Chemical Geology 150 Ž1998.

293–315

Carbonatation processes at the El Berrocal natural analogue

granitic system žSpain /: inferences from mineralogical and stable
isotope studies
a,)
E. Reyes ´ del Villar b, A. Delgado a, G. Cortecci c , R. Nunez
, L. Perez ´ ˜ a,
M. Pelayo b, J.S. Cozar
´ b
a
´
Departamento Ciencias de la Tierra y Quımica ´ Experimental del Zaidın
Ambiental, Estacion ´ (CSIC), Prof. Albareda 1. 18008 Granada,
Spain
b
´
Centro de InÕestigaciones Energeticas, ´
Medio Ambientales y Tecnologicas (CIEMAT), IDAE, C.H.E. AÕda. Complutense, 22, 28040
Madrid, Spain
c
Dipartimento Science della Terra e Geologico Ambientale, UniÕersita` di Bologna, Piazza Porta S. Donato, 1, 40126 Bologna, Italy
Received 28 November 1997; revised 24 June 1998; accepted 24 June 1998

Abstract

The El Berrocal graniterU-bearing quartz vein system has been studied as a natural analogue of a high-level radioactive
waste repository. The main objective is to understand the geochemical behaviour of natural radionuclides occurring under
natural conditions. In this framework, the carbonatation processes have been studied from a mineralogical and isotopic Ž d13C
and d18 O. point of view, since carbonate anions are powerful complexing agents for UŽVI. under both low-temperature
hydrothermal and environmental conditions. The carbonatation processes in the system are identified by the presence of
secondary ankerite, with minor calcite, scattered in the hydrothermally altered granite, and Mn calcite in fracture filling
materials. The isotopic signatures of these carbonates lead us to conclude that ankerite and calcite from the former were
formed at the end of the same hydrothermal process that altered the granite, at a temperature range of between 728 and 618C
for ankerite, and between 528 and 358C for calcite. The effect of edaphic CO 2 on both carbonates, greater on calcite than on
ankerite, is demonstrated. Calcites from fracture fillings are, at least, binary mixtures, in different proportions, of
hydrothermal calcite, formed between 258 and - 1008C, and supergenic calcite, formed at F 258C. According to their d13C
signatures, the effect of edaphic CO 2 in both calcites is also evident. It is assumed that: Ži. hydrothermal calcite from
fracture fillings and ankerite from the hydrothermally altered granite are the result of the same hydrothermal process, their
chemical differences being due to the intensity of the waterrrock interaction which was stronger in the altered granite than
in the fractures; and Žii. all of these carbonatation processes are responsible for ancient and recent migrationrretention of
uranium observed in the hydrothermally altered granite and fracture fillings. q 1998 Elsevier Science B.V. All rights
reserved.

Keywords: Granite; Fracture fillings; Carbonates; Isotopes; Carbon; Oxygen; Natural analogue

)
Corresponding author. Fax: q34 58 12 96 00; e-mail: ereyes@eez.csic.es

0009-2541r98r$ - see front matter q 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 5 4 1 Ž 9 8 . 0 0 1 1 1 - 9
294 E. Reyes et al.r Chemical Geology 150 (1998) 293–315
1. Introduction
The study on radionuclide migration and transport
is a controversial subject in environmental and earth
sciences and the studies made have mainly focused
on laboratory experiments using simple physico-
chemical systems ŽChoppin and Wong, 1996.. This
methodology does not, however further our knowl-
edge of the complex processes occurring in natural
systems or their long-term effects. Consequently,
there is a need to study the behaviour of radionu-
clides under natural conditions and in suitable geo-
logical formations to host a high level radioactive
waste repository ŽHLRWR. ŽParneix, 1992; Smellie
et al., 1997; Hidaka and Holliger, 1998.. The El
Berrocal site has indeed satisfied this requirement
´ del Villar et al., 1993a..
ŽPerez
The isotopic study of secondary carbonates in
granitic formations is useful since carbonate anions
are powerful complexing agents for UŽVI. and the
sources of carbon and oxygen usually lie outside the
granitic formations. Thus, the sources of oxygen of
secondary carbonates may be percolating meteoric
waters, ancient seawaters, and the water from min-
eral dehydration or magmatic dewatering ŽWhite,
1974.. However, in some magmatic systems, where
the waterrrock ratio is very low, magmatic minerals
must also supply small amounts of oxygen to the
groundwaters ŽCriss and Taylor, 1986.. The occur-
rence of carbon usually absent in granitic formations,
as secondary carbonates can be explained by degra-
dation of the plant cover, magmatic degassing of
CO 2 , or decarbonization of sedimentary rocks,
ŽCraig, 1953; Arnorsson and Barnes, 1983; Barnes et
al., 1988..
Therefore, the isotopic study of secondary carbon-
ates in granitic formations can supply information on
potential sources of carbonate solutions, their circula-
tion paths, rockrwater interaction processes and the
temperature of formation of these carbonates ŽCraig,
1953; Truesdell and Hulston, 1980; Clauer et al.,
1989; Fritz et al., 1989; White et al., 1990..
Both secondary carbonate disseminated in the hy-
drothermally altered granite and carbonates from
fracture fillings of the El Berrocal granitic site have
been studied in order to establish: Ž1. their formation
temperature, Ž2. the relative sequence and chronolog-
ical evolution of the carbonatation processes within
the geothermal history of the El Berrocal system, and
Ž3. a conceptual model involving ancient and recent
waterrrock interaction phenomena.
2. Geological and geochemical background
2.1. Geological setting
The El Berrocal site is located approximately 90
km southwest of Madrid, near the small town of
Nombela, in the province of Toledo ŽSpain.. The site
takes its name from the El Berrocal granitic pluton,
which forms the hill upon which the site is located,
at an altitude of 900 m a.s.l. The El Berrocal pluton
is located at the central part of the Centro-Iberian
Zone, in the Spanish Hercynian Massif ŽJulivert et
al., 1972., near the contact between the Tajo River
Tertiary basin and the Sierra de Gredos ŽFig. 1..
The main granitic facies of the El Berrocal pluton,
the so-called El Berrocal facies, is the host rock of a
U-mineralised quartz vein ŽUQV. mined in the 1960s
and also known as the El Berrocal U-mine ŽArribas,
1965.. Together, the host-rock and the UQV make
up the El Berrocal system.
From a mineralogical point of view, the reference
granite was classified as a weakly altered alkaline-
feldspar granite with two micas, with muscovite
´ del Villar
being dominant relative to biotite ŽPerez
and De la Cruz, 1989.. Among the accessory miner-
als, ilmenite, zircon, monazite, xenotime, apatite,
uraninite, cassiterite and primary sulphides are high-
lighted. Muscovite II, fluorite, sericite, chlorite, ru-
tile, anatase, potassium feldspar and albite II are
secondary minerals formed during deuteric andror
early postmagmatic hydrothermal processes. The
geochemical features indicate a highly evolved
hypocalcic granite, rich in silica and phosphorus and
peraluminous. This granite is ‘fertile in U’ and be-
longs to the ilmenite granite series or to the S-type
´ del Villar and De la Cruz, 1989..
granites ŽPerez
The UQV is composed of quartz and sulphides
Žfirst mineralization phase. and pitchblende, pyrite,
minor barite and carbonates, the latter being detected
by the presence of dissolution moulds filled with
FeŽMn. oxyhydroxides Žsecond mineralization
phase..
 E. Reyes et al.r Chemical Geology 150 (1998) 293–315 295

