Applied

Geochemistry
Applied Geochemistry 20 (2005) 465–485
www.elsevier.com/locate/apgeochem

Hydrogeochemical evolution and C isotope study of

groundwaters from ‘‘Mina Fe’’ U deposit (Salamanca,
Spain): implications for processes in radwaste disposal
L. Pérez del Villar a,*, A. Garralón a, A. Delgado b, E. Reyes b, J.S. Cózar a,
P. Gómez a, R. Núñez b, L. Sánchez a, J. Raya b
a
CIEMAT/DIAE/CHE/Ed.20, Avda. Complutense 22, 28040 Madrid, Spain
b
CSIC, Estación Experimental del Zaidı́n, Prof. Albareda 1, 18008 Granada, Spain

Received 21 July 2003; accepted 28 September 2004

Editorial handling by M. Gascoyne

Abstract

Within the framework of the ENRESA natural analogue programme, the U ore deposit of ‘‘Mina Fe’’, western
Spain, has been studied as a natural analogue of radioactive spent fuel behaviour after burial, in spite of being an extre-
mely perturbed geological environment due to mining activities. The main objectives of this project are to determine the
hydrogeochemical evolution of the system and identify the main water/rock interaction processes that control the
physicochemical variables (pH and Eh) of groundwaters, including the role-played by the organic matter.
The hydrogeochemical results from 3 consecutive groundwater sampling campaigns, separated by a phase of resto-
ration works, indicate that the groundwater of the site shows an evolutionary trend from Ca–SO2
4 acid oxidising waters
towards alkaline-reducing waters, though their evolution with respect to the alkaline and alkaline-earth elements is not
clear. The SO2

4 -acid waters are the result of the oxidation processes affecting the primary sulphide-rich U mineralisa-
tion, while the alkaline-reducing waters result from the buffer capacity of carbonates from fracture filling materials, as
the d13C values of DIC demonstrate. The reducing character of these waters mainly results from the microbiologically
mediated partial oxidation of the abundant organic matter existing in the clayey walls of the major faults at the site,
since other dissolved inorganic redox pairs are insufficient to explain the in situ measured redox potential. Thus, the
high content in DOC of these waters is also explained, since the soil at the site is poorly developed. DOC, DIC or both
can be responsible for the high U concentration measured in these groundwaters, in spite of its reducing character.
The restoration works performed in the exploitation quarry have also restored the aforementioned evolutionary
trend, which was the normal evolution of groundwater in the site before mining. Finally, the results are discussed in
terms of the geochemical processes expected in a radioactive disposal site after closure.
Ó 2004 Elsevier Ltd. All rights reserved.

1. Introduction

Uranium deposits have been extensively studied as

*
Corresponding author. Fax: +34 1 3466542. natural analogues of the deep geological disposal of
E-mail address: 1.pvillar@ciemat.es (L. Pérez del Villar). radioactive waste (Chapman et al., 1990; Murphy and

0883-2927/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2004.09.015
466 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485
Pearcy, 1992; Blanc, 1996; Rivas et al., 1997; Bruno
et al., 1997; Reyes et al., 1998; Gauthier-Lafaye et al.,
2000; Blomqvist et al., 2000; Pérez del Villar et al.,
2003). These investigations constitute an essential ele-
ment of both national and international research pro-
grammes focussed on the assessment of geological
repositories in crystalline, clayey and even schistose
rocks. In this context, within the framework of the EN-
RESA natural analogue programme, the U deposit of
‘‘Mina Fe’’, western Spain, (Arribas, 1962, 1985; Man-
gas and Arribas, 1984; Martı́n-Izard, 1989; Both et al.,
1994; Martı́n-Izard et al., 2002) has been studied as a
natural analogue of the nuclear spent fuel behaviour
after burial, in spite of its unsuitable geological condi-
tions. This U mineralisation is hosted in highly fractured
geological media, which are extremely perturbed by the
exploration and mining activities. However, the similar-
ities with some of the repository features and the analo-
gies with the processes involved in the degradation of
this U deposit favoured its study as a natural analogue.
This subject has been the general aim of a research pro-
ject known as the ‘‘MATRIX project’’, which was stra-
tegically divided into two 3-year phases.
Phase I was mainly focussed on the geology, mineral-
ogy and elemental geochemistry of the solid phases,
hydrogeology and hydrogeochemistry, in order to estab-
lish: (i) the analogies between the natural system and a
deep geological radwaste repository; (ii) the most rele-
vant geochemical processes in the system; and (iii) the
implications for performance assessment of a spent nu-
clear fuel repository (Pérez del Villar et al., 2001, 2002a).
Among the objectives envisaged in Phase II are the
determination of: (i) pitchblende-coffinite transformation
mechanisms under reducing conditions and ambient tem-
perature; (ii) the role played by the fracture minerals as
scavengers of trace analogue elements, mainly U (Pérez
del Villar et al., 2002b; Quejido et al., 2004); (iii) the
approximate time scale of the recent and recent-past up-
takes or losses of U in the system (Crespo et al., 2003);
(iv) the hydrogeochemical evolution of the system after
its restoration performed in 2000; and (v) the main
water/rock interaction processes that control the physico-
chemical variables (pH and Eh) of groundwaters, includ-
ing the origin and role of the organic matter in the redox
potential observed in these groundwaters (Gómez et al.,
2000; Pérez del Villar et al., 2001, 2002a).
In order to achieve the last two objectives, groundwa-
ters from the site have been sampled 3 times (1999, 2001
and 2002) and characterised from physicochemical and
isotopic (stable, radioactive and radiogenic isotopes)
perspectives. Plants, humus, soil, and organic matter
from the host rocks and carbonaceous-clayey walls of
some major faults in the site (Boa and Graphitic faults)
were also sampled and analysed for C isotopes, in order
to decipher the origin of the dissolved inorganic and or-
ganic C (DIC and DOC) in groundwaters. Furthermore,
the anomalous features observed in the groundwaters
sampled during the first campaign (1999), specifically
concerning the negative Eh values and the high U and
dissolved organic C concentrations, encouraged the
achievement of these objectives. These anomalous
hydrochemical characteristics, reported in Gómez et al.
(2000) and Pérez del Villar et al. (2001, 2002a), favoured
a comprehensive study of this anomalous and unusual
groundwater system. Furthermore, reasoning by anal-
ogy, the implications of processes that can occur during
the degradation of a radwaste repository after burial
have been deduced and discussed.
2. Geological background
The ‘‘Mina Fe’’ is the most important U deposit in
the Spanish Iberian Massif. It is located around 10 km
NW of Ciudad Rodrigo (Salamanca) (Fig. 1). The U
mineralisation either fills open fractures or cements the
fault breccia affecting metasediments of the Upper Pro-
terozoic-Lower Cambrian Schist-Graywacke Complex,
known as ‘‘Complejo Esquisto-Grauváquico’’ (CEG).
In the ‘‘Mina Fe’’ area, the CEG rocks mainly consist
of a weakly metamorphosed sequence of carbonaceous
pelitic and fine-grained psammitic rocks, in which sedi-
mentary textures are frequently observed. The grade of
metamorphism is mainly greenschist facies, the main
rock types being carbonaceous slates, quartzites, con-
glomerates, sericitic and chloritic phyllites and micas-
chists, with some interbedded calc-silicate rocks, which
represent metamorphosed layers of impure carbonate
sediments (Martı́n-Izard, 1989).
The U mineralisation is the result of a hydrothermal
process in which 3 main phases have been distinguished.
The first occurred after a brecciation process that caused
chloritisation of the host rocks and breccia fragments, as
well as the formation of small ankerite-pyrite bearing
veins, with minor galena, sphalerite and chalcopyrite.
The second phase took place after another brecciation
process, producing most of the U ore. During this phase,
adularia, pyrite, pitchblende, coffinite and carbonates
were formed. The third phase is characterised by the epi-
sodic, laminated and repeated precipitation of pyrite,
carbonates and collophormic pitchblende. This type of
U mineralisation fills open fractures and breccia voids
(Arribas, 1985). The age of the U mineralisation, deter-
mined by the 207Pb/204Pb ‘‘vs’’ 235U/204Pb isochron, is
34.8 ± 1.6 Ma; the same age as of the Pyrenean tectonic
phase of the Alpine orogeny (Both et al., 1994). Re-
cently, Martı́n-Izard et al. (2002) suggested that this de-
posit was formed in a transpressional shear-zone of
Alpine age, affecting carbonaceous slates with a high
background concentration of U.
Based on fluid inclusion data and on the chemical
composition of the early chlorite, the temperature of
 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485 467

Fig. 1. Geographical location of the U-deposit of ‘‘Mina Fe’’ and ‘‘Mina D, Hole 01’’. ESPERANZA, ALAMEDA and SAGERAS
are other explored but non-mined uraniferous zones in the region (Pérez del Villar et al., 2002a).

