DAR- DAR- DAR-
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 1 2 3 4
Q 55 34 24 30 25 30 23 27 41 100 100 100 100 100 100 22 25 50 46
Ab 1 traces 7 4 3 – 3 4 4 – – – – – – 3 – 3 4
K-Fd – 7 15 8 9 8 7 8 – – – – – – – – – – –
Ap traces traces traces traces traces traces traces traces traces – – – – – – traces traces 5 traces
T.Ph. 43 59 54 58 63 62 66 60 54 – – – – – – 74 74 44 50
Q: quartz; Ab: albite; K-Fd: K-feldspar; Ap: apatite (determined by stoichiometry); T.Ph: total phyllosilicates; – : undetectable.

251 mass spectrometer, according to the ClF3 techni-
que (Borthwick and Harmon, 1982), later modified by
Vennemann and Smith (1990). These isotopic values
are reported using the d notation in units per mil (x)
relative to V-SMOW, d18O values being reproducible
to F 0.2. Using this procedure, the d18O values of
NBS-30 (biotite) and NBS-28 (quartz) are + 5.1xand
+ 9.7x , respectively.
For geothermometric purposes, the following frac-
tionation equations were used:
1000lna ¼ 3:38 ð106 T
2 Þ
3:40
for quartz (Clayton et al., 1972);
1000lna ¼ 2:43 ð106 T
2 Þ
4:80
for illite and sericite (Eslinger and Savin, 1973);
1000lna ¼ 2:5 ð106 T
2 Þ
2:9
for kaolinite (Land and Dutton, 1978); and
1000lna ¼ 2:6 ð106 T
2 Þ
4:28 ð4Þ
for smectite (Savin and Lee, 1988). In addition, two
approaches were tested to calculate the temperature of
palygorskite formation. The first, by using the equa-
tion for smectite, since experimental fractionation
equation for palygorskite is not yet available in the
specialised literature, and smectite and palygorskite
are chemically similar (Torres-Ruiz et al., 1994). The
second, by applying the equation proposed by Gauth-
ð1Þ ier-Lafaye et al. (1993).
However, two main problems arise in determining
the temperature of the formation of these minerals.
Firstly, all the samples are mixtures either of different
ð2Þ clay minerals or clay minerals and other granite-
forming silicates, mainly quartz and albite. Secondly,
no data could be gathered on isotopic signatures of
water in equilibrium with these minerals. However,
ð3Þ fluid inclusion studies performed on quartz samples

Table 5
Mineralogical composition and isotopic signature of the < 2 Am fractions from samples taken in the El Berrocal uranium mine gallery
Min Hydrothermally altered granite affected by weathering Quartz from UQV Clayey walls
(%) LAR- LAR- LAR- LAR- LAR- LAR- LAR- LAR- LAR- DQ- DQ- DQ- DQ- DQ- DQ- DAR- DAR- DAR- DAR-
1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 1 2 3 4
Q 19 18 17 18 17 14 18 14 12 100 100 100 100 100 100 9 16 13 11
Ab – – – – – – – – – – – – – – – – – – –
K-Fd – 14 23 10 11 12 16 5 17 – – – – – – – – – 18
Ap – – – – – – – – – – – – – – – – – 7 –
Ill 50 31 21 35 32 32 31 43 45 – – – – – 64 27 48 42
Sm 30 35 38 36 40 42 34 30 26 – – – – – – 26 48 32 28
K – 2 1 – – – – – – – – – – – – – 9 – –
d18O 11.2 11.9 13.6 13.7 13.6 14.7 14.4 12.9 8.6 14.2 14.4 15.3 12.7 14.2 12.6 9.7 14.3 10.2 10.1
Q: quartz; Ab: albite; K-Fd: K-feldspar; Ap: apatite (determined by stoichiometry); Ill: illite; Sm: smectite; K: kaolinite; – : undetectable; d18O:
in xV-SMOV.
282 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293

Table 6 and the isotopic signatures of bulk sericite-enriched

Chemical composition and structural formula of sericite – illite s. samples, pure quartz and albite from the reference
str., with < 5% of expanding layers
granite (Lawrence and Taylor, 1971; Ruiz-Cruz and
Samples DAR-3 DAR-4 DAR-3 LAR-1 DAR-3 DAR-3
Reyes, 1998). The theoretical d18O value for pure
Oxides (%) 1 2 3 4 5 6 illite was calculated from d18O signatures of several
SiO2 50.63 48.90 49.62 49.15 51.03 51.29 < 2 Am binary mixtures formed by illite + smectite
Al2O3 32.92 32.53 36.83 38.23 36.54 36.54 from fracture filling samples (RF series). For this,
Cr2O3 – – – – – –
the regression line between d18O values of the binary
Fe2O3 4.62 6.87 2.53 2.03 1.14 2.08
MgO – – – – – – mixtures and the illite/smectite ratios were calculated.