Fig. 1. Location and geological map of the El Berrocal granitic pluton. Žafter Varea and Iglesias, 1981. Ža. Two-mica porphiritic granite Žthe
El Berrocal facies.. Žb. Two-mica leucogranite, fundamentally muscovitic. Žc. Biotitic granite of San Vicente Type. Žd. Almorox–Nava-
morcuende aplitic dyke. Že. U-mineralised quartz vein. Žf. Nondifferentiated Tertiary sediments Žsands, clays and conglomerates..

For a detailed study of the El Berrocal x:system,
the following geological materials have been taken
into account: Ži. the El Berrocal facies or reference
granite; Žii. the hydrothermally altered granite, with
scattered secondary carbonates; Žiii. the hydrother-
mally altered granite affected by weathering, Živ. the
weathered-reference granite, Žv. the UQV, including
its clayey walls, and Žvi. the fracture infill materials,
mainly formed by clays and carbonates ŽFig. 2.
´ del Villar et al., 1996b..
ŽPerez
296 E. Reyes et al.r Chemical Geology 150 (1998) 293–315

Fig. 2. N–S cross section of the El Berrocal system, showing the boreholes drilled, the location of samples and the hydraulically conductive
zones.
 E. Reyes et al.r Chemical Geology 150 (1998) 293–315
2.2. Geothermal history
Based on a Rb–Sr isochron as well as structural
and textural relationships among the materials of the
El Berrocal system and the mineral paragenesis, the
geothermal history of this system has been estab-
lished. The El Berrocal pluton intruded 297 " 1 Ma
ago, with an initial 87 Srr86 Sr ratio of 0.7175 "
0.0029 which is a typical value for parent magma
derived from the continental crust ŽFaure and Powell,
1972.. Further, the El Berrocal facies was affected
by a first set of hydrothermal events, at high temper-
ature ŽT ) 3508C., and defined as deuteric andror
early postmagmatic alteration processes which trans-
form the original facies into the so-called reference
granite. These processes are weak but pervasive
since they affect the whole granitic mass. The inter-
nal isochron obtained from apatite, albite, potassium
feldspar, biotite and bulk-rock sample of the El
Berrocal facies suggests that the bulk rock remained
a closed system for the Rb–Sr pair during late
alteration processes, and that the minerals were closed
for Sr isotopes around 289 " 1 Ma ago. Conse-
quently, the difference between the intrusion age and
the age obtained from the internal isochron Ž9 Ma.
represents the time during which the first set of
hydrothermal alteration processes took place in the
´ del Villar et al., 1996a..
El Berrocal facies ŽPerez
The second hydrothermal event recorded in the
site is related to N80E and N110E fracture families.
This process transforms the reference granite into the
hydrothermally altered granite adjacent to these frac-
tures. The alteration is evidenced by the sericitization
of feldspars, mainly albite, the presence of secondary
carbonates scattered through the rock, and the yel-
´ del Villar et al.,
low-green colour of the rock ŽPerez
1995.. The minimum temperature of formation of
secondary sericite, determined from its d18 O values,
ranges between 808 and 1208C ŽPerez ´ del Villar et
al., 1996b..
In relation to this process and using up the silica
released by feldspar alteration, sulphide-bearing
quartz veins and their clayey walls were formed,
´ del Villar
filling the abovementioned fractures ŽPerez
et al., 1996b.. According to the d18 O values of
quartz from quartz veins and values found for illite
from their clayey walls, both quartz veins and clayey
walls were formed at about 1008C ŽPerez ´ del Villar
297
et al., 1993b.. Somewhat later, the U-mineralization
took place mainly in N110E quartz veins, formed by
pitchblende, pyrite, carbonates and minor barite.
Fracture fillings, mainly composed of illite, kaoli-
nite, beidellite, carbonates and minor secondary
quartz, are the result of the interaction between the
granitic fracture gouges and hydrothermal solutions,
´ del Villar
with overlapping weathering effects ŽPerez
et al., 1996c.. Thus, the d18 O values of illite and
kaolinite indicate that these two clay minerals were
formed at the same temperature Ž1008C. as the quartz
veins and secondary sericite in the hydrothermally
altered granite.
Finally, 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 hydrothermally altered granite and UQV and
fracture fillings Žsee Fig. 2.. As far as the fracture
fillings are concerned, beidellite and a second gener-
ation of kaolinite were formed during these pro-
´ del Villar et al., 1997..
cesses ŽPerez
2.3. Relationships between alteration processes and
U, Th, Zr and REE mobilisation
All alteration processes recorded in the El Berro-
cal system produced the remobilization, migration
and retention, mainly by precipitation, of UŽIV. and
ThŽIV., as analogues for PuŽIV. and NpŽIV., UŽVI.,
for PuŽV and VI. and NpŽV., light rare earth ele-
ments ŽLREE., for Am, Cm and PuŽIII. ŽChapman
and Smellie, 1986., and Zr as a fission product
´ del Villar et al., 1994, 1995, 1996a,b,c and
ŽPerez
´ del Villar et al., 1996d..
