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: [email protected]

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 geothermal history of the El Berrocal system, and

Ž3. a conceptual model involving ancient and recent
The study on radionuclide migration and transport waterrrock interaction phenomena.
is a controversial subject in environmental and earth
sciences and the studies made have mainly focused
on laboratory experiments using simple physico- 2. Geological and geochemical background
chemical systems ŽChoppin and Wong, 1996.. This
methodology does not, however further our knowl-
edge of the complex processes occurring in natural 2.1. Geological setting
systems or their long-term effects. Consequently,
there is a need to study the behaviour of radionu- The El Berrocal site is located approximately 90
clides under natural conditions and in suitable geo- km southwest of Madrid, near the small town of
logical formations to host a high level radioactive Nombela, in the province of Toledo ŽSpain.. The site
waste repository ŽHLRWR. ŽParneix, 1992; Smellie takes its name from the El Berrocal granitic pluton,
et al., 1997; Hidaka and Holliger, 1998.. The El which forms the hill upon which the site is located,
Berrocal site has indeed satisfied this requirement at an altitude of 900 m a.s.l. The El Berrocal pluton
´ del Villar et al., 1993a..
ŽPerez is located at the central part of the Centro-Iberian
The isotopic study of secondary carbonates in Zone, in the Spanish Hercynian Massif ŽJulivert et
granitic formations is useful since carbonate anions al., 1972., near the contact between the Tajo River
are powerful complexing agents for UŽVI. and the Tertiary basin and the Sierra de Gredos ŽFig. 1..
sources of carbon and oxygen usually lie outside the The main granitic facies of the El Berrocal pluton,
granitic formations. Thus, the sources of oxygen of the so-called El Berrocal facies, is the host rock of a
secondary carbonates may be percolating meteoric U-mineralised quartz vein ŽUQV. mined in the 1960s
waters, ancient seawaters, and the water from min- and also known as the El Berrocal U-mine ŽArribas,
eral dehydration or magmatic dewatering ŽWhite, 1965.. Together, the host-rock and the UQV make
1974.. However, in some magmatic systems, where up the El Berrocal system.
the waterrrock ratio is very low, magmatic minerals From a mineralogical point of view, the reference
must also supply small amounts of oxygen to the granite was classified as a weakly altered alkaline-
groundwaters ŽCriss and Taylor, 1986.. The occur- feldspar granite with two micas, with muscovite
rence of carbon usually absent in granitic formations, ´ del Villar
being dominant relative to biotite ŽPerez
as secondary carbonates can be explained by degra- and De la Cruz, 1989.. Among the accessory miner-
dation of the plant cover, magmatic degassing of als, ilmenite, zircon, monazite, xenotime, apatite,
CO 2 , or decarbonization of sedimentary rocks, uraninite, cassiterite and primary sulphides are high-
ŽCraig, 1953; Arnorsson and Barnes, 1983; Barnes et lighted. Muscovite II, fluorite, sericite, chlorite, ru-
al., 1988.. tile, anatase, potassium feldspar and albite II are
Therefore, the isotopic study of secondary carbon- secondary minerals formed during deuteric andror
ates in granitic formations can supply information on early postmagmatic hydrothermal processes. The
potential sources of carbonate solutions, their circula- geochemical features indicate a highly evolved
tion paths, rockrwater interaction processes and the hypocalcic granite, rich in silica and phosphorus and
temperature of formation of these carbonates ŽCraig, peraluminous. This granite is ‘fertile in U’ and be-
1953; Truesdell and Hulston, 1980; Clauer et al., longs to the ilmenite granite series or to the S-type
1989; Fritz et al., 1989; White et al., 1990.. ´ del Villar and De la Cruz, 1989..
granites ŽPerez
Both secondary carbonate disseminated in the hy- The UQV is composed of quartz and sulphides
drothermally altered granite and carbonates from Žfirst mineralization phase. and pitchblende, pyrite,
fracture fillings of the El Berrocal granitic site have minor barite and carbonates, the latter being detected
been studied in order to establish: Ž1. their formation by the presence of dissolution moulds filled with
temperature, Ž2. the relative sequence and chronolog- FeŽMn. oxyhydroxides Žsecond mineralization
ical evolution of the carbonatation processes within 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, mally altered granite affected by weathering, Živ. the
the following geological materials have been taken weathered-reference granite, Žv. the UQV, including
into account: Ži. the El Berrocal facies or reference its clayey walls, and Žvi. the fracture infill materials,
granite; Žii. the hydrothermally altered granite, with mainly formed by clays and carbonates ŽFig. 2.