CaO – – – – 0.96 – The d18O value thus determined was also assigned to
K2O 11.83 11.71 11.02 10.59 10.32 10.09 illite from the clayey walls of UQV. The isotopic
Total 100 100 100 100 99.99 100 signature of pure smectite was measured on only one
sample from fracture fillings, formed by only smectite
Si4 + 6.467 6.308 6.265 6.180 6.395 6.413
Al3 + 1.533 1.692 1.735 1.820 1.605 1.587 (RF series). This value was also assigned to smectite
Total 8.000 8.000 8.000 8.000 8.000 8.000 from the clayey walls of the UQV. The theoretical

Al3 + 3.424 3.254 3.747 3.850 3.792 3.797

Fe3 + 0.444 0.667 0.240 0.190 0.110 0.200 Table 7
Cr3 + – – – – – – Chemical composition and structural formulae of beidellitic
Mg2 + – – – – – – smectite
Total 3.868 3.921 3.987 4.040 3.902 3.997 Samples DAR-2 DAR-2 DAR-2

K+ 1.927 1.927 1.775 1.700 1.651 1.610 Oxides (%) 39 40 41

Ca2 + – – – – – – SiO2 55.92 61.53 58.91
Mg2 + – – – – – – Al2O3 33.57 29.24 36.74
Total 1.927 1.927 1.775 1.700 1.781 1.610 Cr2O3 1.10 – –
Fe2O3 3.18 2.86 1.87
D
1.533
1.692
1.735
1.820
1.605
1.587 MgO 3.32 3.40 –
w
0.396
0.237
0.039 0.120
0.294
0.009 CaO 1.55 0.64 1.41
= 1.929 1.929 1.774 1.700 1.899 1.596 K2 O 1.38 1.25 1.07
Si/Al 1.304 1.275 1.142 1.089 1.184 1.191 Total 100.02 100.02 100.02
% 79.47 87.71 97.80 100 84.52 99.43
D: tetrahedral charge; w: octahedral charge; =: interlayer charge; Si4 + 6.700 7.290 6.928
%: of tetrahedral charge. Al3 + 1.300 0.710 1.072
Total 8.000 8.000 8.000

Al3 + 3.440 3.370 4.020

from the UQV have shown that primary fluid inclu- Fe3 + 0.290 0.260 0.165
sions are monophasic and that temperatures lower Cr3 + 0.100 – –
than 100 jC can therefore be inferred. Furthermore, Mg2 + 0.170? 0.370? –
the average d18O value (
7.6x) of the present day Total 4.000 4.000 4.185
meteoric waters at the El Berrocal site (Pérez del
K+ 0.210 0.190 0.161
Villar et al., 1997) was also considered for geother- Ca2 + 0.200 0.220 0.177
mometric purposes. Mg2 + 0.420? 0.23? –
Under these restraints, an approximate d18O value Total 0.830 0.64 0.338
for water in equilibrium with quartz from the UQV
was firstly established. For sericite from the hydro- D
1.300
0.710 1.072
w
0.170
0.37 0.555
thermally altered granite, an approximate theoretical = 1.450 ? 1.090 0.517
d18O value was calculated taking into account: the Si/Al 1.413 1.786 1.360
semi-quantitative mineralogical composition of the % 88.43 65.74 100
samples; the molar fraction of oxygen in each of the D: tetrahedral charge; w: octahedral charge; =: interlayer charge;
quantified minerals; the structural formula of sericite; %: of tetrahedral charge.
 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293 283

Table 8 values, while the d18O values for albite (An3) showed
Chemical composition and structural formula of kaolinite greater variability. These variations were even more
Samples DAR-2 DAR-2 DAR-2 DAR-2 DAR-2 DAR-2 accentuated in biotite – chlorite mixtures due to the
Oxides 42 43 44 45 46 47 nature of the samples. However, two values for almost
(%) pure biotite and one value for almost pure chlorite are
SiO2 54.08 52.83 52.22 53.69 54.93 52.98 also recorded.