Perez
Thus, during the first set of deuteric andror
hydrothermal events, uraninite, monazite, xenotime
and apatite in the granite were partially destabilized
by F-rich fluids in such a way that when these
minerals are surrounded by fluorite, uraninite is to-
tally or partially pseudomorphized by complex U
silicophosphates; monazite is totally or partially de-
pleted in REE, xenotime shows U and REE-poor
altered zones and apatite is partially dissolved. The
presence of U silicophosphates coating chloritized
biotite and filling the cleavage planes of muscovite
298 E. Reyes et al.r Chemical Geology 150 (1998) 293–315
and microfissures in quartz support the migration of
U away from uraninite and its retention in the rock
matrix, respectively. On the other hand, Th from
monazite remains immobile and no secondary REE-
bearing minerals have been found. Based on these
textural features, F is probably responsible for the
alteration of the U, Th and REE-bearing minerals, as
well as for the transport of U and REE, probably as
fluoride complexes. This hypothesis was confirmed
by the presence of secondary fluorite and U silicate
compounds filling dissolution voids in albite.
The second hydrothermal process, responsible for
the hydrothermally altered granite and quartz veins,
mobilised and also reprecipitated U, Th, REE and
Zr. The mineralogical evidences of these processes
are: the occurrence of U silicophosphates lining and
filling microfissures in secondary pyrite; the precipi-
tation of botryoidal ‘mineraloids’, whose composi-
tion varies from U ) Th to Th ) U silicophosphates;
the presence of Th and Zr silicates filling microfis-
sures in quartz; the neoformation of florencite and
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.
In relation to this second hydrothermal event, the
uranium-ore body hosted in the main quartz vein was
originated, formed by pitchblende, carbonates, pyrite
and minor barite. This paragenesis suggests that U
scattered in the granite was oxidised, remobilized
and transported, downwards and through the frac-
tures as uranyl–carbonate complexes. These solu-
tions, reheated at depth by the tectonic events that
fractured the quartz veins, moved upwards, probably
by convective flow. After destabilisation of uranyl–
carbonate complexes caused by rock–water interac-
tion processes and a drop in temperature and pres-
sure, uranyl cations were probably reduced by H 2 S,
precipitating pitchblende, carbonates and pyrite. The
coexistence of pyrite and barite suggests that the
precipitation took place between y200 and y300
mV ŽKrivovichev, 1979.. The same process also
affected the hydrothermally altered granite close to
the UQV and, to a lesser extent, the intra-granitic
fractures.
The effects of weathering on U of each part of the
system may be summarised as follows.
v The effects on the uraninite of the reference
granite vary according to the nature and fracturing
degree of its host mineral. Thus, if uraninite is
included in feldspars, the former is usually dissolved
and only the outlines of the crystals remain, with
residual Th–Ca silicophosphates inside. The U from
uraninite, forming U silicophosphates, is usually fill-
ing adjacent microfissures, or is adsorbed, together
with P, onto Fe oxyhydroxides.
v Weathering on the hydrothermally altered
granite mainly caused a distribution of U, which
forms large autunite crystals andror is adsorbed onto
secondary sericite and Fe oxyhydroxides.
v The effects of weathering on the U-ore body
are represented by strong oxidation of pitchblende
and sulphides, dissolution of carbonates and neofor-
mation of secondary U minerals such as uranotyle,
autunite, in secular equilibrium, torbernite and ura-
nocircite. Furthermore, U is also adsorbed onto Fe
oxyhydroxides.
v Similar weathering effects have been observed
on the fracture filling materials. Thus, uranium forms
uranyl silicates and phosphates, such as uranotyle,
autunite and phosphuranylite, and is adsorbed onto
Fe oxyhydroxides. At present, the uranyl carbonate
complexes are the dominant soluble species in oxi-
dising groundwaters in the system ŽGomez ´ et al.,
1996..
3. Sampling and methods
Twelve samples analysed from the carbonate-
bearing hydrothermally altered granite were taken
from borehole S-13, at both sides of the UQV. The
average sample size is shaped like a cylinder, 1 cm
long and 8.6 cm in diameter.
Samples from fracture fillings come from bore-
holes ŽS. 13, 14, 15, 16 and 17, amounting to 122
samples, and distributed as follows: S-13 Ž21.; S-14
Ž9.; S-15 Ž16.; S-16 Ž54. and S-17 Ž22.. The sam-
pling is representative of both high-and-low hy-
draulic conductivity fracture zones ŽFig. 2.. Due to
the scarcity of infill material above a depth of 50 m,
the sampling in S-13, 15 and 16 started below this
level. Samples were usually scraped from both sides
of the fractures or loosened when the fracture fillings
were thicker. Consequently, the available amount of
 E. Reyes et al.r Chemical Geology 150 (1998) 293–315 299