scattered secondary carbonates; Žiii. the hydrother- ´ 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) 293–315 297

2.2. Geothermal history et al., 1993b.. Somewhat later, the U-mineralization

took place mainly in N110E quartz veins, formed by
Based on a Rb–Sr isochron as well as structural pitchblende, pyrite, carbonates and minor barite.
and textural relationships among the materials of the Fracture fillings, mainly composed of illite, kaoli-
El Berrocal system and the mineral paragenesis, the nite, beidellite, carbonates and minor secondary
geothermal history of this system has been estab- quartz, are the result of the interaction between the
lished. The El Berrocal pluton intruded 297 " 1 Ma granitic fracture gouges and hydrothermal solutions,
ago, with an initial 87 Srr86 Sr ratio of 0.7175 " ´ del Villar
with overlapping weathering effects ŽPerez
0.0029 which is a typical value for parent magma et al., 1996c.. Thus, the d18 O values of illite and
derived from the continental crust ŽFaure and Powell, kaolinite indicate that these two clay minerals were
1972.. Further, the El Berrocal facies was affected formed at the same temperature Ž1008C. as the quartz
by a first set of hydrothermal events, at high temper- veins and secondary sericite in the hydrothermally
ature ŽT ) 3508C., and defined as deuteric andror altered granite.
early postmagmatic alteration processes which trans- Finally, the intensity and depth of the weathering
form the original facies into the so-called reference effects on the El Berrocal system are related to the
granite. These processes are weak but pervasive degree of fracturing and hydrothermal alteration of
since they affect the whole granitic mass. The inter- the granite, as well as the mineralogical composition
nal isochron obtained from apatite, albite, potassium of the hydrothermally altered granite and UQV and
feldspar, biotite and bulk-rock sample of the El fracture fillings Žsee Fig. 2.. As far as the fracture
Berrocal facies suggests that the bulk rock remained fillings are concerned, beidellite and a second gener-
a closed system for the Rb–Sr pair during late ation of kaolinite were formed during these pro-
alteration processes, and that the minerals were closed ´ del Villar et al., 1997..
cesses ŽPerez
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.
2.3. Relationships between alteration processes and
represents the time during which the first set of
U, Th, Zr and REE mobilisation
hydrothermal alteration processes took place in the
´ del Villar et al., 1996a..
El Berrocal facies ŽPerez
The second hydrothermal event recorded in the All alteration processes recorded in the El Berro-
site is related to N80E and N110E fracture families. cal system produced the remobilization, migration
This process transforms the reference granite into the and retention, mainly by precipitation, of UŽIV. and
hydrothermally altered granite adjacent to these frac- ThŽIV., as analogues for PuŽIV. and NpŽIV., UŽVI.,
tures. The alteration is evidenced by the sericitization for PuŽV and VI. and NpŽV., light rare earth ele-
of feldspars, mainly albite, the presence of secondary ments ŽLREE., for Am, Cm and PuŽIII. ŽChapman
carbonates scattered through the rock, and the yel- and Smellie, 1986., and Zr as a fission product
´ del Villar et al.,
low-green colour of the rock ŽPerez ´ del Villar et al., 1994, 1995, 1996a,b,c and
ŽPerez
1995.. The minimum temperature of formation of ´ del Villar et al., 1996d..