Al2O3 43.40 46.29 45.40 46.31 44.56 45.79
Fe2O3 1.46 – 1.18 – 0.51 0.83
4.2. Mineralogy and d18O values of the hydro-
MgO – – – – – –
CaO – – 0.67 – – 0.40 thermally altered granite
K2O 1.07 0.89 0.52 – – –
Total The mineralogical composition and d18O values of
the bulk samples from the hydrothermally altered
Si4 + 4.045 4.060 4.000 4.040 4.060 4.013
granite intersected by borehole S-13 are listed in Table
Al3 + – – 0.09 – – –
Total 4.045 4.060 4.090 4.040 4.060 4.013 3. These data show that the main phyllosilicate in the
samples is sericite, while chlorite is also present in
Al3 + 3.82 3.82 3.910 3.980 3.890 3.940 three samples. The d18O values of the bulk samples
Fe3 + 0.08 – 0.070 – 0.030 0.47 ranged between 7.5xand 13.5xV-SMOV. For iso-
Mg2 + – – – – – –
topic purposes, it is noticeable that in the four first
Total 3.900 3.930 3.980 3.980 3.920 3.987
samples (DTG.10554 to DTG.10557) K-feldspar,
K+ 0.10 0.08 0.05 – – – chlorite and calcite were absent. Consequently, these
Ca2 + – – 0.053 – – – samples were used only for determining the theoret-
Mg2 + – – – – – – ical d18O value for pure sericite.
Total 0.10 0.08 0.156 – – 0.064

D 0.180 0.240 0.27 0.16 0.24 0.050

w
0.300
0.210
0.060
0.060
0.240
0.039 Table 9
= 0.120 0.030 0.15 0.10 0 0.013 Mineralogical composition and oxygen isotope composition of soft
Si/Al 1.06 1.06 1.00 1.01 1.04 1.018 fractions from fracture fillings intersected by boreholes S-13, S-14,
D: tetrahedral charge; w: octahedral charge; =: Interlayer charge. 42: S-15, S-16 and S-17
analysed point. Samples Q K-Fd Ab Chl Ill Sm K Pgk d18
OV-SMOW
d18O values of pure kaolinite and palygorskite were RF.13-6 2 – 3 – 61 33 1 – 9.5
calculated from samples enriched in these clay min- RF.13-7 – – – – 82 17 1 – 8.2
erals (DAR and RF series), by using the d18O values RF.13-14 5 6 4 4 11 70 – – 13.2
RF.13-17 – – – – 1 51 48 – 11.7
of their respective mixtures together with those meas- RF.14-10 – – – – 19 66 15 – 12.8
ured and calculated for pure minerals present in the RF.15-17 – – – – 46 54 – – 8.4
mixtures. In these cases, the same method as for RF.15-18 9 – 4 – 87 – – – 6.3
estimating of the isotopic signature for pure sericite RF.15-29 – – – – 79 21 – – 10.3
was also applied. RF.16-54 – – – – 13 30 57 – 10.4
RF.16-55 – 5 – – 9 40 46 – 11.6
RF.16-8 – – – – 73 27 – – 10.0
RF.16-10 8 – – 89 3 – – – 7.9
4. Results RF.16-21 – – – – – 100 – – 16.5
RF.16-23 3 3 3 – 3 88 – – 15.1
4.1. d18O values of pure quartz, albite, muscovite and RF.16-40 – – – – 10 90 – – 16.8
RF.16-45 – – – 68 27 5 – – 9.4
chlorite –biotite mixtures from the reference granite RF.17-12 1 – – – 7 21 – 71 15.1
RF.17-15 5 5 3 – 8 79 – – 15.4
The isotopic signatures (d18O values) of these RF.17-27 1 5 3 – 11 78 2 – 14.4
minerals (Table 2) were measured for correction Q: quartz; K-Fd: K-feldspar; Ab: albite; Chl: chlorite; Ill: illite; Sm:
purposes. Both quartz and muscovite gave constant smectite; K: kaolinite; Pgk: palygorskite; d18OV-SMOW: x.
284 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293
 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293
4.3. Mineralogy and d18O values of the weathered
hydrothermally altered granite, quartz from the UQV
and its clayey walls
The mineralogical composition of the bulk sam-
ples from these materials (Table 4) shows that phyl-
losilicates are generally the main components in the
samples, except in those from the UQV. The minera-
logical composition of their corresponding < 2 Am
fractions (Table 5) shows that the main clay minerals
in the samples, except for the quartz ones, are illite
and smectite, the former predominating over the
latter. Only three samples (LAR-2, LAR-3 and
DAR-2) contain minor kaolinite. The d18O values
for hydrothermal pure quartz ranged between 12.6x
and 15.3xV-SMOV, while for clay mixtures the
range was between 8.6xand 14.7xV-SMOV (see
Table 5).