Fig. 3. Ža. Patches of secondary carbonates on totally sericitised ŽSer.. albite Žsample from hydrothermally altered granite, photography
under polarised light, X65.. Žb. Back-scattered electron image of secondary carbonates Ž1., surrounded by secondary TiO 2 . Žc. EDX pattern
of carbonates Ž1. in which Mg, Ca, Mn and Fe peaks are reported.
300 E. Reyes et al.r Chemical Geology 150 (1998) 293–315

Table 1 Carbonates from hydrothermally altered granite

d13 C and d18 O values and temperature of formation of the calcitic were detected and examined by polarising mi-
fractions of carbonates from the hydrothermally altered granite
croscopy ŽPM. and scanning electron microscopy,
SAMPLE d 13 C ŽPDB . d 18 OŽPDB . T Ž8C.
coupled to an energy dispersive X-ray analyser
ZA.23 y7.4 y13.3 47 ŽSEM q EDX.. The identification and semiquantifi-
ZA.24 y7.6 y12.8 44
cation of carbonates from fracture filling materials
ZA.25 y7.2 y12.6 43
ZA.26 y7.3 y12.2 41 were performed by SEM q EDX, X-ray diffraction
ZA.27 y7.3 y11.7 39 ŽXRD. and differential thermal and thermogravimet-
ZA.31 y7.2 y12.6 43 ric analyses ŽDTA and TGA..
ZA.32 y7.5 y13.2 47 For isotopic measurements, all samples were
ZA.34 y7.3 y12.7 44
ground to - 200 mesh, then treated with 100%
ZA.36 y7.1 y11.1 35
ZB.22 y7.7 y14.2 52 phosphoric acid for 12 h in a thermostatic bath at
ZB.25 y7.2 y12.1 40 258C ŽMcCrea, 1950.. Samples containing calcite
ZB.30 y10.7 y13.0 46 and ankeritic carbonates, as major, minor or trace
components Žabout 50, including all the samples of
the hydrothermally altered granite., were also treated
the infill material varied as a function of its thickness according to the Al-Aasm et al. Ž1990. method. This
and orientation of the fractures in relation to the core method is as follows: CO 2 is removed after a 2-h
axis Žsee Fig. 2.. reaction with phosphoric acid at 258C and this sam-

Fig. 4. Temperature range in which the secondary carbonates Žcalcitic fractions. of the hydrothermally altered granite were formed, obtained
from the equation of Anderson and Arthur Ž1983..
 E. Reyes et al.r Chemical Geology 150 (1998) 293–315 301

ple is labeled ‘calcite’. The vessel is then closed, and
the reaction is continued for 24 h at 258C, after
which time the released CO 2 is discarded. The sam-
ple may then be allowed to react at 508C for 10 days
and the CO 2 subsequently removed is used to deter-
mine the isotopic composition of ankerite.
Furthermore, nine groundwater samples from
borehole S-16, taken at a depth of 400 m, were used
to determine the d13 C values in the dissolved inor-
ganic carbon ŽDIC.. Carbon was collected by pre-
cipitation of SrCO 3 following the method of
Carothers and Kharaka Ž1980.. Strontium carbonate
was reacted with phosphoric acid to produce CO 2
for C-isotope analysis ŽMcCrea, 1950..

Fig. 5. The sources of carbon in the ‘El Berrocal’ area. SURFACE PROCESSES: Only C3 plants and atmospheric CO 2 have been
considered, since CAMP plants are insignificant in most ecosystems and C4 plants are usually present in arid, hot environments ŽDeines,
1980; Cerling, 1991.. The shaded area shows that the most frequent range of C 3 plants is y30‰ to y25‰ ŽDeines, 1980.. The
pre-industrial atmospheric CO 2 has a d13 C value of y6.5‰ ŽFriedli et al., 1986. Žy8‰ at present.. The soil CO 2 is about 4.5‰ heavier
than the plant biomass ŽCerling, 1984, 1991.. The isotopic difference between CO 2 and dissolved inorganic carbon ŽDIC. depends on the
pH and temperature. This value will be near to 0‰ at value close to pH 5, but is relatively independent of pH between 7.5 and 8 ŽRomanek
et al., 1992.. For the isotopic theoretical calculation ŽDIC and calcites. we considered a calcite–bicarbonate enrichment of 1‰ Žindependent
of the temperature. and the calcite–CO 2 equation described by Romanek et al. Ž1992. for temperatures of 08, 158 and 308C. DEEP
PROCESSES: Highly negative calcites Žmethane-derived cements. and highly positive calcites Žmethanogenic cements. must be discounted,
because the values obtained in this study Ž2. are far from these fields. On the other hand, the current DIC Ž1. range between y20.7‰
and y 17.4‰ Ž9 samples, depth s 400 m. is in agreement with the theoretical considerations. Finally, a number of relevant isotope
compositional fields from the literature are also presented for comparison: 3 s range of pedogenic calcite ŽTalma and Netterberg, 1983;
Salomons and Mook, 1986., 4 s carbonatites ŽHoefs, 1980.; 5 s mantle C ŽKyser, 1986.; 6 s fracture calcites from the Stripa granite
ŽClauer et al., 1989; Fritz et al., 1989..
302 E. Reyes et al.r Chemical Geology 150 (1998) 293–315

Table 2
d13 C and d18 O values and temperature of formation of the
ankeritic fractions of carbonates
SAMPLE d 13 C ŽPDB . d 18 OŽPDB . T Ž8C.
ZA.23 y6.5 y14.0 65
ZA.24 y6.9 y13.9 64
ZA.25 y2.7 y13.4 61
ZA.27 y5.8 y13.9 64
ZA.31 y6.9 y14.9 71
ZA.32 y7.9 y15.1 72
ZA.34 y7.7 y14.9 71
ZA.36 y7.0 y14.1 66
ZB.25 y4.3 y13.6 63