Perez
secondary sericite, determined from its d18 O values, Thus, during the first set of deuteric andror
ranges between 808 and 1208C ŽPerez ´ del Villar et hydrothermal events, uraninite, monazite, xenotime
al., 1996b.. and apatite in the granite were partially destabilized
In relation to this process and using up the silica by F-rich fluids in such a way that when these
released by feldspar alteration, sulphide-bearing minerals are surrounded by fluorite, uraninite is to-
quartz veins and their clayey walls were formed, tally or partially pseudomorphized by complex U
´ del Villar
filling the abovementioned fractures ŽPerez silicophosphates; monazite is totally or partially de-
et al., 1996b.. According to the d18 O values of pleted in REE, xenotime shows U and REE-poor
quartz from quartz veins and values found for illite altered zones and apatite is partially dissolved. The
from their clayey walls, both quartz veins and clayey presence of U silicophosphates coating chloritized
walls were formed at about 1008C ŽPerez ´ del Villar 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 granite vary according to the nature and fracturing
U away from uraninite and its retention in the rock degree of its host mineral. Thus, if uraninite is
matrix, respectively. On the other hand, Th from included in feldspars, the former is usually dissolved
monazite remains immobile and no secondary REE- and only the outlines of the crystals remain, with
bearing minerals have been found. Based on these residual Th–Ca silicophosphates inside. The U from
textural features, F is probably responsible for the uraninite, forming U silicophosphates, is usually fill-
alteration of the U, Th and REE-bearing minerals, as ing adjacent microfissures, or is adsorbed, together
well as for the transport of U and REE, probably as with P, onto Fe oxyhydroxides.
fluoride complexes. This hypothesis was confirmed v Weathering on the hydrothermally altered
by the presence of secondary fluorite and U silicate granite mainly caused a distribution of U, which
compounds filling dissolution voids in albite. forms large autunite crystals andror is adsorbed onto
The second hydrothermal process, responsible for secondary sericite and Fe oxyhydroxides.
the hydrothermally altered granite and quartz veins, v The effects of weathering on the U-ore body
mobilised and also reprecipitated U, Th, REE and are represented by strong oxidation of pitchblende
Zr. The mineralogical evidences of these processes and sulphides, dissolution of carbonates and neofor-
are: the occurrence of U silicophosphates lining and mation of secondary U minerals such as uranotyle,
filling microfissures in secondary pyrite; the precipi- autunite, in secular equilibrium, torbernite and ura-
tation of botryoidal ‘mineraloids’, whose composi- nocircite. Furthermore, U is also adsorbed onto Fe
tion varies from U ) Th to Th ) U silicophosphates; oxyhydroxides.
the presence of Th and Zr silicates filling microfis- v Similar weathering effects have been observed
sures in quartz; the neoformation of florencite and on the fracture filling materials. Thus, uranium forms
the general increase of U, Th, Ce, Y, and Zr contents uranyl silicates and phosphates, such as uranotyle,
in the hydrothermally altered granite. In this case, autunite and phosphuranylite, and is adsorbed onto
the chemical agent that mobilised U, Th, REE and Zr Fe oxyhydroxides. At present, the uranyl carbonate
is not as clearly defined as in the former case. complexes are the dominant soluble species in oxi-
In relation to this second hydrothermal event, the dising groundwaters in the system ŽGomez ´ et al.,
uranium-ore body hosted in the main quartz vein was 1996..
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- 3. Sampling and methods
tures as uranyl–carbonate complexes. These solu-
tions, reheated at depth by the tectonic events that Twelve samples analysed from the carbonate-
fractured the quartz veins, moved upwards, probably bearing hydrothermally altered granite were taken
by convective flow. After destabilisation of uranyl– from borehole S-13, at both sides of the UQV. The
carbonate complexes caused by rock–water interac- average sample size is shaped like a cylinder, 1 cm
tion processes and a drop in temperature and pres- long and 8.6 cm in diameter.