The structural formulae of the main clay minerals
in the samples (Tables 6 –8) correspond to dioctahe-
dral clay micas (sericite/hydromuscovite and illite),
aluminian dioctahedral smectite, specifically beidel-
lite, and kaolinite, respectively.
4.4. Mineralogy and d18O values of fracture fillings
intersected by boreholes drilled at the site
Mineralogy and oxygen isotopic signatures were
determined only in the < 2 Am fractions of these
materials. The results (Table 9) indicate that, in
general, the main clay minerals in the samples are
illite and smectite, while kaolinite and chlorite are
occasionally present. Only one sample (RF.17-12)
contains a significant amount of palygorskite and
another (RF.16-21) consists exclusively of smectite.
Chlorite is inherited from the granite; illite comes
from the alteration of albite and, to a less extent, of
K-feldspar and muscovite (Fig. 4a); and smectite,
with a web-like pore-lining morphology (Fig. 4b),
mainly from the alteration of albite (Fig. 4c). Kao-
linite is idiomorphic, with a face-to-face stack-type
texture (Fig. 4d), and palygorskite shows its typical
Fig. 4. Secondary electron images showing: (a) the transformation of muscovite (1) into illite (2); (b) the web-like pore-lining texture of
smectite; (c) smectite from the alteration of albite. The chemical composition in points 1, 2, 3, 4, 5 and 6 corroborates the gradual albite –
smectite transformation; (d) the first generation of kaolinite (1), with its typical face-to-face stacked texture; (e) fibrous palygorskite coated by
Fe oxyhydroxides with some U and P adsorbed.
285
fibrous habit, but coated by Fe oxyhydroxides (Fig.
4e). The d18O value of pure smectite sample was
16.5xV-SMOW, while the d18O values of the re-
maining mixtures varied between 6.3xand 16.8x
V-SMOW.
5. Estimation of isotopic signatures for pure
minerals and geothermometry
5.1. Isotopic signature of water in equilibrium with
hydrothermal quartz
As mentioned in Section 3, primary fluid inclu-
sions in quartz from the UQV were monophasic, and
temperatures lower than 100 jC can therefore be
inferred. On the basis of the highest d18O values of
these samples (15.3x) and a temperature of approx-
imately 100 jC (or lower), the isotopic signature of
water in equilibrium with quartz could be more
negative than
5.7x. Similarly, given that the range
of isotope values for quartz was between 12.6x
and 15.3x, the d18O range for water in equilibrium
was between
8.3xand
5.7x. However, though
this range can be considered quite likely, d18O va-
lues more negative than
8.3xare possible if the
temperature of formation of quartz was lower than
100 jC.
5.2. Theoretical d18O values for sericite from the
hydrothermally altered granite
Three of the ten samples analysed (DTG.10555 to
DTG.10557, see Table 3) were selected to estimate
the theoretical d18O value of pure sericite, since they
were ternary mixtures of mainly sericite, magmatic
quartz and minor albite, with similar d18OT values.
Sample DTG.10554, with a similar mineralogical
composition, had an extremely high d18OT value
and was therefore rejected. For calculation, the
fraction molar method was used, taking into account
the structural formula of silica, albite (An3) and
286 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293
sericite, and applying the following general equa-
tion:
Xa d18 Oa þ Xb d18 Ob þ Xc d18 Oc þ . . . Xn d18 On
¼ d18 OT ð5Þ
Abbreviated as:
X
c
Xn d18 On ¼ d18 OT ðn ¼ a . . . cÞ
n¼a
where: a, b, c,. . .n = minerals in the sample or
mixture; d18On = isotopic signature of each pure
mineral in the sample or mixture, known from
pure minerals experimentally measured; Xn = num-
ber of mols of oxygen in each mineral, referred as
a fraction of the total mols of oxygen in the
sample or mixture.
X
c the illite/smectite ratios and the experimental d18O
Xn ¼ 1
n¼a
d18OT = d18O experimentally measured in the total
sample or mixture.
For the particular case of the hydrothermally
altered granite, a, b and c are sericite, magmatic quartz
and albite (An3), respectively. For quartz and albite,
the average d18O values were used (Table 2). The
mineralogy and d18OT of the samples used are shown
in Table 3.
For sericite, the structural formula used was (Si6.387
Al1.613)(Al3.339Fe0.555)K1.927O20(OH)4, which repre-
sents the average formula of the first two formulae
(Eqs. (1) and (2)) listed in Table 6 since they are the
most representative for this phyllosilicate. Thus, the
theoretical d18O value for pure sericite ranges between
5.2xand 7.8xV-SMOV.