Both d13 C and d18 O were determined using a
Finnigan Mat 251 mass spectrometer. The experi-
mental error found was "0.1‰ for d13 C and d18 O,
using Carrara and EEZ-1 internal standards, previ-
ously compared with NBS-18 and NBS-19 ŽReyes et
al., 1989..
All the samples were compared to a reference
carbon dioxide obtained from a calcite standard pre-
pared at the same time. Thus, oxygen isotope ratios
for ankerite were recalculated taking into account the
fractionation factor for acid decomposition at 508C:
1.01057 for ankerite ŽRosenbaum and Sheppard,
1986. and 1.0090 for calcite ŽFriedman and O’Neil,
1977..
Only the carbonates from the hydrothermally al-
tered granite presented a significant amount of
ankerite. Usually, the amounts of CO 2 from ankeritic
carbonates in fracture filling samples were too scarce
to be analysed by mass spectrometry. However, in
samples whose CO 2 content was high enough, the
isotopic results for carbon and oxygen were very
similar to those obtained using the method of Mc-
Crea Ž1950.. Indeed, the differences were less than
0.2‰ and 0.3‰ for d13 C and d18 O, respectively.
Consequently, only the data obtained by McCrea’s
method will be included and discussed in this work.
Since the differences in isotopic signatures of
carbonates from the hydrothermally altered granite
Fig. 6. Temperature range in which the secondary carbonates
Žankeritic fractions. of the hydrothermally altered granite were
formed, obtained from the Carothers et al. Ž1988. equation for
siderite.
were significant, due to the chemical method used,
the results will be discussed separately.
4. Results and discussion
4.1. Mineralogy, d18 O and d13C of secondary car-
bonates from the hydrothermally altered granite
According to SEM q EDX data, the carbonatation
process that affects the hydrothermally altered gran-
ite is mainly characterised by the occurrence of
ankerite with minor calcite. Based on the textural
relationships between sericite and carbonates ŽFig.
3., the latter could have been formed either simulta-
neously or somewhat later than sericite.
The isotopic results obtained from calcitic frac-
tions of these carbonates ŽTable 1. show the follow-
ing features: Ža. A striking homogeneity of the d13 C
values, which range from y7.7‰ to y7.1‰, except
for sample ZB-30, Žy10.8‰.. Žb. The d18 O values

Fig. 7. Ža. Correlation between the carbonate percentages obtained by DTA-TGA and XRD analyses. Žb. Plot of the chemical composition
of carbonates from fracture fillings in a ŽCaO. – ŽMgO. – ŽFeO q MnO. ternary diagram.
E. Reyes et al.r Chemical Geology 150 (1998) 293–315 303
304 E. Reyes et al.r Chemical Geology 150 (1998) 293–315

Fig. 8. Distribution of the main neoformed minerals along the boreholes studied.
 E. Reyes et al.r Chemical Geology 150 (1998) 293–315
vary to a larger extent than the d13 C values, ranging
from y14.2‰ to y11.1‰. Žc. The temperatures
obtained, taking into account the equation of Ander-
son and Arthur Ž1983. and the annual average value
of d18 O in the El Berrocal current meteoric waters
Žy7.6‰., vary within a narrow range, between 358
and 528C ŽFig. 4..
The relative negative d13 C values of these calcitic
fractions indicate that the main source of carbon was
the edaphic cover ŽSalomons and Mook, 1986; Cer-
ling, 1991.. This effect was more evident in sample
ZB-30, with a typical edaphic d13 C ŽTable 1 and Fig.
5.. Furthermore, the temperatures obtained are con-
sistent with low-temperature hydrothermal processes.
However, calcite from sample ZB-30, which pre-
sented an anomalous d13 C value, probably caused by
the existence of a mixture of hydrothermal and mete-
oric calcites, might have partially formed at higher
temperatures. In this respect, the location of this
sample close to the UQV, where the intense circula-
tion of meteoric waters is currently taking place as it
did in the past, would suggest the coexistence of old
Žhydrothermal. and recent Ženvironmental. calcites,
the latter being enriched in light carbon.
The isotopic signatures of the ankeritic fractions
ŽTable 2. follow a similar trend to those observed in
calcite, though they also present the following differ-
ences: Ža. Generally, the effect of edaphic CO 2 in
ankeritic carbonates is slightly lower than on calcitic
fractions ŽTable 2 and Fig. 5.. In samples ZA-25 and
ZB-25, The effect is even lower. This enrichment in
heavy carbon could be explained by dissolution–pre-
cipitation processes. Žb. The temperatures obtained
between 618 and 728C ŽFig. 6. were calculated using
the equation of Carothers et al. Ž1988. for siderite,
because no equation has been found for ankerite in
the specialised literature. These temperature values
are higher than those of calcitic fractions. Žc. Only
three samples, ZA-26, ZB-22 and ZB-30 contain no
ankeritic fraction.
In short, the hydrothermally altered granite was
affected by a very-low-temperature hydrothermal
carbonatation process, during which ankeritic car-
bonates were firstly precipitated, followed by calcite,
at lower temperature. It also appears that the influ-
ence of edaphic CO 2 in both carbonates followed the
cooling of the system. This carbonatation event prob-
ably took place after the sericitization process, ac-
305
cording to the temperature of formation and the
textural relationships between these carbonates and
sericite.
4.2. Mineralogy, d13C and d18 O of carbonates from
fracture fillings
The carbonate content obtained by XRD ranges
from 94% to below the detection limit. These data
were confirmed by TGA and both methods are in
good agreement ŽFig. 7a.. Calcite is the main car-
bonate species and was identified in most of the
samples. Only in S-13 Ž54 m. and S-15 Ž49 to 75 m.,
did calcite and dolomite coexist. The semiquantita-
tive chemical analyses by EDX show the constant
presence of Mn in both carbonates. The percentage
of Mn is so variable in calcite that the Ca–Mn-
carbonate series Žcalcite–kutnahorite–rhodochrosite.
can be defined ŽFig. 7b.. However, kutnahorite and
rhodochrosite are always below the XRD detection
limit. From a textural and structural point of view,
carbonates occur as veinlets of xenomorphic calcite,
but more frequently they appear as - 1-mm-thick
layers coating both fracture walls. In the latter case,
calcite forms a mosaic in which pit etchings are
frequent. Sometimes, in some fracture walls, calcite
is more developed and shows the typical rhombohe-
dral habit.
Wherever calcite and dolomite coexist, their tex-
tural relationships are not clear enough for their
crystallization sequence to be established. However,
both carbonates are more recent than neoformed
quartz, because they fill voids between the quartz
crystals. Kutnahorite and rhodochrosite seem to be
more recent than calcite and smectite, since they
always appear as small single rhombohedral crystals
on calcite or smectite. In the first case, the crystals
are usually oriented parallel to the cleavage planes of
calcite.
The mineralogical distribution of the five bore-
holes studied ŽFig. 8. shows that: Ži. in boreholes
S-14 and S-17, carbonates appear below 60 and 80
m, respectively. This is due to the dissolution of
carbonates by meteoric waters in the upper zones of
the site. In these fractures, residual Fe–Mn oxyhy-
droxides are present instead of carbonates. Žii. No
relationship between carbonate concentration and
depth is observed in any of the boreholes. Neverthe-
306 E. Reyes et al.r Chemical Geology 150 (1998) 293–315