the U mineralisation varies from 230 to 60 °C during the
first two phases, while the third took place at a tem-
perature lower than 60 °C (Mangas and Arribas, 1984).
Later on, the basement rocks and U mineralisation
have been intensively eroded and oxidised. The minera-
logical characteristics of the oxidised cap of this miner-
alised system indicate that the main geochemical
process has been the oxidation and supergene enrich-
ment that occur in sulphide-rich deposits when they
are exposed to weathering (Pérez del Villar et al., 2001,
2002a). Continental Tertiary and Quaternary sediments
of the Ciudad Rodrigo Basin also cover the system in
places, their thickness varying between 5 and 20 m in
the mining area. Numerous secondary U minerals, such
as yellow gummites, ianthinite, epi-ianthinite, alpha
uranotyle, autunite, metaautunite, torbernite, saleeite
and uranopilite were formed as a result of weathering
processes (Arribas, 1962, 1975).
3. The site, sampling and methods
3.1. The site
After a comprehensive review of the existing docu-
mentation concerning the mining activities at ‘‘Mina
Fe’’, the sector named ‘‘Mina D, Hole H-01’’ was se-
lected as the experimental site. It is located approxi-
mately 1 km to the SW of the central part of the main
quarry of ‘‘Mina Fe’’(see Fig. 1), and represents an open
pit excavated to extract high-grade U mineralisation
hosted in the breccia zone of a very important normal
fault known as the Boa fault (Fig. 2). The exploitation
front shows some remains of Tertiary and Quaternary
sediments; the Boa fault zone, with an apparent width
from 30 to 70 cm, including the mineralised breccia
and the carbonaceous-black clayey walls; small hydro-
thermal quartz veins, and different types of slate rocks
from the CEG.
The carbonaceous clayey walls, which are mineralog-
ically composed of illite + smectite + kaolinite + minor
chlorite (62%), quartz (30%), feldspars (3%), goethite
(4%), as average values, contain up to 0.6% of organic
matter, expressed as organic C. They are the result of
the mechanical and hydrothermal alteration processes
that affected the country rock along the Boa surface fault
(Pérez del Villar et al., 2001). Thus, the organic C in these
clayey walls is approximately twice as high as the organic
C content of the country rocks, which is 0.35% on aver-
age (Martı́n-Izard, 1989), while in the Graphitic fault,
with 1.9% of organic C (Martı́n-Izard, 1989), the concen-
tration is 5 times higher than in the country rocks.
468 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485

625 RO

AG
AD

UE
D
4900
4700
630 N
C-C'

AR
D
RA
4300 4300

IN
B-B'

IVE
PI
PE
SM-4

605

600

R
A-A'
55
635

610
40
SM-2 SM-3

615
50
SM-1 N-600

N-606
75
LT
FAU
618.14

BOA
0
N-63

MINE TAILINGS
N-636
CHA

N-625
NNE
L

AD
RO
0
4700

4900
64
5
64

4100 635 0 4100

62
630 5 50 m
62

Fig. 2. Topographic map of ‘‘Mina D, Hole H-01’’ in which the Boa fault, the location of boreholes SM-1 to SM-4 and the orientation
of cross-sections A–A 0 , B–B 0 and C–C 0 in Fig. 3 are shown (Pérez del Villar et al., 2002a).

The geometrical and statistical analyses of the Boa
fault and other fractures in the site indicate that:
 The Boa fault, with variable direction N60-80E and
30–60°N dip, is an ancient Hercynian compression
fault, which was reactivated as a normal fault during
the Alpine orogenesis, when the U-ore deposit was
formed (Pérez del Villar et al., 2002a)
 Fracture frequency, direction density and the number
of fracture intersections indicate that the area is
intensively tectonised, the fracturing intensity being
larger in the sunken block, to the north, than in the
uplifted one to the south of the Boa fault. This fact
would explain the higher weathering and more inten-
sive U leaching in this northern block. In spite of the
large dispersion in fracture directions, it is possible to
classify them into the following groups: N120°E,
N60°E, N20°E and N170°E. The spacing distribution
among the fractures is lognormal with a spacing var-
ying from 0.35 to 0.53 m (Pérez del Villar et al.,
2002a)
The following conclusions were derived from the
hydrogeological investigation of the site (Pérez del Villar
et al., 2002a):
 The Boa fault is not a preferential flow path, but is
part of a larger set of hydraulically active faults and
fractures.
 Fractures associated with the Boa fault do not have a
substantial influence on groundwater circulation,
while other fractures without any relation to this
fault have a similar or larger transmissivity.
 The permeability distribution of fractures in the sys-
tem is quite heterogeneous, showing fracture zones
with low permeability, because of their size and/or
fracture-infill materials, and others with higher
permeability.
 In general, according to the measured hydraulic
heads, the shallow groundwater flow is quite slow
(0.01 m/d) and directed towards the bottom of Hole
H-01. The deep groundwater flow is controlled by
the regional flow system, which is conditioned by
the Águeda River (Fig. 3).
3.2. Sampling
In order to intersect the Boa fault zone, 4 boreholes
with continuous core recovery and low contamination
risk for groundwaters (SM-1 to SM-4) were drilled to
fulfil all the objectives of the project, mainly those re-
lated to the hydrogeochemical evolution of the system
(see Figs. 2 and 4). Three groundwater-sampling cam-
paigns were carried out from 1999 to 2002, all of them
at the beginning of the summertime. Boreholes SM-2,
SM-3 and SM-4 were sampled in the first campaign,
while only boreholes SM-2 and SM-3 were sampled in
 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485 469

SW NE
Topographic levels (m) Flow lines

640
SM2 SM3
S M 2
S M 3
Hole H-01 Water table
630

620 Águeda River

610 SM4
S M 4

Caldera
C a l d e r a

600
Fa
590 Boa Fault
580

570
Deduced fault trace
560
0 50 100 m
0 5 0 1 0 0 m

550

Fig. 3. Idealised cross-section showing the hydrogeological model of the Boa fault zone (Pérez del Villar et al., 2002a). This cross-
section is sub-parallel to the trace of the Boa fault. For location, see Fig. 2.

the last two. Borehole SM-1 was never sampled, since it after pumping at least 3 times the volume of the
only intersected the unsaturated zone of the site. Bore- packed-off sections, and after stabilisation of the afore-
hole SM-4 was not sampled in the last two campaigns mentioned physicochemical parameters was achieved.
due to the high contamination level observed in its Sampling was carried out in a portable glove box under
water, as a result of its proximity to the sump formed anoxic atmosphere (N2), previously filtered by 0.45 lm
by Hole H-01 (see Fig. 4). This was continuously flooded (ASTM, 1976; US EPA, 1983) for the first two cam-
with very acid SO2
4 water (pH 2.9) and high concentra- paigns, and by 0.45 and 0.22 lm filters for the third
tion of dissolved metals, including U (Gómez et al., one. The piezometric levels were measured before and
2000; Pérez del Villar et al., 2001, 2002a). These circum- after sampling.
stances hampered any possibility of understanding the Samples for conventional chemical analysis were ta-
original water chemistry of this borehole. Consequently, ken in triplicate and preserved with: (i) HNO3 at
only boreholes SM-2 and SM-3 were systematically sam- pH < 1.5 for cations, trace elements and U; (ii) H2 SO4
pled, their samples being the only ones used to fulfil the at pH <1.5 for ammonium and (iii) HCl at pH <1.5
aims of this research work. for Fe speciation. Unacidified samples were used for an-
Water samples of the Boa Fault come from packed- ions. Samples for DOC and its isotopic signature were
off sections of boreholes SM-2, between 36 and 45 m also collected in triplicate at the beginning, at the middle
deep (T2), and SM-3, between 38 and 51 m deep (T1). and at the end of the sampling. All of them were stabi-
For groundwater pumping, the gas-lift system, previ- lised with HCl at pH 2. Sample volumes varied from
ously installed inside the boreholes, was used. Before 250 mL for borehole SM-2 to 1 L for SM-3, since
sampling, the physicochemical parameters of the groundwaters from the former were enriched in DOC
groundwater (pH, Eh, T, EC and O2 dissolved) were (29.6 mg/L) compared to the latter (5.1 mg/L) in the
measured, on line and on the surface, by means of a 1999 campaign (Gómez et al., 2000; Pérez del Villar
Hydrolab Series 4a datasonde multiprobe, equipped et al., 2001, 2002a).
with: In order to determine the source of the DIC by means
of its isotopic signature (d13C), 30 water samples, col-
 A Pt electrode for redox potential measurements lected after every 500 mL of extracted water, were taken
(accuracy ± 20 mV, resolution 1 mV). from each borehole during each campaign. Approxi-
 A temperature thermistor in a 316 stainless steel tube mately, half of the samples were taken under anoxic
(accuracy ± 0.10 °C, resolution 0.01 °C). atmosphere, while the other half were taken under oxic
 A graphite electrode for specific conductance (accu- conditions. The samples consisted of 2 mL of water in-
racy ± 0.001 mS/cm, resolution 0.001 mS/cm). jected in special vials for mass spectrometry, previously
 A Clark Cell dissolved O2 electrode (accuracy ± 0.2 filled with a mixture of extremely pure phosphoric acid
mg/L, resolution 0.01 mg/L). and He (Salata et al., 2000). Prior to the analyses, all
 A standard pH glass sensor with flowing junction ref- the samples were maintained at 4 °C
erence electrode (accuracy ± 0.2 units, resolution 0.01 Samples of organic materials for d13C determina-
units). tions consisted of the most representative plants in
the site, undetermined lichen, dead leaves, humus, two
In order to ensure that the water samples were represent- soil horizons (A1 and A2), unaltered carbonaceous
ative of the in situ conditions, samples were collected slates and carbonaceous clayey materials from the
470 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485

Fig. 4. Schematic cross-sections of ‘‘Mina D, Hole 01’’, showing the intersections between boreholes and the Boa fault from which
groundwater samples were taken. Notice that boreholes SM-2 and SM-3 intersect the Boa fault in the reduced zone. Vertical redox
zoning was established based on fracture filling mineralogy (Pérez del Villar et al., 2002a). The location of profiles is shown in Fig. 2.