For calculating an approximate temperature of
formation of sericite, the range of the d18O values
(
8.3xand
5.7x) for waters in equilibrium with
hydrothermal quartz from the UQV was used since it
was assumed that both UQV and hydrothermally
altered granite resulted from the same geological
process. According to these parameters, the minimum
temperature varies from 70 to 117 jC (Fig. 5a).
5.3. Theoretical d18O values for smectite, illite,
kaolinite and palygorskite from the clayey walls of
UQV, weathered hydrothermally altered granite and
fracture fillings
The wide range of isotopic values found in these
samples is attributable to the fact that all the < 2 Am
fractions were mixtures of different minerals that in
turn were impossible to separate physically (see
(Tables 4, 5 and 9)). This circumstance enabled the
calculation of only an approximate d18O value for
each pure clay mineral. However, sample RF.16-21
consists exclusively of smectite with an d18O value of
16.5x, which agrees with the theoretical d18O value
for a smectite in equilibrium with the current meteoric
waters at El Berrocal (d18O =
7.6x), at a near-
surface temperature.
For estimating the theoretical d18O value of illite
from the clay mixtures, an initial approach was used
following a method similar to that of Whitney and
Northrop (1988). Thus, from the correlation between
values determined from samples RF.13-7, RF.15-17,
RF.15-29, RF.16-8, RF.16-21 and RF.16-40, which
were binary mixture of illite and smectite (see Table
9), a theoretical d18O value ( + 6.7x) for illite was
estimated (Fig. 6). A second approach was used to
calculate the d18O value of illite, using the oxygen
fraction molar method (Eq. (5)) on samples formed
mainly of smectite and illite, with minor quartz or
quartz and albite (samples LAR-1; DAR-1, RF.13-6
and RF.15-18). For calculation, the d18O values used
were 16.5xfor smectite and 11.5xand 9.5xas
average values for magmatic quartz and albite, respec-
tively (see Table 2). With this second approach and
data, the d18O value for illite ranged between 4.6x
and 8.0x.
The temperature of illite formation is difficult to
estimate since no data are available on the isotopic
signature of water in equilibrium with illite. However,
from the structural relationships among UQV, its
clayey walls and the hydrothermally altered granite,
it can also be assumed that these materials are formed
as a result of the same hydrothermal process. Con-
sequently, the isotopic range for water in equilibrium
with quartz from the UQV (
8.3xand
5.7x)
and the equation for illite –water fractionation (Eq. (2))
can be used to estimate the illite formation temper-
 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293 287

Fig. 5. (a) Plot of the Eslinger and Savin (1973) equation, from which the temperature range for sericite from the hydrothermally altered granite
has been estimated. (b) Idem for illite from fracture fillings and clayey walls of the UQV. (c) Plot of the Land and Dutton (1978) equation on
which the temperature of formation for the second generation of kaolinite has been calculated. (d) Idem for the first generation of kaolinite. (e)
Plot of the Savin and Lee (1988) equation for smectite – water fractionation, applied to palygorskite. (f) Plot of the Gauthier-Lafaye et al. (1993)
equation for palygorskite – water fractionation, also applied to the El Berrocal palygorskite.
288 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293
Fig. 6. Correlation between the illite/smectite ratios and the experimental d18O values obtained from the illite/smectite samples from which a
theoretical d18O value for pure illite has been estimated.
ature, this is ranging from 69 to approximately 124 jC
(Fig. 5b).
Prior to the estimation of the isotopic signature and
thermometry of the remaining clay minerals in the
samples, kaolinite and palygorskite, it is appropriate
to take into account the following assumption. Weath-
ering under acidic and intensive cation leaching con-
ditions or low-temperature hydrothermal processes
(Raymahashay, 1968) are usually the main geological
mechanisms that originate kaolinite, if the country
rocks are suitable. On the contrary, palygorskite is
usually formed in very restricted geological environ-
ments, under alkaline conditions, with high activities
of silica and magnesium.
In the El Berrocal system, kaolinite occurs either in
the shallow and oxidised zone of the UQV-clayey
walls, where pyrite is almost totally oxidised and
sulphate acid percolating waters (pH 3– 4) are present
today, or in deeper fractures, where reducing, neutral
or weakly alkaline conditions prevail.
On these bases, kaolinites from these two different
environments were considered separately to determine
their respective d18O values and formation temper-
atures. Sample DAR-2, formed by smectite, illite,
kaolinite and hydrothermal quartz, has been consid-
ered for shallow kaolinite, while samples RF.13-17,
RF.14-10 and RF.16-54, which are mixtures of illite,
smectite and kaolinite, have been retained for deeper
kaolinites.