sure, uranyl cations were probably reduced by H 2 S, Samples from fracture fillings come from bore-
precipitating pitchblende, carbonates and pyrite. The holes ŽS. 13, 14, 15, 16 and 17, amounting to 122
coexistence of pyrite and barite suggests that the samples, and distributed as follows: S-13 Ž21.; S-14
precipitation took place between y200 and y300 Ž9.; S-15 Ž16.; S-16 Ž54. and S-17 Ž22.. The sam-
mV ŽKrivovichev, 1979.. The same process also pling is representative of both high-and-low hy-
affected the hydrothermally altered granite close to draulic conductivity fracture zones ŽFig. 2.. Due to
the UQV and, to a lesser extent, the intra-granitic the scarcity of infill material above a depth of 50 m,
fractures. the sampling in S-13, 15 and 16 started below this
The effects of weathering on U of each part of the level. Samples were usually scraped from both sides
system may be summarised as follows. of the fractures or loosened when the fracture fillings
v The effects on the uraninite of the reference 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 borehole S-16, taken at a depth of 400 m, were used
the reaction is continued for 24 h at 258C, after to determine the d13 C values in the dissolved inor-
which time the released CO 2 is discarded. The sam- ganic carbon ŽDIC.. Carbon was collected by pre-
ple may then be allowed to react at 508C for 10 days cipitation of SrCO 3 following the method of
and the CO 2 subsequently removed is used to deter- Carothers and Kharaka Ž1980.. Strontium carbonate
mine the isotopic composition of ankerite. was reacted with phosphoric acid to produce CO 2
Furthermore, nine groundwater samples from 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 Fig. 6. Temperature range in which the secondary carbonates
Finnigan Mat 251 mass spectrometer. The experi- Žankeritic fractions. of the hydrothermally altered granite were
mental error found was "0.1‰ for d13 C and d18 O, formed, obtained from the Carothers et al. Ž1988. equation for
siderite.
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
were significant, due to the chemical method used,
carbon dioxide obtained from a calcite standard pre-
the results will be discussed separately.
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, 4. Results and discussion
1986. and 1.0090 for calcite ŽFriedman and O’Neil,
1977.. 4.1. Mineralogy, d18 O and d13C of secondary car-
Only the carbonates from the hydrothermally al- bonates from the hydrothermally altered granite
tered granite presented a significant amount of
ankerite. Usually, the amounts of CO 2 from ankeritic According to SEM q EDX data, the carbonatation
carbonates in fracture filling samples were too scarce process that affects the hydrothermally altered gran-
to be analysed by mass spectrometry. However, in ite is mainly characterised by the occurrence of
samples whose CO 2 content was high enough, the ankerite with minor calcite. Based on the textural
isotopic results for carbon and oxygen were very relationships between sericite and carbonates ŽFig.
similar to those obtained using the method of Mc- 3., the latter could have been formed either simulta-
Crea Ž1950.. Indeed, the differences were less than neously or somewhat later than sericite.
0.2‰ and 0.3‰ for d13 C and d18 O, respectively. The isotopic results obtained from calcitic frac-
Consequently, only the data obtained by McCrea’s tions of these carbonates ŽTable 1. show the follow-
method will be included and discussed in this work. ing features: Ža. A striking homogeneity of the d13 C
Since the differences in isotopic signatures of values, which range from y7.7‰ to y7.1‰, except
carbonates from the hydrothermally altered granite 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) 293–315 305

vary to a larger extent than the d13 C values, ranging cording to the temperature of formation and the
from y14.2‰ to y11.1‰. Žc. The temperatures textural relationships between these carbonates and
obtained, taking into account the equation of Ander- sericite.
son and Arthur Ž1983. and the annual average value
of d18 O in the El Berrocal current meteoric waters 4.2. Mineralogy, d13C and d18 O of carbonates from
Žy7.6‰., vary within a narrow range, between 358 fracture fillings
and 528C ŽFig. 4..
The relative negative d13 C values of these calcitic The carbonate content obtained by XRD ranges
fractions indicate that the main source of carbon was from 94% to below the detection limit. These data
the edaphic cover ŽSalomons and Mook, 1986; Cer- were confirmed by TGA and both methods are in
ling, 1991.. This effect was more evident in sample good agreement ŽFig. 7a.. Calcite is the main car-
ZB-30, with a typical edaphic d13 C ŽTable 1 and Fig. bonate species and was identified in most of the
5.. Furthermore, the temperatures obtained are con- samples. Only in S-13 Ž54 m. and S-15 Ž49 to 75 m.,
sistent with low-temperature hydrothermal processes. did calcite and dolomite coexist. The semiquantita-
However, calcite from sample ZB-30, which pre- tive chemical analyses by EDX show the constant
sented an anomalous d13 C value, probably caused by presence of Mn in both carbonates. The percentage
the existence of a mixture of hydrothermal and mete- of Mn is so variable in calcite that the Ca–Mn-
oric calcites, might have partially formed at higher carbonate series Žcalcite–kutnahorite–rhodochrosite.