Boa fault walls and another parallel major fault, known
as the Graphitic fault. The samples from the first fault
come from the exploitation front of ‘‘Mina D’’, Hole 1
and from the cores of boreholes SM-1, 2, 3 and 4, while
the sample from the Graphitic fault was taken in an
outcrop located approximately 1 km to the N of the
experimental site, outside of Fig. 2. This outcrop is
intensively affected by percolating acid water (pH <3),
as a result of pyrite oxidation, which is a very abundant
sulphide in the mineralised zones, such as the Boa and
Graphitic faults.
3.3. Methods
The filtered water samples were chemically analysed
by combining various analytical techniques. Inductively
coupled plasma atomic emission spectrometry (ICP-
AES) for Al, Ca, Mg, total Fe, Mn and Li. Inductively
coupled plasma mass spectrometry (ICP-MS, Finnigan
Mat SOLA) for As, Be, Bi, Cd, Ce, La, Co, Cu, Hg,
Mo, Ni, Pb, Rb, Sb, Se, Sn, Sr, Th, Ti, V, W, Y and
Zn. UV-visible spectrophotometry for Fe speciation
and SiO2 determination, by using the ferrozine and/or
orthophenanthroline methods depending on Fe concen-
trations, and the ammonium molybdate methods, respec-
tively. Ion chromatography (DIONEX 4500i) has been
used for Cl
, Br
, F
, NO
3
2

3 , PO4 and SO4 analysis,
while ion selective electrodes have been employed for
I
and NHþ 4 determinations. Potentiometric titration
for alkalinity measurements was used in both field and
laboratory determinations. The fluorimetric method
and laser induced kinetic phosphorimetry were used to
 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485 471

determine U. Potassium and Na were determined by
atomic absorption and flame emission spectrometry,
respectively. DOC was determined by means of a Tocor
C analyser, and the filters used were examined by scan-
ning electron microscopy coupled to an energy dispersive
X-ray analytical system (SEM + EDX), in order to deter-
mine suspended particles and colloids. Both, the fibre
pre-filter and the membrane filter itself were studied.
Prior to stable isotope analysis, DOC in water was
concentrated, dried and homogenised using an agate
mortar. Then, DOC, plants, humus, soil, carbonaceous
rock and carbonaceous clayey samples were burned,
with additional O2, at 1020 °C, in a Carlo Erba NA
1500 NC series 2 elemental analyser, coupled to a Delta
Plus XL mass spectrometer. The mixture of C oxides
and N2 thus obtained was transformed into a mixture
of CO2, N2 and H2O that was passed through a column
containing elemental Cu at 650 °C. Water was elimi-
nated by a Chromosorb trap, and CO2 and N2 were sep-
arated by chromatography before isotopic analysis.
have been compared with those obtained after restora-
tion. Thus, a significant increase of the pH values was
observed in water from borehole SM-2 that evolves from
neutral in 1999 (pH 7.1) to clearly alkaline in 2001 (pH
8.7) and 2002 (pH 8.2). A similar trend occurs in waters
from borehole SM-3 that evolve from weakly acid in
1999 (pH 6.4) to weakly alkaline in 2001 (pH 7.9) and
2002 (pH 7.4) (Fig. 5(a)).
Regarding redox potential, waters from SM-2 were
already reducing before restoration of the site (
300
mV), evolving toward more reducing, particularly in
2001 (
390 mV). A more drastic change is observed in
waters from borehole SM-3 that evolve from weakly
(
90 mV) to clearly reducing waters (
350 mV in
9.00
1999
8.75
2001
8.50
8.25
2002
8.00

For d13C measurements in DIC, samples were previ- 7.75

7.50
ously poisoned with a drop of HgCl2 solution. The gas
pH

7.25
mixture (He + CO2 + N2 + H2O etc) formed in the sam- 7.00
pling vials was automatically extracted using a Gas- 6.75
Bench-II system, and then passed through a Nafion 6.50

capillary, in order to eliminate the water vapour. Prior 6.25

6.00
to the isotopic analysis in the aforementioned mass spec- SM2 SM3

trometer, CO2 was separated by chromatography. In this (a) Boreholes

way, the error is less than 0.2% for d13C determinations.
-50
The 234U/238U activity ratios (AR) in groundwaters 1999
-100
were measured by alpha spectrometry, using Tennelec 2001
TC257 alpha spectrometers. The samples were radio- -150 2002
chemically purified by anion exchange with addition of -200
236
Eh (mV)

U as yield tracer (Aceña et al., 1994). The U fraction -250

was electrodeposited onto stainless-steel discs, according
-300
to the Hallstadius (1984) method. Sources were meas-
ured using passivated ion-implanted silicon detectors -350

of 450 mm2 active area. The good resolution of the spec- -400

tra allowed the measurement of the area under the peaks -450
by simple integration. Peaks of 236U were corrected for SM2 SM3
(b) Boreholes
the small contribution of 235U.
The 3H determinations were made by liquid scintilla-
tion after electrolytic enrichment of water, according to 3000 1999
the method of Allen et al. (1966). 2001
2500
2002
EC (µS/cm)

2000

4. Results and discussion 1500

4.1. Groundwater features and hydrogeochemical 1000

evolution
500

4.1.1. Physicochemical parameters 0

SM2 SM3
The evolution of the in situ measured physicochemi-
(c) Boreholes
cal parameters of the groundwater from the Boa fault is
shown in Fig. 5. For interpretation, data obtained be- Fig. 5. Evolution of the main physico chemical parameters of
fore restoration of the ‘‘Mina D’’ Hole 01 (July, 1999) groundwaters from the Boa fault: (a) pH; (b) Eh and (c) EC.
472 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485
2001 and 2002), with similar Eh values to those of waters
from borehole SM-2 (Fig. 5(b)).
As a consequence of the evolution of the pH and Eh
values, the electric conductivity (EC) of the waters from
both boreholes was significantly lower (approximately
half) after restoration of the site than before (Fig.
5(c)). This is due to the precipitation of pH-Eh depend-
ent elements.
These evolutionary trends are directly related to the
restoration works that essentially consisted of the top-
ographic smoothing of the quarry front, by removing
the exploitation benches, and infilling Hole H-01, for-
merly flooded with oxidising SO2
4 -acid waters. For
these works, the mine tailing materials, mainly com-
posed of carbonaceous slates, phyllites, carbonate-bear-
ing micaschists and calc-silicate rocks, were used,
which acted as buffer materials for the acid-SO2
4 water
from Hole H-01. Besides this, the hydraulic connec-
tions between the boreholes and Hole H-01 were also
partially stopped, thus minimising the mixing process
observed between water from Hole H-01 and ground-
waters from the rock formation (Gómez et al., 2000;
Pérez del Villar et al., 2001, 2002a). These facts are
demonstrated by the drastic changes observed in the
physicochemical parameters of the SM-3 groundwater,
since this borehole is the closest to Hole H-01 and,
therefore, the most contaminated with the SO2
4 -acid
waters in 1999.
According to NETPATH (Plummer et al., 1991) mix-
ing calculations, groundwater taken from SM-3 in 1999
is the result of a 56/44 mix between groundwater from
the rock formation (water from SM-2) and SO2
4 -acid
water from Hole-01, following reaction (1), expressed
in mmol/kg (Gómez et al., 2000; Pérez del Villar et al.,
2001, 2002a).
56% water from SM-2 þ 44% water from Hole

01 þ 2:93FeðOHÞ3 þ 0:01 siderite
þ 0:12 ankerite½CaMg0:7 Fe0:3 ðCO3 Þ2 
! water from SM-3 þ 0:89 gypsum þ 2:31CO2 ð1Þ
Furthermore, the current groundwaters from SM-3
show similar physicochemical characteristics to those
from borehole SM-2 in 1999, which were then consid-
ered as the most representative of the system. Conse-
quently, this means that groundwater from SM-3 has
evolved from a 56/44 mix between groundwater from
the rock formation (water from SM-2) and SO2
4 -acid
water from Hole-01, to groundwaters almost in equilib-
rium with the rock formation. However, the minor
changes also observed in groundwaters from borehole
SM-2 indicate that they were also contaminated in
1999, though to a lesser extent than those from borehole
SM-3.
Although the hydrogeological investigations sug-
gested that the deep groundwater flow is controlled by
the regional flow system, which is conditioned by the
Águeda River (see Fig. 3), the hydrogeological explana-
tion of the water-mix process described above could be
the local disturbances generated in the flow-lines of the
system by the presence of Hole-01 itself. Furthermore,
the pumping effects on borehole SM-3 could also facili-
tate the reverse circulation of the SO2