From sample DAR-2, the d18O value estimated for
pure shallow kaolinite is 19.1xV-SMOW by apply-
ing Eq. (5) and using the d18O values for smectite
(16.5x), the average value for hydrothermal quartz
(13.9x) and the highest values for illite (8.0x). In
the same way, for pure deeper kaolinites the d18O
values vary between 2.6xand 8.3xV-SMOW. The
difference between the isotopic signatures of the shal-
low and deeper kaolinites seems to corroborate the
different geological environments in which they were
formed, as mentioned above. Consequently, for esti-
mating the formation temperature of shallow kaolinite,
it seems reasonable to assume that it was formed in
equilibrium with the present-day meteoric waters, with
a weighted average d18O value of
7.6xV-SMOW.
Thus, the maximum formation temperature estimated
for shallow kaolinite was 26 jC (Fig. 5c).
On the other hand, as kaolinite can also be formed
in hydrothermal systems under conditions similar to
 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293
those that form illite (Raymahashay, 1968), deeper
kaolinites can also be equilibrated with waters in
equilibrium with both hydrothermal quartz and illite,
provided that the three minerals resulted from the
same hydrothermal process. Thus, the temperature of
formation of deeper kaolinites ranged from 88 to
133 jC (Fig. 5d). A similar temperature range re-
sulted when present-day meteoric waters were used
for this purpose since both hydrothermal and mete-
oric waters at the site have very similar isotopic
signatures.
The presence of different generations of kaolinites
(specifically dickites), including one of Quaternary
age (dickite from sample DAR-2), has also been
confirmed in the El Berrocal system, by using Fourier
transform infrared spectroscopy (FTIR) (Allard et al.,
submitted for publication).
Regarding palygorskite, sample RF.17-12, formed
essentially by this mineral and smectite together with
minor illite and quartz, was considered only for
isotopic and geothermometric purposes. For pure
palygorskite the d18O value varied from 15.5xto
15.8xV-SMOW, and the estimated temperature
ranged between 31 and 45 jC, when the assumption
proposed by Torres-Ruiz et al. (1994) was applied
(Fig. 5e). However, this temperature range was
approximately 10 jC lower (19 –32 jC) when the
equation proposed by Gauthier-Lafaye et al. (1993)
was used (Fig. 5f). In any case, both temperature
ranges agree with those estimated for low-temperature
carbonates from the hydrothermally altered granite
(52 – 35 jC) and for low-temperature carbonates from
fracture fillings, some of them formed at ambient
temperature ( V 25 jC) (Reyes et al., 1998). Finally,
palygorskite as well as carbonates need similar phys-
icochemical conditions for precipitation.
6. Discussion and conclusions
6.1. Argillization processes
The approximate isotopic signature (d18O) esti-
mated for the hydrothermal waters at the El Berrocal
site is very similar to that for the present-day meteoric
waters, despite boiling and water – rock interactions
that could affect the hydrothermal ones. In this sense,
Reyes et al. (1998), on the basis of the isotopic
289
signatures (d18O and d13C) of carbonates, suggested
that the hydrothermal water at the El Berrocal site had
a meteoric origin, being reheated in depth and moving
upwards by convective flow.
The d18O range estimated for sericite from the
hydrothermally altered granite and the intensity of
the sericitisation process suggests that this mineral
was formed at around 100 jC, with a high water/
rock ratio, as corresponds to a highly fractured
geological environment. Illite from fracture fillings
and clayey walls of the UQV was probably the result
of the same hydrothermal process, since its forma-
tion temperature is also around 100 jC. Both pro-
cesses—sericitisation of reference granite and illiti-
sation of fault gouges—were probably controlled by
the following two well-known general chemical
reactions:
K
feldspar þ bicarbonate
carbonate H2 O
Zsericite or illite þ SiO2 þ Kþ þ Carbonates ð6Þ
Albite þ bicarbonate
carbonate H2 O þ Kþ
Zsericite or illite þ SiO2 þ Naþ þ Carbonates ð7Þ
In the hydrothermally altered granite, these reac-
tions are supported by the presence of K-feldspar and
albite pseudomorphised by a mixture of sericite,
carbonates and microcrystalline quartz. Furthermore,
potassium released from reaction (6) was used in Eq.
(7) and sodium released from Eq. (7) probably
migrated outside the system. Neoformed sodium min-
erals have not been found in the samples. Similarly,
silica released from both reactions was probably spent
in the formation of quartz veins, particularly the UQV.
This quartz was also formed at approximately 100 jC.
