Вы находитесь на странице: 1из 16

JOURNAL OF

Contaminant
Hydrology
ELSEVIER Journal of Contaminant Hydrology 26 (1997) 45 -60

Mineralogical and geochemical evidence of the


migration/retention processes of U and Th in
fracture fillings from the E1 Berrocal granitic site
(Spain)
L. P~rez del Villar a,*, M. Pelayo a, J.S. Cdzar a, B. de la Cruz a,
J. Pardillo a, E. Reyes h, E. Caballero b, A. Delgado u, R. Nufiez b,
M. Ivanovich c, S.E. Hasler c
a Centro de Investigaciones Energ~ticas, Medio Ambientales y Tecnoldgicas, Instituto de Medio Ambiente,
Geologla, Avda. Complutense 22, 28040 Madrid, Spain
b Centro Superior de Investigaciones Cient~cas, Estacidn Experimental del Zaidln, ProfesorAlbareda 1,
Granada, Spain
c AEA-Technology, Hatwell, Oxfordshire, OXII ORA, UK

Received 15 March 1996; accepted 15 August 1996

Abstract
The fracture fillings in the E1 Berrocal site are the result of several overlapping alteration
processes of the granite since the formation of the fractures. They are essentially composed of
quartz, feldspars, clay minerals, carbonates and minor pyrite and Fe oxyhydroxides. The U(IV)
oxides occur only in some samples, whereas uranyl phosphates and silicates, sometimes with Th
and REE, are present in almost all the samples. Adsorption a n d / o r coprecipitation of U onto Fe
oxyhydroxides were also observed. In relation to the granite, the fracture fillings are enriched in U
by a factor ranging between 60 and 2, and in Th by a factor of 3.
6 ]SO values in clay minerals, quartz and carbonates and 613C in the latter indicate that quartz,
illite and kaolinite were formed at a minimum temperature of 100 °C, the CO 2-, of edaphic
origin, was formed between 15 °C and at least 60 °C. Smectite and a second generation of
kaolinite were formed at ambient temperature. Just under half of the bulk samples of the fracture
fillings are in secular equilibrium with respect to U isotopes. The rest have at least one activity
ratio less or larger than unity.

* Corresponding author.

0169-7722/97/$17.00 © 1997 Elsevier Science B.V. All rights reserved.


PI1 S 0 1 6 9 - 7 7 2 2 ( 9 6 ) 0 0 0 5 7 - 5
46 L. P£rez del Villar et al./ Journal of Contaminant Hydrology 26 (1997) 45-60

The existence of uranyl minerals and the U-Th enrichment factors observed indicate retention
processes mainly by precipitation of both natural radionuclides. The different values of the
234U//238U activity ratio observed show that fixation or leaching of U may be currently in
progress at various locations in the fracture system. However, some samples in equilibrium for the
234U/238U pair are taking up 228Ra (22syh)from the waters, whereas samples with 234U/238U 4:1
generally function as a close system for the 228Ra(228Th)/232Th pair. This is consistent with the
extremely open character of the site studied. © 1997 Elsevier Science B.V.

Keywords: Fracture filling; Stable and radioactive isotopes; U, Th migration/retention; E1 Berrocal site;
Natural analogs

1. Introduction

The El Berrocal fracture fillings have been studied in order to broaden the under-
standing of the past and recent past migration/retention processes of natural radionu-
clides in a granitic environment. Other similar studies have been carried out mostly in
Sweden and Canada. In Spain, P&ez del Villar et al. (1993b) started these studies on
N 1 0 0 ° - l l 0 ° E fractures which affect the El Berrocal site, including the U-sulphide-
bearing quartz vein (UQV).
The E1 Berrocal site is located in a granitic pluton, which is in the central part of the
Central Iberian Zone (Julivert et al., 1972), close to the contact between the Tajo River
tertiary basin and the Sierra de Gredos. The E1 Berrocal granite hosts UQV, mined some
30 years ago (Arribas, 1965).
The dominant facies in the pluton is an alkali feldspar quartz-granite, with two micas,
muscovite being dominant which constitutes the reference granite. The most important
accessory minerals for the purposes of this work are: zircon, monazite, xenotime,
apatite, uraninite and thorite-auerlite. This facies is rich in SiO 2 (75.3%), A 1 2 0 3
(13.6%), P205 (0.29%), F (0.22%), Li (200 ppm), Rb (400-500 ppm), Zn (70-90 ppm)
and U (15-17 ppm) and poor in CaO (0.40-0.50%), MgO (0.20%), Ba (20-40 ppm), Sr
(5 ppm) and Th (7-8 ppm). The U / T h ratio ranges between 2.26 and 2.50, typical of
U-fertile granites (Prrez del Villar et al., 1994).
Four alteration events have been established in the site: (1) the pervasive deuteric
a n d / o r early post-magmatic process at a temperature range between 315 and 350 °C; (2)
the high-temperature hydrothermal process related to the main fractures (N80°-ll0°E)
in the granite at = 250 °C; (3) the low-temperature hydrothermal process between 60
and 100 °C, divided in two phases: formation of sulphide-bearing quartz veins, barren in
U and at 100 °C, and formation of the U mineralization at lower temperatures ( < 100
°C) and composed of pitchblende, carbonates, pyrite and barite; and (4) weathering,
which affects the UQV/granite system to different degrees (Prrez del Villar et al.,
1993a).
The fracture fillings studied in this work come from the deeper zones of the site, the
principal aims being (i) the determination of the role of these fracture fillings in the
migration/retention processes of the natural radionuclides and (ii) the interpretation of
these processes in terms of rock/water interaction.
L. P£rez del Villar et aL / Journal of Contaminant Hydrology 26 (1997) 45-60 47