Table 3 Table 3 Žcontinued.

d13 C and d18 O values of carbonates from fracture fillings inter- Depth Žm. d 13 C PD B d 18 O PDB
sected by boreholes S-13, 14, 15, 16 and 17
BOREHOLE 16
Depth Žm. d 13 C PD B d 18 O PDB 72.65 y12.8 y8.9
BOREHOLE 13 84.10 y14.3 y7.5
50.55 y10.4 y12.4 86.70 y12.1 y11.5
53.43 y6.6 y15.1 100.65 y13.2 y9.0
53.86 y9.2 y12.0 102.53 y14.5 y7.5
84.29 y10.6 y13.2 115.32 y14.3 y8.1
90.75 y12.9 y9.4 126.51 y12.0 y12.5
91.47 y12.5 y10.0 140.37 y13.5 y10.4
91.69 y12.5 y9.8 163.68 y11.1 y13.2
109.16 y11.1 y15.8 215.27 y14.6 y8.4
113.31 y11.2 y13.9 230.34 y12.7 y12.7
113.53 y13.1 y15.3 232.17 y13.2 y12.1
126.77 y13.0 y9.8 233.02 y13.8 y11.0
151.66 y12.9 y11.0 234.24 y10.2 y7.9
154.02 y11.7 y12.0 248.02 y13.7 y9.7
155.15 y9.6 y14.7 249.31 y13.2 y13.2
156.38 y8.8 y15.1 249.49 y13.2 y13.3
157.91 y11.1 y13.6 249.98 y13.1 y13.4
158.25 y11.3 y12.8 279.59 y15.3 y11.6
158.61 y11.7 y12.7 313.54 y11.3 y11.3
158.64 y11.4 y14.2 334.24 y10.9 y7.9
159.21 y11.9 y13.4 350.50 y14.9 y8.7
159.25 y11.8 y12.4 386.45 y9.1 y10.7
442.09 y13.8 y10.1
BOREHOLE 14 445.60 y14.0 y9.8
61.77 y12.1 y10.0 446.14 y13.8 y10.0
61.91 y10.9 y10.6 463.42 y15.6 y11.8
74.51 y11.4 y10.6 465.57 y13.0 y10.4
94.70 y12.9 y10.2 465.64 y16.2 y11.0
100.41 y14.0 y7.5 467.70 y14.5 y11.6
141.78 y14.0 y8.9 470.73 y14.9 y11.3
153.04 y13.4 y9.3 471.10 y14.4 y11.4
209.55 y13.1 y11.6 474.85 y13.6 y12.6
209.78 y13.5 y11.6 475.03 y14.8 y14.2
476.45 y13.7 y13.7
BOREHOLE 15 476.97 y16.4 y13.4
70.05 y12.0 y8.5 514.16 y13.2 y11.0
89.74 y12.4 y8.7 526.96 y14.0 y11.7
98.47 y13.0 y8.2 527.64 y13.7 y12.4
105.64 y8.3 y14.5 528.64 y12.8 y13.8
108.28 y10.2 y13.4 531.22 y12.6 y12.4
110.66 y12.9 y8.7 549.98 y13.5 y12.2
115.13 y12.8 y9.2 550.13 y13.4 y12.3
116.01 y12.5 y9.7 354.85 y13.1 y12.6
119.29 y12.8 y9.0 558.76 y13.3 y12.8
123.25 y12.9 y8.9 565.02 y13.6 y12.2
123.78 y11.4 y11.5 568.32 y13.4 y11.8
137.61 y12.6 y11.0 576.62 y12.4 y12.5
138.67 y8.4 y13.1 589.02 y12.8 y13.4
151.94 y12.8 y10.2 589.34 y11.4 y12.7
151.95 y8.4 y14.7 590.32 y11.2 y14.5
154.54 y9.6 y11.4 593.78 y9.7 y13.8
 E. Reyes et al.r Chemical Geology 150 (1998) 293–315 307

Table 3 Žcontinued.
Depth Žm. d 13 C PD B d 18 O PDB
BOREHOLE 16
598.71 y8.4 y15.1
602.82 y13.9 y12.1