The presence of kaolinite formed at the same
temperature as illite suggests that both clay minerals
were also formed during the same alteration pro-
cesses, but only in those fractures where the phys-
icochemical conditions were suitable for its formation.
In this sense, the pH – log [H4SiO4] stability diagram
(Raymahashay, 1968) shows that the boundary
between the muscovite and kaolinite stability fields
at 95 jC is located at pH = 8 for a log [H4SiO4] range
between
4 and
3 (Fig. 7). Consequently, illite
290 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293
Fig. 7. Stability fields of gibbsite, kaolinite, muscovite, K-feldspar
and montmorillonite in alkaline environment after Raymahashay
(1968).
and this first generation of kaolinite are assumed to be
paragenetic in those fractures where the pH ap-
proached 8. Above this pH value, only illite would
be formed.
These parameters agree with the presence in the
hydrothermally altered granite and fracture fillings of
carbonates formed below 100 jC and with some
influence of edaphic carbon (Reyes et al., 1998),
thereby corroborating the meteoric origin of the
hydrothermal waters circulating in the system.
According to the textures observed by SEM, smec-
tite comes mainly from the alteration of albite, prob-
ably as a result of the following general reaction:
Albite þ bicarbonate
carbonate H2 O
ZSiO2 þ Smectite þ Carbonates
Illite can also be transformed into smectite by the
reaction:
Illite þ SiO2 þ bicarbonate
carbonate H2 O
ZSmectite þ Kþ þ Carbonates
Furthermore, geothermometric studies indicate that
smectite was formed at ambient temperature (e.g. in
relation to weathering processes) under alkaline con-
ditions. This agrees with the stability diagram at 25 jC
(see Fig. 7) and with the presence of carbonates formed
at environmental temperature, which also have a sub-
stantial influence of edaphic carbon (Reyes et al.,
1998).
Kaolinite formed at approximately 25 jC can be
explained as having formed under the acid conditions
caused by the oxidation of sulphides from the UQV.
Under these physicochemical conditions, mainly
smectite is transformed into kaolinite, according to
the following general reaction:
Smectite þ acid H2 O
ZKaolinite þ Ca2þ þ Mg2þ þ Kþ þ Quartz ð10Þ
The fact that only one sample from the oxidised
zone of the clayey walls of the sulphide-bearing UQV
contains minor kaolinite (9%) is probably due to the
extremely low permeability of these clayey walls that
hindered the water – rock interactions between the
sulphate acid percolating waters and smectite.
For palygorskite, an occasional mineral in the
fracture filling materials, only one datum concerns
the temperature of its formation (31 – 45 or 19 –32 jC)
is available. This mineral was therefore probably
formed either during the thermal tail of the hydro-
thermal process described above and simultaneously
with the lower temperature carbonates or during
weathering processes. In both cases, palygorskite
must have formed from alkaline Si– Mg-rich solu-
tions. In any case, this fibrous clay mineral appears to
have formed specifically in those fractures of the
system where these physicochemical conditions
ð8Þ occurred.
6.2. Implications for the performance assessment
Some analogies between El Berrocal system and a
deep geological radwaste repository can be drawn:
ð9Þ The UQV contains pitchblende (UO2 + x), which is
analogous to the main component of the spent
nuclear fuel (source term).
The geometry of the UQV is very simple and it is
bordered on two clayey walls analogous to the
engineered clayey barrier envisioned to isolate the
spent nuclear fuel (near field).
 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293
The UQV is hosted in highly evolved S-type
granites (store rock or far field), which are well
represented in the European Hercynian Belt.
On the contrary, the UQV, highly fractured and
very permeable, is perturbed by mining activities and,
particularly, contains considerable amounts of sul-
phides and carbonates, which in principle are two
‘‘poisonous’’ minerals under oxidising conditions.
Their dissolution also facilitates the destabilisation
of pitchblende and encourages the migration of ura-
nium.
Finally, the granite country rock of the El Berrocal
UQV contains uraninite and is therefore the second
source of U in the system. This feature hampers the
delimitation of the dispersion haloes of U from the
UQV and from the granite itself. In addition, the El
Berrocal granite shows a very high fracture density,
though fractures are generally filled by clay minerals,
minor Fe oxyhydroxides and other minerals, mainly
phosphates, that participate in the retardation of U
(VI).
According to these geological and mineralogical
features, the El Berrocal system cannot be considered
a completely natural analogue of a deep geological
radwaste repository. However, in terms of the pro-
cesses affecting the system, both low-temperature
hydrothermal and weathering processes can be com-
pared to those expected in a nuclear repository after
burial, under extremely adverse circumstances.