4 -acid waters from
Hole H-01 to SM-3 (T-1) packed-off section, through the
numerous fractures in the site.
4.1.2. Hydrochemical features and evolution
The hydrochemical evolution of groundwaters from
boreholes SM-2 and SM-3 is summarised in Table 1,
in which the hydrochemical features of the water from
Hole H-01 are also included for comparison. According
to these data, the evolutionary trend observed in the
waters from the Boa fault is mainly defined by a signif-
icant decrease of the dissolved ions. However, the waters
from SM-2 evolve from Ca–Mg SO2
4 water, with some
large HCOtextsubscript3 concentration, to
Mg–Ca–HCO
2

3 –SO4 water, while SM-3 waters remain


as Mg–Ca–SO2
4 waters. In both cases, the HCO3 con-
2

centration tends to increase while SO4 decreases. Chlo-
ride concentration remains practically constant. This
tendency is explained by the slight influence of the
SO2

4 -acid water from Hole H-01 on groundwaters from
the site, after its restoration. The massive oxidation of
pyrite from the mineralised zones is responsible for the
SO2

4 -acid character of the waters from Hole H-01 (Pér-
ez del Villar et al., 2001, 2002a).
Calcium and Mg contents decrease, in general, to-
wards the last campaign, while the behaviour of Na
and K is quite uneven. Though it seems that groundwa-
ters from SM-3 tend to be enriched in Na and even K
and impoverished in Ca and Mg, a clear evolutionary
trend is not observed.
Total Fe and Mn decrease significantly in boreholes
SM-3 and SM-2, respectively, while these elements tend
towards stabilisation in boreholes SM-2 and SM-3,
respectively. Similarly, the concentrations of Fe(II) and
Fe(III) in borehole SM-3 decrease in parallel with total
Fe. In contrast, the Fe(II)/Fe(III) ratios show a quite
uneven behaviour, though the Eh values are constant
in the last two sampling campaigns. In borehole SM-2,
the behaviour of Fe (II) and Fe (III) in the last two cam-
paigns is even more heterogeneous, since for an almost
constant amount of total Fe, the Fe(II)/Fe(III) ratios
are reversed, being much higher in 2002 than in 2001.
In contrast, the Eh value in 2002 is lower than in 2001.
Concerning minor and trace elements, Ni and Zn
show a similar behaviour in groundwater from the two
boreholes, in such a way that, in general, their contents
decrease towards the last sampling campaign. This fact
indicates less influence of water from Hole H-01. Stron-
tium follows a parallel trend to those of Ca and Mg in
both boreholes, which is probably related to the dissolu-
 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485 473

Table 1
Hydrochemical evolution of the Boa fault groundwaters intersected by boreholes SM-2 and SM-3
Borehole/section SM-2-T2 SM-2-T2 SM-2-T2 SM-3-T1 SM-3-T1 SM-3-T1 Hole H-01
Date 1999 2001 2002 1999 2001 2002 1999
HCO
3 mg=L 236 161 262 54,2 58 78,3 <3
Cl
mg/L 10 18 13 11 12 12 15.5
SO2
4 mg=L 294 135 108 2267 573 935 4975
F
mg/L 0.3 0.3 ND 0.1 0.8 ND <0.1
I
mg/L 1.1 0.4 ND 0.1 0.1 ND <0.02
Br
mg/L <0.1 <0.1 ND <0.1 <0.1 ND <0.1
NHþ 4 mg=L 0.4 0.4 ND 0.2 0.2 ND 1.1
Ca mg/L 83 47 43 240 77 132 510
Mg mg/L 65 33 47 285 71 152 561
Na mg/L 28 23 27 45 34 61 42
K mg/L 3.4 3 4.3 3.5 2.5 4.5 7.7
Fe mg/L 4.7 0.8 0.9 172 48.9 36.0 10.5
Mn mg/L 1.3 0.7 0.2 21.0 5.5 5.9 96.75
Li mg/L 0.06 0.04 0.05 0.12 0.07 0.11 0.89
U lg/L 272 1160 312 49 30 48 102250
As lg/L 7.9 12 5 18.7 2.5 6 ND
Sr lg/L 310 225 252 1466 443 557 2.02
Ni lg/L 53 77 31 843 144 139 7850
Zn lg/L 1013 179 24 8700 366 127 ND
Fe2+ (lg/L) 4667 236 740 171000 47300 35233 4075
Fe3+ (lg/L) 0 532 146 1500 1600 700 5975
Fe2+/Fe3+ 1 0.44 5.07 114 29.6 50.3 0.68
EC (uS/cm) lab 887 584 570 2757 1020 1463 ND
pH lab. 7.67 7.2 7.2 5.8 6.4 6.1 2.9
DOC mg C/L 29.6 30.5 50.7 5.1 6.7 28.2 1.4
234
U/238U AR ND ND 2.80 ND ND 1.97 ND
3
H (T.U.) (r)1 2.64 (.34) 2.10 (.50) 1.79 (.65) 4.80 (.50) 2.79 (.53) 1.56 (.61) 5.11 (3.12)
ND: non-determined. (r)1: 3 samples.
Hydrochemistry of water from Hole H-01 is also included for comparison.

tion of fracture-infill carbonates. Finally, the similar
behaviour of As and U is surprising since they have no
relationship with the evolutionary trend of the physico-
chemical variables of the groundwaters. This is particu-
larly relevant for U, whose concentrations are extremely
high in relation to the pH and Eh values of ground-
waters, especially in those from SM-2 that were sampled
in 2001. Thus, under the alkaline and reducing condi-
tions measured in the SM-2 groundwaters, all the U the-
oretically should have precipitated as U(IV), either as
oxide or silicate as a function of the SiO2 activity. How-
ever, several reasons can justify the high amount of dis-
solved U in these groundwaters:
(i) The slow reaction kinetic to transform U(VI) into
U(IV), which is the expected species in these
groundwaters (Langmuir, 1997).
(ii) The role-played by the HCO
3 ion as a complexing
agent for U(VI) that would increase the stability
and solubility of the U (VI) even under reducing
conditions. In this sense, Andersson (1987) sug-
gested that the dominant species in solution is the
uranyl ion ðUO2þ2 Þ, even under high reducing con-
ditions. Cotton and Wilkinson (1988) state that the
uranyl-carbonate complexes are particularly stable
and difficult to reduce under alkaline conditions,
since this reducing reaction is pH-dependent
(Langmuir, 1997).
(iii) The presence of U(IV)–organic matter complexes
that would increase the solubility of U(IV). In this
sense, the high amount of DOC determined in
these groundwaters is remarkable, particularly in
borehole SM-2, as well as its large increase
observed in the last sampling campaign (see Table
1).
(iv) The existence of small U(IV)-enriched colloidal
particles with sizes lower than 0.45 lm that were
eventually incorporated in the filtered water sam-
ples and then dissolved and analysed.
In order to investigate the fourth reason, groundwa-
ters from the last sampling campaign were also filtered
at 0.22 lm. Then, the chemical results from 0.45 to
0.22-lm filtered waters were compared and both >0.45
lm sized particles and 0.45–0.22 lm colloids were stud-
ied by SEM + EDX. The chemical results (Table 2)
474 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485

show only minor differences between the two filtered
groundwaters. Thus, the most significant difference ob-
served in the SM-2 groundwaters concerns the total Fe
and Fe(II)/Fe(III) ratio that is 5 times higher for the
0.45-lm filtered water than for the 0.22-lm filtered
one. However, the high uncertainty observed in the Fe
(III) determinations suggests that the differences are
mainly due to Fe (II). This can be explained considering
the negative Eh values of these waters and the possible
existence of neoformed Fe-sulphide particles with sizes
ranging between 0.45 and 0.22 lm. The other two differ-
ences concern DOC and U contents, the first being
slightly higher in the 0.45-lm filtered water than in the
0.22-lm filtered one. This means that minor organic C
can be as colloidal particles, probably inherited from
the Boa fault carbonaceous clayey walls, the remaining
C being as DOC. Concerning U, the difference observed
is opposite to that expected, since the highest values cor-
respond to the 0.22-lm filtered waters. However, this
apparent contradiction can be due to the uncertainties
of the analytical method, since the largest difference be-
tween both average values is approximately 20 lg/L.
This difference is consistent if 3 times the uncertainty va-
lue (r = 6.8) is considered (3r = 20.4), since this value
indicates a 99.5% confidence of the analytical data.
The differences observed in groundwaters from bore-
hole SM-3 concern the same elements as in ground-
waters from borehole SM-2 plus Mn. Nevertheless, the
behaviour of Fe and U is the opposite to that already ex-
plained for the SM-2 groundwaters, in such a way that
the highest Fe and U values have been measured in
0.22-lm filtered and 0.45-lm filtered waters, respec-
tively. This is expected for U but not for Fe. Besides this,
the uncertainties observed in both Fe (II) and Fe (III)
make any interpretation of these results difficult. As ex-
pected, the Mn content in 0.45-lm filtered waters is
much higher than in 0.22-lm filtered waters, thus indi-
cating the presence of Mn-rich particles with sizes rang-
ing between 0.45 and 0.22 lm. Finally, the DOC content
follows the same trends as in waters from borehole
SM-2.
Summarising, groundwaters from the Boa fault show
an evolutionary trend towards stabilisation and equilib-
rium with the rock formation, though a more extended
control must be performed, in order to corroborate this
tendency. Furthermore, no significant differences can be

Table 2
Chemical features of Boa fault groundwaters (boreholes SM-2 and SM-3) filtered by 0.45 and 0.22 lm (2002 campaign)
Borehole/section SM-2-T2 (0.45 lm) SM-2-T2 (0.22 lm) SM-3-T1 (0.45 lm) SM-3-T1 (0.22 lm)
Third campaign (2002) X
r X
r X
r X
r
HCO