2. Experimental

The samples studied come from the cores of boreholes (B) 13 to 17. Thus, the
sampling is representative of both high and low hydraulic conductivity fractures (Fig. 1).
Samples were usually scraped from both sides of the fracture or loosened when the
fracture fillings were thicker.
Given that most of the analytical methods used are known (Fig. 2), only the
methodology followed to determine stable and radioactive isotopes will be described.
The 6180 values in clays and quartz were determined using a MA-251 Finnigan mass
spectrometer, following the method of Borthwick and Harmon (1982), later modified by
Vennemann and Smith (1990). 8180 and 813C in carbonates were determined using the
same mass spectrometer, following the method of McCrea (1950).
The 6180 average value (-7.4%o) of the current meteoric water at the E1 Berrocal
site, and the equations

10001n a = 3.38(106T - 2 ) - 3.40 (1)


for quartz (Clayton et al., 1972);

10001n a = 2.43(106T - 2 ) - 4.8 (2)


for illite (Eslinger and Savin, 1973);

10001n a -- 2.6(106T -2 ) - 4.28 (3)


for smectite (Savin and Lee, 1988);

10001n a = 2.5(106T - z ) - 2.9 (4)


for kaolinite and palygorskite (Land and Dutton, 1978); and

T°C = 1 6 - 4 . 1 4 ( 8 c - 6 w ) + 0.13(6 c - 6 w ) 2 (5)


for calcite (Anderson and Arthur, 1983) have been used in the geothermometric study.
However, the main problem in determining the temperature of formation of the different
clay minerals was that all the samples analyzed were mixtures of clay minerals. This
problem was solved in two ways. Firstly, the theoretical 6180 value of smectite was
calculated from the 8180 values determined on several illite-smectite mixtures taking
into account the regression between 6180 values and the illite/smectite ratio. Thus, the
theoretical 6~So value for smectite is 17.4%o and the 6180 values for illite range
between 5.7 and 8.6%o. Secondly, the 6180 values of the clay minerals were determined
by considering the isotopic values of the clay mixtures, the semiquantitative mineralogi-
cal composition of the mixtures and the molar percentages of oxygen of each clay phase.
According to this method, the 6180 value for smectite is 17.9%o and for illite it ranges
from 4.7 to 8.6%o. Thus, the data calculated were in agreement and both methods were
validated.
The U and Th isotopes were determined by isotope dilution/alpha spectrometry. The
U content of the bulk samples was initially monitored by gamma spectrometry using a
gamma well-type detector. Powdered samples were then subjected to acid digestion by a
48 L. P~rez del Villar et a l . / Journal of Contaminant Hydrology 26 (1997) 45-60

COs - Fe=O a
H~O ~ SO;, ÷ C ~ p t f =6-7 F n g ~ re lrdtlbll~d
N
AL'IT~jDE
J
|4 B16
.o,so: c,-p. ~ ~Bt3-,~-~.-:I

ili
9O0 s ~,.~,.~, ;.',
4: f

"2.~t
~,~.~
B1 1
8OO
•:.......
:..'-%i-,,.;*.~c.:.;~::.i,.~.~
........ ~:~:i.:..
, ! ,:, "~ ~.~:i:.%:~.-:!~:.~.....
. .. :~.:::~/. ..! i. ~)~::i]::ii!::.!!ii~i:~",.:~;g.~,.~.".'.9;~i?~,~L.~.:.

\ t :>.,:

7OO ? ~.
\ \
\
LEGEND
\ \
R~ee grm~lte \ ~,

(toO

~ltlde-beerll~ Q dyke 7 \ : 5,::! ~ :i


\ \ ,!: ii.;~I
Clayey malerlals ~ ~ i?:. ":-:;,:~ :

SO0

\ ~'.