The low-temperature hydrothermal process could
be similar to that expected in a radwaste repository
after burial, since a thermal peak related to radioactive
decay of fission products from the spent fuel is
envisaged (less than 100 jC in the ENRESA con-
ceptual model).
In the natural system under investigation, the low-
temperature hydrothermal process caused:
The accumulation in the UQV of U scattered in the
granite, as a result of a first downward step of U
mobilisation, under oxidising and weakly acidic or
alkaline conditions, and environmental tempera-
ture; and a second upward step of U (IV) preci-
pitation, under weakly alkaline and reducing con-
ditions at higher temperatures, but below 100 jC.
The argillization of the fault gouges, including the
UQV walls, and the hydrothermal alteration of the
291
reference granite close to fractures, increasing their
clay contents and therefore their retention capa-
bilities for natural nuclides and other analogous
elements (Pérez del Villar et al., 1995, 1997).
If a similar process occurs in a nuclear repository,
two possibilities can be considered. The first would be
that the oxidising meteoric waters percolate down to
the spent fuel, and the second that the meteoric waters
lose their oxidising capability (by rock – water inter-
action processes) before interaction with the spent
fuel. In the first case, the source term would be
destabilised, and U and other nuclides would be
dispersed as a function of their solubility in these
reheated waters. However, clays from an engineered
barrier, fracture fillings and country rock itself would
work against the migration of radionuclides as in the
El Berrocal natural system (Pérez del Villar et al.,
1997). In the second case, the source term would
remain totally or partially unaltered. Only coffinitisa-
tion of the UO2 + x from the spent fuel could be
expected (Pérez del Villar et al., 2002). Furthermore,
the hydrothermal system artificially created in the
nuclear repository would alter the granitic storage
rock, mainly through the fracture zones, increasing
its clay content and therefore its retention capability.
In addition, past and recent past weathering pro-
cesses were more intensive and deeper on the UQV
than in the hydrothermally altered and reference
granites due to their different secondary permeability.
The pH of these waters in the upper part of the UQV is
usually around 3 – 4, but close to 7 in the other
hydraulically active fractures. In both cases, waters
become weakly alkaline in depth (Pérez del Villar et
al., 1995). Accordingly, the following analogies can
be established:
(a) In the UQV itself or source term, oxidation due
to weathering caused the total oxidation and
dissolution of pitchblende, sulphides (mainly
pyrite), and carbonates, as well as the precip-
itation of jarosite (pH 3 – 4) and Fe (Mn)
oxyhydroxides with minor U and P adsorbed
(Pérez del Villar et al., 1995, 1997). Conse-
quently, this intense downward oxic and acid
alteration in the upper part of the UQV is of no
relevance in assessing repository behaviour. How-
ever, once the conditions of neutrality – alkalinity
292 L. Pérez del Villar et al. / Chemical Geology 193 (2003) 273–293
and reducing potential are restored in depth, the
original mineral paragenesis [pitchblende, sul-
phides (mainly pyrite) and carbonates] becomes
stable, illustrating again the well-known stability
of natural UO2 + x under reducing conditions. In the
transition between oxidised and reduced zones, in
situ transformation of pitchblende into uranocircite
and autunite together with the precipitation of
torbernite occur, this zone being therefore relevant
as a geochemical discontinuity for natural nuclide
retardation.
(b) In the clayey walls or near field, with lower per-
meability than UQV itself, inherited albite and
particularly illite were transformed firstly into
smectite under weakly alkaline conditions increas-
ing therefore the buffer capability of this natural
clayey barrier. After this transformation, the
system became acid by the oxidation of sulphides
and minor smectite was occasionally transformed
into kaolinite, a clay mineral without any adequate
buffer and physicomechanical properties to work
as barrier against migration of U and other trace
analogue elements. Consequently, smectite – kao-
linite transformation must be avoided regardless
of the geological site selected for radwaste
disposal.
(c) In the shallow hydrothermally altered granite and
fracture fillings (far field), weathering also trans-
formed illite and residual albite into smectite,
generally increasing their retention and buffer
capabilities against the mobility of natural radio-
elements. Uranium is usually trapped by the
clayey minerals in the rock, Fe oxyhydroxides
and sometimes precipitated as autunite, as a result
of the presence of significant amounts of phos-
phorous in the system. This is a relevant anion-
forming element for the retention, by precipita-
tion, of the complex uranyl cation and other
analogous elements.
Acknowledgements
ENRESA, CIEMAT and EU provided the financial
supports for this work. Dr. N. Clauer and another
anonymous reviewer are also thanked for their useful
criticisms, comments and suggestions that improved
the manuscript. [PD]
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