BOREHOLE 17
85.60 y12.1 y10.4
98.83 y12.6 y9.6
100.73 y12.5 y9.8
108.61 y13.9 y8.2
112.03 y13.3 y8.8
138.64 y13.2 y11.3
141.40 y13.4 y10.2
159.55 y12.9 y12.3
160.84 y13.7 y10.8
161.31 y13.3 y10.7
166.08 y13.6 y9.2
174.53 y12.1 y11.7
188.45 y13.0 y10.8
192.02 y11.4 y12.5
192.71 y12.6 y12.0
227.04 y13.2 y9.8
228.42 y13.4 y9.5
231.54 y11.6 y12.0
233.08 y12.8 y9.8
235.91 y12.6 y10.9
240.98 y12.1 y10.6
278.49 y13.2 y10.0

less, in brecciated zones of the UQV, intersected by

boreholes S-13 and S-15, carbonates are absent due Fig. 9. Histograms of d13 C and d18 O values of carbonates from
to dissolution by acid waters of meteoric origin fracture filling samples.
produced by the oxidation of sulphides existing in
the UQV.
creased dissolution of preexisting carbonates ŽFig.
The d13 C and d18 O values ŽTable 3, Fig. 9. vary
5.. All these results indicate that carbonates located
broadly from y6.6‰ to y16.4‰ and from y7.5‰
down to a depth of 250 m correspond to a mixture of
to y15.8‰ respectively. The effect of edaphic CO 2
various carbonate phases, formed under different
in the formation of carbonates is generally greater
than that of atmospheric CO 2 ŽFig. 5.. This suggests
that the CO 2 of these carbonates mainly derives from Table 4
the plant cover of the site, essentially constituted by Temperatures of formation of carbonates from fracture filling
C 3-type plants, with a d13 C value of y26‰ ŽCer- samples
ling, 1991.. T Ž8C. B-13 B-14 B-15 B-16 B-17 Total
The variations of d13 C and d18 O values with 15–25 5% 30% 44% 17% 23% 20%
depth in each borehole ŽFig. 10. show a striking 25–35 19% 60% 31% 31% 54% 36%
symmetry of both isotopic signatures. Thus, the de- 35–45 38% – 12% 41% 23% 30%
pletion of 18 O in carbonates, which may indicate a 45–55 29% 10% 12% 11% – 12%
55–65 10% – – – – 2%
higher temperature of formation, is accompanied by T Ž8C max.. 59 35 52 54 40 59
an enrichment in 13 C. This indicates either a lower T Ž8C min.. 24 15 19 16 19 15
edaphic contribution in the total carbon or an in-
 308
E. Reyes et al.r Chemical Geology 150 (1998) 293–315
Fig. 10. Variations of d13 C and d18 O values with depth in each borehole.
 E. Reyes et al.r Chemical Geology 150 (1998) 293–315 309

Fig. 11. Temperature intervals in which the carbonates from fracture filling samples were formed, obtained from the equation of Anderson
and Arthur Ž1983..
310 E. Reyes et al.r Chemical Geology 150 (1998) 293–315

Fig. 12. Ža. Regression lines between d18 O and d13 C considering all the samples analysed Ž r s 0.46. and considering only the samples
located between 0 m and 215 m Ž r s 0.74.. Žb. Theoretical quaternary diagram obtained from d18 O and d13 C experimental data, in which
the vertices represent the isotopic signatures of the different carbonate components of the mixed carbonate assemblage.
 E. Reyes et al.r Chemical Geology 150 (1998) 293–315
conditions. Only in S-16, below 215 m, does the
symmetrical distribution of both isotopic signatures
seem to be broken. This exception may be due to the
existence of carbonates precipitated from a mixed
solution of deep and shallow bicarbonate waters.
Furthermore, some d13 C values are more negative
than those of the edaphic typical carbonates
ŽSalomons et al., 1978; Talma and Netterberg, 1983;
Salomons and Mook, 1986.. This could be explained
by taking into account that in granitic recharge wa-
ters are usually weakly acidic, and under such condi-
tions the d13 C values of DIC are very close to those
of the soil-CO 2 ŽFritz et al., 1989; Romanek et al.,
1992.. This is in agreement with the d13 C values
obtained from the El Berrocal DIC, ranging between
y20.7‰ and y17.4‰.
The geothermometric study was carried out based
on the equation T Ž8C. s 16 y 4.14Ž dc y d w . q
0.13Ž dc y d w . 2 ŽAnderson and Arthur, 1983. and
the d18 O annual average value of the El Berrocal
current meteoric water Žy7.56‰. ŽReyes et al.,
1995.. The results ŽTable 4, Fig. 11. demonstrate
that 80% of these carbonates were formed at temper-
atures between 258C and at least 658C, while the
remaining 20% were formed at ambient temperature.
These data would seem to point towards a mixture
between carbonates formed at ambient conditions
and carbonates formed at temperatures higher than
those calculated. Consequently, at least two genera-
tions of carbonates are superimposed in the system.
In order to confirm this hypothesis, d18 O values
of all the samples were plotted vs. d13 C values ŽFig.
12a.. The regression line obtained has a correlation
coefficient of 0.46 and a negative slope, suggesting a
mixture of carbonates formed under different condi-
tions. Likewise, if only data from samples located
between 0 m and 250 m are considered, a regression
line with a higher correlation coefficient of 0.74 is
obtained ŽFig. 12a.. In order to determine the iso-
topic signature of each carbonate component, a qua-
ternary diagram was plotted, where the vertices rep-
resent the isotopic signatures of carbonates that could
have been mixed ŽFig. 12b.. Vertex C was defined
taking into account d18 O and d13 C values of a
theoretical hydrothermal carbonate formed at 1008C,
scarcely influenced by edaphic CO 2 and similar to
carbonates studied by Feux and Baker Ž1973. in
granitic environments. By joining this vertex to the
311
outermost experimental data lines CD and CB were
obtained. Lines AD and AB were plotted parallel to
the x and y axes respectively, starting from samples
richest in 13 C and 18 O. Vertices B and D almost
coincide with the experimental values. Therefore, the
vertices of this quaternary diagram would indicate
the theoretical isotopic signatures of the carbonate
end-members that formed the mixtures. Conse-
quently, the carbonates of fracture fillings corre-
spond to mixtures of carbonates of edaphic origin
Ž d13 C between y10‰ and y16.5‰. formed at
ambient temperature, and of other hydrothermal car-
bonates with predominant edaphic carbon and pre-
cipitated at a temperature between 508 to below
1008C.
5. Conclusions
In the El Berrocal hydrothermally altered granite,
two types of disseminated carbonates have been
identified according to their chemical composition,
temperature of formation and C and O isotopic com-
position. The first is ankeritic and precipitated at a
temperature range between 728 and 618C, whereas
the second is calcitic and formed between 528 and
358C. The effect of edaphic CO 2 has been demon-
strated, and is stronger in calcite than in ankerite.
Consequently, in both cases, carbonate-bearing
groundwaters have a meteoric origin and were re-
heated at depth and moved upwards by convective
flow. ŽFig. 13.. Furthermore, the influence of edaphic
CO 2 in these carbonates has increased during the
cooling of the system.
The difference between the temperature of forma-
tion of ankerite and calcite suggest that both phases
formed during the same low-temperature hydrother-
mal event. This carbonatation process can also be
considered as the thermal tail of the same hydrother-
mal event that originated the hydrothermally altered
granite, the quartz veins and the most important
process of mobilizationrmigration of U from urani-
nite in the granite, that originated the U-ore body.
This conclusion seems to be confirmed by the tem-
perature of formation of sericite, which ranges from
808 to 1208C, quartz veins, at about 1008C, the
textural relationships between sericite and carbonates
in the hydrothermally altered granite and by the
312 E. Reyes et al.r Chemical Geology 150 (1998) 293–315