3 ðmg=LÞ 262 1.5 267 2.1 78.3 13.5 89 4.0


Cl (mg/L) 13 1.0 14 1.0 12 2.1 12 1.5
SO2

4 ðmg=LÞ 108. 0.6 100 1.2 935 103.8 860 21.2
SiO2 (mg/L) 30.3 0.1 29.7 0.2 13.4 0.3 13 0.1
Ca (mg/L) 43 1.7 45 4.7 132 13.9 140 2.3
Mg (mg/L) 47 0.6 44 0.6 152 21.9 123 2.6
Na (mg/L) 27 0.0 27 0.6 61 2.5 59 0.0
K (mg/L) 4.3 1.0 3.3 1.7 4.5 2.2 3.4 0.0
Total Fe (mg/L) 0.886 0.2 0.179 0.04 36 3.4 47.3 2.2
Mn (mg/L) 0.24 0.0 0.23 0.0 5.9 0.8 1.06 0.1
Li (mg/L) 0.05 0.0 0.05 0.0 0.11 0.0 0.11 0.0
U (lg/L) 312 3.0 332 6.8 48 4.0 38 1.5
As (lg/L) 5 0.2 9.7 7.2 6 2.1 6 0.3
Sr (lg/L) 252 56.7 232 89.5 557 72.0 538 8.5
Ni (lg/L) 31 3.2 25 2.6 139 33.5 119 3.5
Zn (lg/L) 24.3 16.3 25 12.1 127 3.8 116 14.6
Fe2+ (lg/L) 740 292.9 92 53.7 35233 3493.3 46633 1778.6
Fe3+ (lg/L) 146 124.6 87 94.8 700 264.6 667 665.8
Fe2+/Fe3+ 5.07 1.06 50.33 69.91
EC (lS/cm) Lab 570 552 1463 1400
EC (lS/cm) ‘‘in situ’’ 645 645 1500 1500
pH Lab 7.2 7.8 6.1 6.2
pH in situ 7.1 7.1 7.4 7.4
T (°C) 22 22 24 24
Eh (mV)
325
325
350
350
DOC (mgC/L) 50.7 5.3 43.5 3.1 28.2 2.3 19.6 2.3
 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485 475

established between 0.45 and 0.22-lm filtered waters
from the two boreholes studied, except for Fe, Mn and
DOC. The behaviour of 3H, that largely decreases to-
wards the last sampling campaign, particularly in bore-
hole SM-3 (see Table 1), indicates a minor influence of
the acid waters from Hole H-01 on the groundwaters
from the site. This corroborates the evolutionary trend
of these groundwaters towards stabilisation and equilib-
rium with the rock formation. Finally, the 234U/238U
activity ratio (AR) in groundwaters from the last sam-
pling campaign (SM-2: 2.80 and SM-3: 1.97) are higher
than unity, as in most oxidising waters of the world. This
is due to the preferential leaching of 234U from the U
minerals that is facilitated by the a-recoil processes.
4.1.3. Mineral equilibrium
As mentioned before, the groundwaters from the Boa
fault show an evolutionary trend towards equilibrium
with the rock formation, particularly those from bore-
hole SM-3. This fact is also observed in the saturation
indices of some minerals (Table 3), which have been cal-
culated by means of the EQ3/6 code, using the GEMB-
OCHS database (Johnson and Lundeen, 1994).
However, this tendency is not clear for groundwaters
from borehole SM-2, in which some variations are ob-
served as a function of the sampling campaign. Thus,
the saturation indices for the last campaign indicate that
these waters are practically in equilibrium with chalced-
ony, rhodochrosite and siderite, while they are oversatu-
rated with respect to calcite and coffinite. In contrast,
the tendency towards equilibrium is clearer in ground-
waters from SM-3, as confirmed by the evolutionary
trend of the saturation indices for chalcedony and calcite
and, to a lesser extent, for coffinite and siderite. These
minerals have been identified in the fracture fillings of
the system (Pérez del Villar et al., 2001, 2002a).
Minor differences are observed between the satura-
tion indices obtained for 0.45 and 0.22-lm filtered
groundwaters from both boreholes, except for rhodo-
chrosite in waters from borehole SM-3 that changes
from equilibrium to an undersaturated state.
4.2. Suspended particles and colloids
The results obtained from the study performed by
SEM + EDX on the 0.45 lm filters used in the 2001
campaign are summarised as follows:
Mineral particles in groundwaters from borehole
SM-2 were plagioclase, muscovite, quartz, K-feldspar,
chlorite and Ti oxides, sometimes coated by undeter-
mined and complex metallic sulphides. Furthermore,
Fe–Zn and Zn–Fe sulphides; aggregates of Fe-oxyhy-
droxides; complex compounds of Si, Fe, Zn, S, Cu with
minor Ca, Al, Mg; of S, Cu, Fe, Zn with minor Si; of Fe,
P, Si, Ca, Zn and Pb; of Fe, S, Si, Zn, Ca, U with minor
Mn and Cu; of S, Cu, Mn; of Si, Sn, Fe, Zu, Cu; as well
as particles of calcite and barite were also detected.
In groundwaters from borehole SM-3, chlorite is the
main inherited mineral, usually coated by S or sulphides,
and inherited particles of pyrite are also present. Aggre-
gates of Fe-oxyhydroxides with minor Zn, Mn and Cu,
barite and patches of Cu–Fe (Zn) sulphides were also
detected.
Besides the inherited minerals, the textural features of
the remaining compounds suggest that they were neo-
formed in groundwaters, as a result of the physicochem-
ical changes that affected them, after the restoration
works performed at the site. These complex compounds,
which are of great interest to this work, are responsible
for the decrease observed in the metal concentrations in
samples taken in 2001 with respect to those taken in
1999 (see Table 1).

Table 3
Evolution of the saturation indices of some minerals in waters from boreholes SM-2 and SM-3
Boreholes and campaigns: SM-2-T2 SM-2-T2 SM-2-T2 SM-2-T2 SM-3-T1 SM-3-T1 SM-3-T1 SM-3-T1
0.45 lm 0.45 lm 0.45 lm 0.22 lm 0.45 lm 0.45 lm 0.45 lm 0.22 lm
1999 2001 2002 2002 1999 2001 2002 2002
Minerals Saturation indexes
Albite –
0.753 0.507
0.080 1.358
0.029
0.136
0.184
Calcite
0.344 1.003 0.550 0.581
1.694
0.308
0.405
0.317
Chalcedony 0.438 0.007 0.281 0.278 0.419 0.275 0.168 0.155
Coffinite
7.473
0.221 0.769 0.793 2.607
0.697
0.616
0.727
Mn(OH)2(am)
6.453
3.544
5.144
5.182
6.905
4.472
5.203
5.938
Ni(OH)2
5.257
1.632
3.323
3.419
5.707
3.465
4.273
4.304
Rhodochrosite
0.276 0.787 0.063 0.034
0.911 0.402 0.100
0.580
Siderite 0.175 0.113
0.373
0.526
0.010
2.370 0.847 1.028
Smithsonite
1.075
0.329
1.557
1.529
1.843
1.405
2.178
2.157
U4O9
0.705 4.251 3.997 4.024 1.258 2.576 2.590 2.491
Zincite
2.418 0.154
1.950
1.932
3.002
1.467
2.669
2.703
476 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485
Filters used in the 2002 sampling campaign show sig-
nificant differences with respect to those described
above. Thus, extremely scarce inherited minerals have
been detected in 0.45 lm filters used for both boreholes.
Similarly, complex compounds of metallic transition ele-
ments are scarce with respect to the 2001 sampling cam-
paign, except for the large amount of amorphous Fe-
oxyhydroxides with minor S, Si, Mg, Al, Ca and Mn de-
tected in the 0.45 lm filter used in borehole SM-3.
In contrast, particles, aggregates and precipitates of
more or less complex K chlorides and sulphates, Ca car-
bonates and probable Fe carbonates, both forming idio-
morphic crystals, and probable elemental S have been
mainly detected in both 0.45 and 0.22 lm filters used
in borehole SM-2 (Fig. 6(a)–(d)). The textural features
of these salts suggest that they were mainly neoformed
during the filtering processes and/or filter drying.
Besides the Fe-oxyhydroxides detected in the 0.45 lm
filter used for borehole SM-3 sampling, large crystal
aggregates of Ca sulphates, probably gypsum, have been
observed in both 0.45 and 0.22 lm filters (Fig. 6(e)).
Their textural characteristics also suggest a neoforma-
tion process during filtering and/or filter drying. Fur-
thermore, a generalised precipitation of complex
compounds of S, Fe, Si, Mn and Ca was observed in
both 0.45 and 0.22 lm membrane filters (Fig. 6(f)).
In summary, all these complex compounds reflect the
chemical characteristics of groundwaters and they are
generally the results of the precipitation processes that
take place inside the filters, either during filtering or dur-
ing filter drying. Minor suspended particles have been
detected in the last sampling campaign, but without U.
This means that U in groundwaters is dissolved either
as U(VI), forming stable complexes with HCO
3 , or as
U(IV)–DOC stable complexes.
4.3. d13C as a tracer for the source of DOC in
groundwater
In spite of the intensive oxic disturbance due to the
mining activities in the site, the Eh value measured in
the SM-2 (T-2) groundwater, around
300 mV in the
first sampling campaign (July, 1999) (see Fig. 4(b)), indi-
cates the large redox buffer capacity of the system. How-
ever, applying the EQ3/6 code to the measured
concentrations of Fe (II) and Fe (III), an Eh value of
138 mV was obtained, indicating that other redox pairs
and even organic matter contribute to the Eh values
measured in this groundwater (Gómez et al., 2000; Pérez
del Villar et al., 2001, 2002a). In this sense, microbiologi-
cal mediation of SO2
4 reduction by organic matter may
decrease the redox potential of groundwaters be-
tween
200 and
400 mV (Stumm and Morgan, 1981),
which are values very similar to those measured in
SM-2 (T-2) (Gómez et al., 2000; Pérez del Villar et al.,
2001, 2002a).
The origin of DOC in these groundwaters was also
an open question (Pérez del Villar et al., 2002a), since
it could have originated in soil of the site, and/or be
the result of the microbiologically mediated oxidation
of the organic matter (OM) in the clayey walls of the
Boa fault, in accordance with the following general
reaction:
OM þ 2Hþ þ SO2