temperatures. In this respect, the location of this can be defined ŽFig. 7b.. However, kutnahorite and
sample close to the UQV, where the intense circula- rhodochrosite are always below the XRD detection
tion of meteoric waters is currently taking place as it limit. From a textural and structural point of view,
did in the past, would suggest the coexistence of old carbonates occur as veinlets of xenomorphic calcite,
Žhydrothermal. and recent Ženvironmental. calcites, but more frequently they appear as - 1-mm-thick
the latter being enriched in light carbon. layers coating both fracture walls. In the latter case,
The isotopic signatures of the ankeritic fractions calcite forms a mosaic in which pit etchings are
ŽTable 2. follow a similar trend to those observed in frequent. Sometimes, in some fracture walls, calcite
calcite, though they also present the following differ- is more developed and shows the typical rhombohe-
ences: Ža. Generally, the effect of edaphic CO 2 in dral habit.
ankeritic carbonates is slightly lower than on calcitic Wherever calcite and dolomite coexist, their tex-
fractions ŽTable 2 and Fig. 5.. In samples ZA-25 and tural relationships are not clear enough for their
ZB-25, The effect is even lower. This enrichment in crystallization sequence to be established. However,
heavy carbon could be explained by dissolution–pre- both carbonates are more recent than neoformed
cipitation processes. Žb. The temperatures obtained quartz, because they fill voids between the quartz
between 618 and 728C ŽFig. 6. were calculated using crystals. Kutnahorite and rhodochrosite seem to be
the equation of Carothers et al. Ž1988. for siderite, more recent than calcite and smectite, since they
because no equation has been found for ankerite in always appear as small single rhombohedral crystals
the specialised literature. These temperature values on calcite or smectite. In the first case, the crystals
are higher than those of calcitic fractions. Žc. Only are usually oriented parallel to the cleavage planes of
three samples, ZA-26, ZB-22 and ZB-30 contain no calcite.
ankeritic fraction. The mineralogical distribution of the five bore-
In short, the hydrothermally altered granite was holes studied ŽFig. 8. shows that: Ži. in boreholes
affected by a very-low-temperature hydrothermal S-14 and S-17, carbonates appear below 60 and 80
carbonatation process, during which ankeritic car- m, respectively. This is due to the dissolution of
bonates were firstly precipitated, followed by calcite, carbonates by meteoric waters in the upper zones of
at lower temperature. It also appears that the influ- the site. In these fractures, residual Fe–Mn oxyhy-
ence of edaphic CO 2 in both carbonates followed the droxides are present instead of carbonates. Žii. No
cooling of the system. This carbonatation event prob- relationship between carbonate concentration and
ably took place after the sericitization process, ac- 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) 293–315 311

conditions. Only in S-16, below 215 m, does the outermost experimental data lines CD and CB were
symmetrical distribution of both isotopic signatures obtained. Lines AD and AB were plotted parallel to
seem to be broken. This exception may be due to the the x and y axes respectively, starting from samples
existence of carbonates precipitated from a mixed richest in 13 C and 18 O. Vertices B and D almost
solution of deep and shallow bicarbonate waters. coincide with the experimental values. Therefore, the
Furthermore, some d13 C values are more negative vertices of this quaternary diagram would indicate
than those of the edaphic typical carbonates the theoretical isotopic signatures of the carbonate
ŽSalomons et al., 1978; Talma and Netterberg, 1983; end-members that formed the mixtures. Conse-
Salomons and Mook, 1986.. This could be explained quently, the carbonates of fracture fillings corre-
by taking into account that in granitic recharge wa- spond to mixtures of carbonates of edaphic origin
ters are usually weakly acidic, and under such condi- Ž d13 C between y10‰ and y16.5‰. formed at
tions the d13 C values of DIC are very close to those ambient temperature, and of other hydrothermal car-
of the soil-CO 2 ŽFritz et al., 1989; Romanek et al., bonates with predominant edaphic carbon and pre-
1992.. This is in agreement with the d13 C values cipitated at a temperature between 508 to below
obtained from the El Berrocal DIC, ranging between 1008C.