Fig. 13. Idealised conceptual model of the mobilisation, transport and precipitation of uranium in the El Berrocal system. Ž1. Biotitic granite
of San Vicente type. Ž2. The El Berrocal granitic facies or reference granite. Ž3. Pegmoaplites. Ž4. Hydrothermally altered granite, with
scattered secondary carbonates. Ž5. The UQV, including its clayey walls. Ž6. The fracture infill materials. Ž7. Granitic soil and
weathered-reference granite. Ž8. Percolating meteoric waters. Ž9. Intrusive contact between the El Berrocal pluton and the San Vicente-type
granite. ŽA–E. Idealised convective flow of meteoric waters. ŽA. Oxidising and bicarbonate meteoric waters, enriched in light carbon of
edaphic origin ŽS. type plants.. Oxidation of uraninite scattered in the granite occurs in this zone. ŽB. Uranium transport as uranyl carbonate
complexes. ŽC–D. Reheating of uranyl solutions at T - 100qC by fracturing effects. ŽD. Upward flow, uranyl complexes destabilisation,
reducing conditions and precipitation of pitchblende, pyrite and carbonates, mainly in the UQV. No scale considered.

structural relationships between the main quartz vein
and the U-ore body.
As for the hydrothermally altered granite, at least
two types of carbonates have been identified in
fracture filling materials, according to their tempera-
tures of formation. The first carbonate was formed
under hydrothermal conditions, between 258 and at
most 1008C, and the second at ambient temperature
F 258C. Almost all the samples correspond to mix-
tures of both components. In addition, the isotopic
signatures of carbon in both carbonates indicate the
influence of edaphic carbon and, consequently, the
meteoric origin of the water. To explain the precipi-
tation of hydrothermal carbonates, we suggest a re-
heating at depth and upward movements of carbon-
ate solutions.
According to the temperatures of formation of
ankeritic carbonates in the hydrothermally altered
granite and hydrothermal carbonates from fracture
fillings, it is suggested that both types are the result
of the hydrothermal process described above. Their
chemical differences may be due to different intensi-
ties of waterrrock interactions. Thus, the hydrother-
mally altered granite is closely related to a major
tectonic accident which affected a very important
granitic mass, whereas the fracture filling materials
are linked to minor tectonic accidents, whose effects
are only affective in thin granitic bands at both sides
of the fractures. In this way, significant amounts of
Fe, Mg and Mn were released during the alteration
of biotite and transferred to carbonate solutions. This
caused the precipitation of ankerite in the hydrother-
 E. Reyes et al.r Chemical Geology 150 (1998) 293–315
mally altered granite, whereas in the fractures only
Ca and minor Mn were supplied to form Mn-calcite.
As for the U-ore body, the hydrothermal carbon-
atation processes that affected the intra-granitic frac-
tures could also be responsible for the ancient migra-
tionrretention of uranium, mainly by precipitation of
minor pitchblende, observed in fracture infill materi-
als. Currently, this UŽIV. oxide is almost totally
oxidized by weathering, with the uraniun retained as
uranyl minerals and adsorbed onto Fe oxyhydrox-
ides. To explain the latter process, we suggest that
bicarbonate meteoric waters, enriched in light car-
bon, oxidized and dissolved pitchblende, transporting
UŽVI. as uranyl–carbonate complexes. After destabi-
lization of these complexes by rock–water interac-
tion processes, uranyl cations were precipitated as
uranyl silicates and phosphates, or adsorbed onto Fe
oxyhydroxides. Carbonate anions were precipitated
as calcite, with minor Mn. In this sense, the uranyl
carbonate complexes are, at present, the dominant
soluble species in the oxidising groundwaters of the
El Berrocal system.
Acknowledgements
Financial support for this work was provided by
ENRESA, CIEMAT and CEC. We are grateful to
´
Mr. Francisco Sanchez, Francisco Orden and
´
Jeronimo Navea for the preparation of the samples.
The authors would also like to thank the Chemical
Geology reviewers ŽDr. R. Bros and the anonymous
reviewer. for their comments and constructive criti-
cisms which have notably improved the paper.
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