4 ! DOC þ H2 S þ CO2 ð2Þ
In this H+ and SO2
4 come from the oxidation of pyr-
ite, which is a very abundant sulphide in the site, and
DOC should be a mixture of humic, fulvic and hydro-
philic acids (Buckau et al., 2000).
In order to answer the aforementioned question, the
isotopic signatures of C from DOC have been measured
(Table 4) and compared with those obtained from all its
possible sources. (Tables 5–8).
The d13C values for DOC are in agreement with those
of organic matter and they are very similar to those of
the C3 plants that vary between
34& and
23&, the
most frequent values ranging between
30& and

25& (Deines, 1980). Only the SM-3-T1 (2) sample
from the second campaign (June 2001) shows a more
positive value (
21.9&) that those of the C3 plants.
Furthermore, when the d13C values of the solid sam-
ples (plants, soils and rocks) are compared among them-
selves and with the d13C values of DOC from the Boa
fault groundwaters, the following can be stated:
 The organic matter of the geological materials from
the site shows very negative and constant d13C values
that vary between
28.5& and
25.3& (Fig. 7),
except for the carbonaceous clays from the Graphitic
fault with a more positive d13C value (
21.7&).
These values agree with those of the current conti-
nental and marine plants and sediments, and with
those of organic matter from consolidated sediments
and metasediments (Craig, 1953; Deines, 1980; Schid-
lowski, 1993).
 The similarity between the isotopic signatures of the
organic matter from the carbonaceous slates and
from the black-clayey walls of the Boa fault supports
the contention that the organic matter of these fault
walls come from the country rocks by a concentra-
tion process related to the mechanical and hydrother-
mal processes affecting the fault zones.
 Something similar occurs with the isotopic signatures
of the organic matter from the soil horizons and the
parent rocks, suggesting that the organic matter of
the soil can be totally or partially inherited from
the parent rocks, particularly from the carbonaceous
slates.
 Finally, the origin of DOC is difficult to know due to
the similarity among the d13C values of the organic
matter from all the rock samples, current plants
 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485 477

Fig. 6. Backscattered electron images of particles and precipitates retained on 0.45 lm and 0.22 lm filters used in 2002 groundwater
sampling campaign of both SM-2 and SM-3 boreholes. (a) Mixture of subidiomorphic salts from SM-2 groundwaters precipitated on
0.45 lm filter. 1: Potassium chloride with minor S, Fe, Si, Mg. 2: Probable potassium sulphate, with minor Cl, Fe, Si, Mg. 3: fibre from
the pre-filter (SM-2). (b) Idiomorphic Ca carbonate (1) precipitated on 0.22 lm filter membrane (2) used (SM-2). (c) Probable Fe
carbonate with minor S, Cl, K and Si (1) mixed with a chemically complex compound of Cl, Fe, Si, K, Ca (2), both precipitated on 0.45
lm filter membrane (SM-2). (d) Probable elemental S (1) precipitated on 0.22 lm filter membrane (2) (SM-2). (e) Idiomorphic crystal of
Ca sulphate (1) and Fe-oxyhydroxides (2) precipitated on 0.45 lm fibre pre-filter (SM-3). (f) Chemically complex compounds of Cl and
Fe with minor S, Si, Mg, Al, Mn and Ca, precipitated on 0.45 lm membrane filter (SM-3).
478 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485

Table 4
d13C values of DOC from the Boa fault groundwater
Boreholes and samples June 1999 June 2001 June 2002
13 13
DOC* d C (PDB) (&) DOC* d C (PDB) (&) DOC* d13C (PDB) (&)
SM-2-T2 (1) 29.6 ND 30.5
27.6 50.7
25.0
SM-2-T2 (2)
27.2
26.6
SM-2-T2 (3)
26.3
26.6
SM-3-T1 (1) 5.1 ND 6.7
25.2 28.2
26.5
SM-3-T1 (2)
21.9
26.6
SM-3-T1 (3)
26.3
27.0
DOC*, (mgC/L) Average values of three samples. ND, non-determined.

Table 5
d13C values of the more abundant plants at the site in June 2001
Samples Family Specie d13C (PDB) (&)
Leaves Fagaceae Quercus Rotundifolia
28.3
Lichen ND ND
24.5
Plants Graminae Dactylis Glomerata Blade:
28.6
Leave:
26.9
Graminae Agrostis sp. A.Castellana Blade:
23.1
Leave:
29.1
Graminae Vulpia spp Blade:
27.6
Blade:
27.4
Plant mixture Graminae + Cariofoliaceas Vulpia spp + Minuartia pp
25.9
Plant Papilonaceas Retama. Sphaerocarpa Blade:
24.2
Leave:
27.5
ND: Non-determined.

Table 6
organic matter from the Boa fault carbonaceous clayey
d13C of organic matter from soil developed at the site, at 645
m.a.s.l
walls.
The isotopic signatures of DIC are very constant if
Samples d13C(PDB) (&) groundwaters from each borehole and campaign are
Dead leaves
28.7 separately considered. However, the average value of
Humus
27.5 DIC for borehole SM-2 (
11.3 ± 0.6&) is two units
A1 horizon
26.8 more negative than that for borehole SM-3
A2 horizon
25.7 (
9.1 ± 0.6&) in the first sampling campaign; and 4
Carbonaceous slates
25.3
units more negative in the second (
15.1 ± 0.5&
against
11.1 ± 0.5&). Furthermore, the d13C signatures
and DOC from the Boa fault groundwater (Fig. 8). show an evolutionary trend towards more negative val-
However, given that the soil in the site is poorly ues with time, but they have no relationship with the
developed, DOC could come mainly from the carbo- d13C values of the organic matter from the Boa fault car-
naceous clayey walls of the Boa fault, according to bonaceous-clayey walls, around
27& (see Fig. 7 and
reaction (2). In this way, both the redox potential Table 8).
of the Boa fault groundwater and the most probable The average d13C values of DIC from SM-2 water
source of DOC could be accounted for. samples in June 2001 (
11.3 ± 0.6&) and June 2002
(
15.1 ± 0.5&) are in agreement with the isotopic signa-
ture of a theoretical DIC (d13C between
15& and
4.4. d13C as a tracer for the source of DIC in groundwater
9&) derived from soil-CO2 (d13C between
24& and

18&) generated by the oxidation of the existing C3
The d13C values of DIC from groundwater samples plants, at 15 °C that is the approximate annual average
taken during the last two sampling campaigns (June. temperature in the site (Fig. 8). Nevertheless, the d13C
2001 and 2002) are listed in Tables 9 and 10 and are rep- average value of DIC from SM-3 groundwater samples
resented in Fig. 7, in relation to the d13C values of the in June 2001 (
9.1 ± 0.6&) is in the upper positive limit
 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485 479

Table 7
d13C values of the organic mater from the carbonaceous-clayey walls of the Boa and Graphitic faults (exploitation fronts)
Bulk samples d13C(PDB) (&) <2 lm fraction d13C(PDB) (&) Minerals d13C(PDB) (&)
636-FB-1
26.1 636-FB-1
26.6 630-FB-2 (Fe)a
25.7
636-FB-2
27.1 636-FB-2
27.0 630-FB-2 (Cl)b
26.8
636-FB-3
26.5 636-FB-3
26.9 618-FB-2 (Fe)
26.0
630-FB-1
27.0 630-FB-1
27.5 618-FB-2 (Cl)
26.3
630-FB-2
25.9 630-FB-2
26.9 606-FB-2 (Car)c
27.8
630-FB-3
26.3 630-FB-3
26.7 606-FB-2 (Cl)
28.0
624-FB-1
26.7 624-FB-1
26.4 606-FB-2 (OM)d
28.5
624-FB-2
26.2 624-FB-2
26.3 Carbonaceous clays from Graphitic fault
21.7
624-FB-3
26.7 624-FB-3
26.7
618-FB-1
27.8 618-FB-1
27.5
618-FB-2
26.2 618-FB-2
26.1
618-FB-3
26.3 618-FB-3
26.7
612-FB-1
27.9 612-FB-1 ND
612-FB-2
27.5 612-FB-2
28.0
612-FB-3
27.7 612-FB-3
27.5
606-FB-1
28.3 606-FB-1
28.0
606-FB-2
27.8 606-FB-2 ND
606-FB-3
28.3 606-FB-3
28.5
ND: non-determined.
a
Fe-oxyhydroxides.
b
Clays.
c
Carbonates.
d
Organic matter.