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 5. Conclusions
0.13Ž dc y d w . 2 ŽAnderson and Arthur, 1983. and
the d18 O annual average value of the El Berrocal In the El Berrocal hydrothermally altered granite,
current meteoric water Žy7.56‰. ŽReyes et al., two types of disseminated carbonates have been
1995.. The results ŽTable 4, Fig. 11. demonstrate identified according to their chemical composition,
that 80% of these carbonates were formed at temper- temperature of formation and C and O isotopic com-
atures between 258C and at least 658C, while the position. The first is ankeritic and precipitated at a
remaining 20% were formed at ambient temperature. temperature range between 728 and 618C, whereas
These data would seem to point towards a mixture the second is calcitic and formed between 528 and
between carbonates formed at ambient conditions 358C. The effect of edaphic CO 2 has been demon-
and carbonates formed at temperatures higher than strated, and is stronger in calcite than in ankerite.
those calculated. Consequently, at least two genera- Consequently, in both cases, carbonate-bearing
tions of carbonates are superimposed in the system. groundwaters have a meteoric origin and were re-
In order to confirm this hypothesis, d18 O values heated at depth and moved upwards by convective
of all the samples were plotted vs. d13 C values ŽFig. flow. ŽFig. 13.. Furthermore, the influence of edaphic
12a.. The regression line obtained has a correlation CO 2 in these carbonates has increased during the
coefficient of 0.46 and a negative slope, suggesting a cooling of the system.
mixture of carbonates formed under different condi- The difference between the temperature of forma-
tions. Likewise, if only data from samples located tion of ankerite and calcite suggest that both phases
between 0 m and 250 m are considered, a regression formed during the same low-temperature hydrother-
line with a higher correlation coefficient of 0.74 is mal event. This carbonatation process can also be
obtained ŽFig. 12a.. In order to determine the iso- considered as the thermal tail of the same hydrother-
topic signature of each carbonate component, a qua- mal event that originated the hydrothermally altered
ternary diagram was plotted, where the vertices rep- granite, the quartz veins and the most important
resent the isotopic signatures of carbonates that could process of mobilizationrmigration of U from urani-
have been mixed ŽFig. 12b.. Vertex C was defined nite in the granite, that originated the U-ore body.
taking into account d18 O and d13 C values of a This conclusion seems to be confirmed by the tem-
theoretical hydrothermal carbonate formed at 1008C, perature of formation of sericite, which ranges from
scarcely influenced by edaphic CO 2 and similar to 808 to 1208C, quartz veins, at about 1008C, the
carbonates studied by Feux and Baker Ž1973. in textural relationships between sericite and carbonates
granitic environments. By joining this vertex to the 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 According to the temperatures of formation of
and the U-ore body. ankeritic carbonates in the hydrothermally altered
As for the hydrothermally altered granite, at least granite and hydrothermal carbonates from fracture
two types of carbonates have been identified in fillings, it is suggested that both types are the result
fracture filling materials, according to their tempera- of the hydrothermal process described above. Their
tures of formation. The first carbonate was formed chemical differences may be due to different intensi-
under hydrothermal conditions, between 258 and at ties of waterrrock interactions. Thus, the hydrother-
most 1008C, and the second at ambient temperature mally altered granite is closely related to a major
F 258C. Almost all the samples correspond to mix- tectonic accident which affected a very important
tures of both components. In addition, the isotopic granitic mass, whereas the fracture filling materials
signatures of carbon in both carbonates indicate the are linked to minor tectonic accidents, whose effects
influence of edaphic carbon and, consequently, the are only affective in thin granitic bands at both sides
meteoric origin of the water. To explain the precipi- of the fractures. In this way, significant amounts of
tation of hydrothermal carbonates, we suggest a re- Fe, Mg and Mn were released during the alteration
heating at depth and upward movements of carbon- of biotite and transferred to carbonate solutions. This
ate solutions. caused the precipitation of ankerite in the hydrother-
 E. Reyes et al.r Chemical Geology 150 (1998) 293–315 313

mally altered granite, whereas in the fractures only ˜

espanoles de uranio. ‘El Berrocal’, Escalona ŽToledo.. Not.
Ca and minor Mn were supplied to form Mn-calcite. Com. Inst. Geol. Min. Espana ˜ 77, 67–92.