5. Summary and conclusions

Table 8
d13C values of the organic matter from the carbonaceous-clayey
walls intersected by boreholes SM-1, SM-2, SM-3 and SM-4
13
Samples d C(PDB) (&)
SM-1-23B (bulk sample)
27.2
SM-1-23B OM (organic matter)
27.4
SM-2-22A (bulk sample)
28.3
SM-2-22A OM (organic matter)
27.1
SM-3-29 (bulk sample)
26.6
SM-4-14 (bulk sample)
27.4
of the possible values for the theoretical soil-derived
DIC. As water from this borehole is a mixture of water
from the geological formation and the acid water (pH
2.9) from Hole H-01, neutralised by the main fracture
infilling carbonates (calcite. dolomite and ankerite), with
d13C values between
7.2& and
9.6& (Both et al.,
1994), the d13C values of DIC can be explained as a mix-
ture of more negative DIC from the present vegetation
in the site and more positive DIC from the dissolution
of fracture carbonates. The more negative values ob-
served in the DIC of both boreholes from the 2002-cam-
paign could be due to a greater contribution of the
soil-derived DIC (Figs. 9 and 10). This fact suggests that
the neutralisation process between acid water from Hole
H-01 and carbonates is progressively less important
after the restoration works in 2000.
 The evolutionary trend observed in the groundwater
from the Boa fault zone is mainly defined by an
increase of the alkalinity and a decrease of the redox
potential, and consequently by a significant decrease
of the electric conductivity, as a result of the precip-
itation of the dissolved ions. Generally, this evolution
is shown by a tendency towards HCO
3 waters,
though the tendency with respect to the alkaline ele-
ments is not clear.
 Though the [Fe] behaviour is quite uneven, its general
trend is to decrease, like Mn, Ni and Zn. In contrast,
the high U concentration observed in relation to the
pH and Eh conditions of the groundwaters is anom-
alous, since it should be almost totally precipitated.
However, the filtration assays performed in the last
sampling campaign suggest that U in these ground-
waters can occur either as soluble uranyl-carbonate
complexes or as soluble U(IV)–organic matter com-
plexes, because of the high amount of DOC in these
groundwaters. The presence of both types of com-
plexes is possible. Furthermore, these filtration assays
suggest that scarce Fe-rich, Mn-rich and organic mat-
ter small particles (0.22 < x < 0.45 lm) are in suspen-
sion in these groundwaters. This is supported by the
presence of chemically complex aggregates of S, Fe,
Si, Mn (Ca, Al and Mg) in the 0.22 lm filter used,
particularly in borehole SM-3. However, neither U-
480 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485

DIC-2001 OM-2001
14

12

Nº Samples
10

- 13

-1 5

-20

- 25

-27

-29
-30
-14

-16
-17
- 18
-1 9

- 21
- 22
-23
-24

-2 6

-2 8
-10
- 11
- 12
-8
-9
(a) δ13C ‰ (PDB)

DIC-2002
20

15 OM-2001
Nº Samples

10

- 29
-30
-28
-27
-1 6

-1 8

- 20

-24

-26
-10
- 11
-1 2
- 13
-14
-15

-17

-1 9

-21
-22
- 23

-2 5
-9
-8

(b) δ13C ‰ (PDB)

Fig. 7. Frequency diagram of the d13C values of the organic mater (OM) from the carbonaceous-clayey walls of the main faults of the
site. Frequency diagram of the d13C values of the Dissolved Inorganic Carbon (DIC) in groundwaters is also shown for comparison. (a)
2001 sampling campaign, (b) 2002 sampling campaign.

rich nor organic matter particles have been detected.
Carbonates and sulphates detected in the filters were
formed during the filtering processes and/or filter dry-
ing, thus reflecting the chemical composition of
groundwaters.
 Currently, these evolutionary trends, particularly in
the water of borehole SM-3, are directly related
to the restoration works performed in the site, for which
the mine tailing materials were used as both sealing
and buffer materials. In this way, the neutralisation
of acid water from Hole H-01 and the obstruction
of the connections between this Hole and borehole
SM-3 were achieved. As a result, SM-3 waters have
evolved from a 56/44 mix between groundwater from
the rock formation (water from SM-2) and water
from Hole H-01 (Gómez et al., 2000; Pérez del Villar
et al., 2001, 2002a) to a groundwater almost in equi-
librium with the rock formation and similar to that
from SM-2. This process would be similar to the
one that functioned in the U deposit since its forma-
tion, approximately 35 Ma ago, until its exploitation.
During this interval of time it was exposed to contin-
uous and intensive downward weathering processes,
the main chemical processes being the oxidation of
sulphides, mainly pyrite. As a result, SO2
4 -acid
groundwaters were produced with a large dissolution
capacity for light and heavy metals. The rock/water
interaction processes, mainly those involving carbon-
ate infill materials, progressively buffered groundwa-
ters in the deeper zones of the site, increasing their
alkalinity and precipitating those pH-dependent met-
als. These processes generated groundwaters like
those first sampled from borehole SM-2 and then
from SM-3.
 Concerning the redox potential, it is noticeable that
groundwaters in the site restore their reducing condi-
tions very fast and at a shallow level, regardless of
fracture density in the site. This seems to indicate that
the redox buffering capacity is mainly controlled
by the abundant organic matter in the clayey walls
of the Boa fault, in addition to the redox capacity
arising from the Fe(II), Mn(II) and U(IV) bearing
minerals. Although d13C signatures have been unable
to decipher the origin of DOC in groundwaters, the
poorly developed soil in the site and the high concen-
tration of DOC observed in groundwaters from
the last sampling campaign suggest that DOC
could mainly come from the carbonaceous clayey
walls of the Boa fault, according to: OM þ 2Hþ þ
SO2
4 ! DOC þ H2 S þ CO2 . Thus, both the negative
 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485 481

Fig. 8. The most probable sources of C in the ‘‘Mina D Hole 01’’ area. SURFACE PROCESSES: Only plants of the site, with d13C
values in the range of C3 plants (Deines, 1980), and the pre-industrial atmospheric CO2, with a d13C value of
6.5& (Friedli et al.,
1986) (at present
8&), have been considered. The soil-CO2 is about 4.5& heavier than the plant biomass (Cerling, 1984, 1991). The
isotopic difference between CO2 and dissolved inorganic carbon (DIC) depends on the pH and temperature. This value will be near 0&
at pH 5, but close to 9& at pH 8 (Romanek et al., 1992). For the calculation of the isotopic theoretical signature of DIC the authors
have considered equations described by Romanek et al. (1992) for temperatures of 0, 15 and 30 °C. Notice that the isotopic signature of
DIC in the Boa fault groundwaters is mainly in the range of the theoretical isotopic signature of soil CO2-derived DIC at 15 °C, which
can be approximately considered as the average temperature in the site. Dissolved organic C in the Boa fault groundwaters can either
come from the plants of the site or more probably from the partial oxidation of the organic matter present in the clayey walls of the
main faults, such as Boa fault. Furthermore, some DIC can be supplied by the oxidation of organic matter. DEEP PROCESSES:
Highly negative calcites (CH4-derived cements) and highly positive calcites (methanogenic cements) must be discounted, since the most
frequent values obtained for carbonates in the site, between
7.2& and
9.6&, as the most frequent values (Both et al., 1994), are far
from these fields. These isotopic values correspond to carbonates from the early and main crystallisation phase. On the other hand, the
values of current DIC range between
15.1& and
9.1&, which are approximately in the range of the theoretically calculated values.
Finally, a number of relevant isotope compositional fields from the specialised literature are also shown for comparison: 3 = range of
pedogenic calcites (Talma and Netterberg, 1983; Salomons and Mook, 1986); 4 = Carbonatites (Hoefs, 1980); 5 = mantle (Kyser,
1986); 6 = fracture calcite from the Stripa granite (Clauer et al., 1989; Fritz et al., 1989); 7 = carbonates from the El Berrocal fracture
infill materials (Reyes et al., 1998).

Eh values of the Boa fault groundwaters and the
most probable source of DOC would be accounted
for.
 Finally, the isotopic signatures of DIC suggest that
the main source of DIC in groundwater in equilib-
rium with the rock formation (SM-2 groundwater)
is the CO2 generated by the oxidation of the present
C3 plants in the soil zone. However, DIC in the SM-3
groundwaters is a mixture of DIC from the oxidation
of the present C3 plants and DIC from the dissolu-
tion of carbonate infill materials.
6. Implications for processes in a radwaste disposal
The characterisation of the groundwater geochemis-
try and the interpretation and understanding of the
hydrogeochemical evolution constitute an essential part
of the assessment of radionuclide migration in a natural
system that can be extrapolated, by analogy, to a deep
geological radwaste repository. Thus, migration/reten-
tion of natural radionuclides and other analogue ele-
ments are mainly controlled by chemical and
physicochemical processes, such as adsorption, desorp-
tion, dissolution/co-dissolution and precipitation/co-pre-
cipitation, which, in turn, are governed by the
physicochemical properties of groundwater, mainly Eh
and pH. Interaction processes between slightly acidic,
oxidised percolating rainwater and rock-forming miner-
als, particularly those from fracture fillings, mainly con-
trol these physicochemical variables in groundwaters.
The most relevant rainwater/rock interaction process
in the system studied is the continuous oxidation of the
sulphide-rich U deposits, as the mineralogy of its oxida-
tion cap and the hydrochemistry of the waters from
Hole H-01 have demonstrated (Gómez et al., 2000; Pérez
del Villar et al., 2002a). As a consequence, the oxidised
and leached upper part of this system is of no relevance
in assessing the repository system, since these interaction
processes originate the destabilisation of the main
primary minerals, such as sulphides, pitchblende and
482 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485

Table 9 Table 10
d13C values of DIC in samples from Boa fault groundwater d13C values of DIC in samples from Boa fault groundwater
(boreholes SM-2 and SM-3, campaign of June 2001) (boreholes SM-2 and SM-3, campaign of June 2002)
Samples d13C (PDB) Samples d13C (PDB) Samples d13C (PDB) (&) Samples d13C (PDB) (&)
(&) (&)
SM-2-T2 (1)
13.6 SM-3-T1 (1)
10.7
SM-2-T2 (1)
10.0 SM-3-T1 (1)
10.0 SM-2-T2 (2)
15.0 SM-3-T1 (2)
11.2
SM-2-T2 (2)
10.6 SM-3-T1 (2)
10.1 SM-2-T2 (3)
14.8 SM-3-T1 (3)
11.2
SM-2-T2 (3)
10.6 SM-3-T1 (3)
10.0 SM-2-T2 (4)
14.7 SM-3-T1 (4)
11.6
SM-2-T2 (4)
11.1 SM-3-T1 (4)
10.4 SM-2-T2 (5)
15.1 SM-3-T1 (5)
11.5
SM-2-T2 (5)
10.9 SM-3-T1 (5)
9.0 SM-2-T2 (6)
15.0 SM-3-T1 (6)
11.7
SM-2-T2 (6)
11.6 SM-3-T1 (6)
9.6 SM-2-T2 (7)
15.0 SM-3-T1 (7)
11.7
SM-2-T2 (7)
11.5 SM-3-T1 (7)
9.6 SM-2-T2 (8)
14.9 SM-3-T1 (8)
11.6
SM-2-T2 (8)
11.0 SM-3-T1 (8)
8.9 SM-2-T2 (9)
15.2 SM-3-T1 (9)
11.1
SM-2-T2 (9)
10.9 SM-3-T1 (9)
9.4 SM-2-T2 (10)
14.8 SM-3-T1 (10)
11.5
SM-2-T2 (10)
11.7 SM-3-T1 (10)
9.5 SM-2-T2 (11)
15.0 SM-3-T1 (11)
11.6
SM-2-T2 (11)
11.6 SM-3-T1 (11)
9.1 SM-2-T2 (12)
15.3 SM-3-T1 (12)
11.3
SM-2-T2 (12)
11.7 SM-3-T1 (12)
9.4 SM-2-T2 (13)
15.3 SM-3-T1 (13)
11.3
SM-2-T2 (13)
10.7 SM-3-T1 (13) ND SM-2-T2 (14)
15.0 SM-3-T1 (14)
10.3
SM-2-T2 (14)
11.8 SM-3-T1 (14)
9.2 SM-2-T2 (15)
13.8 SM-3-T1 (15)
11.4
SM-2-T2 (15)
11.0 SM-3-T1 (15)
9.0 SM-2-T2 (16)
15.3 SM-3-T1 (16)
11.2
SM-2-T2 (16)
10.6 SM-3-T1 (16)
9.1 SM-2-T2 (17)
15.1 SM-3-T1 (17)
11.2
SM-2-T2 (17)
10.2 SM-3-T1 (17)
8.6 SM-2-T2 (18)
15.4 SM-3-T1 (18)
11.1
SM-2-T2 (18)
11.5 SM-3-T1 (18)
8.1 SM-2-T2 (19)
15.1 SM-3-T1 (19)
10.8
SM-2-T2 (19)
12.1 SM-3-T1 (19)
8.7 SM-2-T2 (20)
15.1 SM-3-T1 (20)
10.8
SM-2-T2 (20) ND SM-3-T1 (20)
8.8 SM-2-T2 (21)
15.3 SM-3-T1 (21)
11.3
SM-2-T2 (21)
11.9 SM-3-T1 (21)
8.2 SM-2-T2 (22)
15.1 SM-3-T1 (22)
10.6
SM-2-T2 (22)
10.7 SM-3-T1 (22)
8.4 SM-2-T2 (23)
14.7 SM-3-T1 (23)
11.2
SM-2-T2 (23)
11.7 SM-3-T1 (23)
9.2 SM-2-T2 (24)
15.5 SM-3-T1 (24)
11.4
SM-2-T2 (24)
12.1 SM-3-T1 (24)
8.4 SM-2-T2 (25)
15.7 SM-3-T1 (25)
10.2
SM-2-T2 (25)
12.0 SM-3-T1 (25)
8.9 SM-2-T2 (26)
15.7 SM-3-T1 (26)
11.4
SM-2-T2 (26)
11.6 SM-3-T1 (26)
9.2 SM-2-T2 (27)
15.7 SM-3-T1 (27)
11.1
SM-2-T2 (27)
11.8 SM-3-T1 (27)
8.6 SM-2-T2 (28)
15.4 SM-3-T1 (28)
11.3
SM-2-T2 (28)
11.2 SM-3-T1 (28)
9.4 SM-2-T2 (29)
15.6 SM-3-T1 (29)
10.9
SM-2-T2 (29)
11.8 SM-3-T1 (29)
9.1 SM-2-T2 (30)
15.3 SM-3-T1 (30)
11.0
SM-2-T2 (30)
11.9 SM-3-T1 (30)
9.1
X
 r
15.1 ± 0.5 X
 r
11.1 ± 0.5
X
 r
11.3 ± 0.6 X
 r
9.1 ± 0.6
ND: non-determined.

carbonates, as well as the dissolution and transport of

natural nuclides and other trace analogue elements.
On the contrary, it is noticeable that groundwaters in
the system quickly become neutral to slightly alkaline,
which is a consequence of the restoration works, as
clearly demonstrated in borehole SM-3. Furthermore,
groundwaters also become reduced at a very shallow le-
vel of the system, regardless of the high degree of frac-
turing at the site and the mining activities, which have
largely disturbed its hydrogeological characteristics.
These drastic and fast changes in the physicochemical
characteristics of groundwaters, which are closely re-
lated to the mineralogy of fracture fillings, including
the presence of important amounts of organic matter,
Fig. 9. Graphical explanation of the influence of fracture infill
are of relevance in the assessment of the disposal behav- carbonates on DIC of SM-3 groundwaters (2001 sampling
iour, even for an extremely perturbed geological media. campaign). Only the most frequent carbonates, corresponding
Thus, these changes in the physicochemical features of to the early and main crystallisation phase, with d13C values
groundwaters determine a significant geochemical dis- between
7.2& and
9.6& (Both et al., 1994), have been
continuity that facilitates the retention, mainly by pre- considered.
 L. Pérez del Villar et al. / Applied Geochemistry 20 (2005) 465–485
Fig. 10. Graphical explanation of the influence of fracture infill
carbonates on DIC of SM-3 groundwaters (2002 sampling
campaign). Only the most frequent carbonates, corresponding
to the early and main crystallisation phase, with d13C values
between
7.2& and
9.6& (Both et al., 1994), have been
considered. Note how the isotopic signature of DIC from both
boreholes evolves towards more negative values.
cipitation, of natural nuclides and other trace analogue
elements and particularly the long-term stability of
pitchblende, which is an U(IV) oxide chemically analo-
gous to the main component of the spent nuclear fuel.
However, it is remarkable that even under reducing con-
ditions, high concentrations of dissolved U can be found
in anomalous organic matter-rich groundwater systems
as ‘‘Mina Fe’’, probably as U(IV)-organic complexes,
though the presence of U(VI) carbonate complexes can-
not be discounted.
The relevance of organic matter in restoring redox
conditions of groundwater in fractured rocks has been
already shown in the REX experiment at the Äspö
hard rock laboratory in Sweden (Banwart, 1995). Sim-
ilarly, the role of the abundant organic matter around
the fossil natural nuclear reactors at Oklo-Okelobondo
(Gabon) has also contributed to their stabilisation
(Gauthier-Lafaye et al., 2000). Consequently, these
natural examples, including the ‘‘Mina Fe’’ U deposit,
demonstrate the importance of the: ‘‘in situ’’ and
introduced organic matter in the post-operational evo-
lution of the redox conditions of a deep geological
disposal.
Acknowledgements
Financial support for this work has been provided by
ENRESA (Spain). We are grateful to the chemist team
of CIEMAT for the chemical analyses, Dr. M.T. Crespo
for 234U/238U AR determinations, Dr. M.A. Simón for
the 3H analyses and Dr. B. de la Cruz for the English
revision. The authors are also grateful to Dr. L. Ahonen,
Dr. D. Bottomley and another anonymous reviewer for
483
their useful comments and suggestions that improved
the manuscript.
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