Barnes, Y., Evans, W.C., White, L.D., 1988. The role of mantle
As for the U-ore body, the hydrothermal carbon- CO 2 in volcanism. Appl. Geochem. 3, 281–285.
atation processes that affected the intra-granitic frac- Carothers, W.W., Kharaka, J.K., 1980. Stable carbon isotopes of
tures could also be responsible for the ancient migra- HCOy 3 in oil-fields waters—implications for the origin of
tionrretention of uranium, mainly by precipitation of CO 2 . Geochim. Cosmochim. Acta 44, 323–332.
minor pitchblende, observed in fracture infill materi- Carothers, W.W., Adami, L.H., Rosenbauer, R.J., 1988. Experi-
mental oxygen isotope fractionation between siderite–water
als. Currently, this UŽIV. oxide is almost totally and phosphoric acid liberated CO2–siderite. Geochim. Cos-
oxidized by weathering, with the uraniun retained as mochim. Acta 52, 2445–2450.
uranyl minerals and adsorbed onto Fe oxyhydrox- Cerling, T.E., 1984. The stable isotopic composition of modern
ides. To explain the latter process, we suggest that sill carbonate and its relationship to climate. Earth Planet. Sci.
bicarbonate meteoric waters, enriched in light car- Lett. 71, 229–240.
Cerling, T.E., 1991. Carbon dioxide in the atmosphere: evidence
bon, oxidized and dissolved pitchblende, transporting from Cenozoic and Mesozoic paleosols. Am. J. Sci. 291,
UŽVI. as uranyl–carbonate complexes. After destabi- 377–400.
lization of these complexes by rock–water interac- Chapman, N.A., Smellie, J.A.T., 1986. Introduction and summary
tion processes, uranyl cations were precipitated as of the workshop. In: Chapman, N.A., Smellie, J.A.T. ŽEds..,
uranyl silicates and phosphates, or adsorbed onto Fe Natural Analogues to the Conditions Around a Final Reposi-
tory for High-level Radioactive Waste. Chem. Geol. 55, 167–
oxyhydroxides. Carbonate anions were precipitated 173.
as calcite, with minor Mn. In this sense, the uranyl Choppin, G.R., Wong, P.J., 1996. Current status of radioactive-
carbonate complexes are, at present, the dominant waste disposal. J. Radioanal. Nucl. Chem. 203, 575–590.
soluble species in the oxidising groundwaters of the Clauer, N., Frape, S.K., Fritz, B., 1989. Calcite veins of the Stripa
El Berrocal system. granite ŽSweden. as records of the origin of the groundwaters
and their interactions with the granitic body. Geochim. Cos-
mochim. Acta 53, 1777–1781.
Craig, H., 1953. The geochemistry of the stable carbon isotope.
Acknowledgements Geochim. Cosmochim. Acta 3, 53–92.
Criss, H., Taylor, H.P., Jr., 1986. Meteoric–hydrothermal sys-
tems. In: Valley, J.W., Taylor, H.P., Jr., O’Neil, J.R. ŽEds..,
Financial support for this work was provided by Stable Isotopes in High Temperature Geological Processes:
ENRESA, CIEMAT and CEC. We are grateful to Reviews in Mineralogy 16, 373–424.
´
Mr. Francisco Sanchez, Francisco Orden and Deines, P., 1980. The isotopic composition of reduced organic
´
Jeronimo Navea for the preparation of the samples. carbon. In: Fritz, P., Fontes, J.C.H. ŽEds.., Handbook of
The authors would also like to thank the Chemical Environmental Isotope Geochemistry, Vol 1. The Terrestrial
Environment, A. Elsevier, pp. 329–406.
Geology reviewers ŽDr. R. Bros and the anonymous Faure, G., Powell, J.L., 1972. Strontium Isotope Geology Mineral,
reviewer. for their comments and constructive criti- Rocks and Inorganic Materials. Springer-Verlag, Berlin, 188
cisms which have notably improved the paper. pp.
Feux, A.N., Baker, D.R., 1973. Stable carbon isotopes in selected
granitic, mafic and ultramafic igneous rocks. Geochim. Cos-
mochim. Acta 37, 2509–2521.
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