4OO

Fig. 1. Cross section of the E1 Berrocal site and location of boreholes and sampling points.
L. Pgrez del Villar et aL / Journal of Contaminant Hydrology 26 (1997) 45-60 49

MAJOR&TRACE SP]gCYROMETRY
[ELEMENTSBYICP-AES+
XRF+AAS+FAES

X OA+TREAT[~EMEN~

[ ~SS sezc'rno~,~-rav I
Fig. 2. Flow-chart of the methodology followed to study the fracture filling samples.

succession of HF/perchloric acid additions and dryings with final dissolution in HNO 3.
The radiochemical separation and counting were performed by ion-exchange column
separation and purification, electrodeposition for alpha counting, data reduction and
spectral analysis.

3. Results

3.1. Essential minerals

In almost all the samples, the essential minerals are: quartz, K-feldspar (KFd), albite,
phyllosilicates and carbonates, the two last mineral groups being the most important for
the objectives of this work.
Phyllosilicates are fundamentally muscovite-sericite, illite, smectite, kaolinite, and
minor palygorskite and chlorite, the latter being inherited from the granite. Muscovite is
also inherited from the granite and, in some cases, is transformed into illite or smectite,
Fig. 3(1). The beidellitic-type smectite presents a webby pore-lining morphology, and is
mainly formed by alteration of albite, Fig. 3(2). Kaolinite is idiomorphic, with a
50 L. P~rez del Villar et a l . / Journal of Contaminant Hydrology 26 (1997) 45-60

face-to-face stack-type texture, Fig. 3(3), and palygorskite is very scarce and presents
the typical fibrous habit.
The most abundant carbonate is Mn-rich calcite, being the Ca-Mn-carbonate series

9 ¸

, L ~ ,1~

~i,~i~!~ ,i!i~?~,~~!i~:
L. P~rez del Villar et al. / Journal of Contaminant Hydrology 26 (1997) 45-60 51

present in the samples. In some samples calcite and dolomite coexist and in the most
superficial zones of the site, F e - M n oxyhydroxides are formed by the dissolution of
carbonates.

3.2. Accessory minerals

These minerals are numerous and sometimes have a complex chemical composition.
A m o n g these minerals a n d / o r mineraloids, only those containing rare earth elements
(REE), Th and U will be described. The REE are generally held in apatite, monazite and
xenotime inherited from the granite and, in some cases, these elements form secondary
parisite or are associated with uranyl phosphate and Th or uranyl silicates.
Uranium and Th minerals, either inherited or newly formed, are frequent in all the
samples. Among the inherited minerals, uranium oxides, similar to uraninite, are present
in zones with weakly reducing waters. Likewise, U - T h oxides, similar to thorianite, and
Th silicates, similar to thorite, were identified in the deepest zone of the site. Other
U - T h - p o o r inherited minerals (zircon, monazite and xenotime), with different degrees
of alteration, were also identified quite frequently. The newly formed U(IV) oxide
(pitchblende or sooty pitchblende) was detected in the weakly reduced zone of all the
boreholes. This oxide usually forms patches of colloidal particles on clayey and
carbonate substrates, Fig. 3(4). The newly formed uranyl minerals were found in all the
boreholes and depths. Among them, the uranyl silicate (uranotile) is worth mentioning,
Fig. 3(5). The U-Ca-phosphates (autunite and phosphuranylite) are frequent in the most
superficial zones of the site, precipitating on Mn oxyhydroxides, Fig. 3(6), or forming
crusts on the clayey materials. The U - C u phosphate (torbernite), U - B a phosphate
(uranocircite) and U - F e phosphate (bassetite) were only detected i n / a n d near the UQV.
Other U - T h - R E E minerals or mineraloids, with complex chemical composition and
ill-defined morphology, are very frequent, and they always appear on the clayey or
carbonate substrate of the samples. These minerals or mineraloids have been classified
as U silicophosphates, Th silicophosphates, U - T h silicophosphates, U - R E E silicophos-
phates and U - T h - R E E silicophosphates, with minor Ca, Cu, Fe and Mg. Finally, U is
less frequently found adsorbed onto Fe oxyhydroxides from the oxidation of pyrite, Fig.
3(7), and onto palygorskite, also coated by Fe oxyhydroxides, Fig. 3(8).

3.3. M a j o r elements

Only twenty bulk samples ( x < 60 Ixm) have been analyzed corresponding to
hydraulically active and inactive fracture zones. Samples rich in carbonates and in
clayey fraction, as well as with intermediate compositions, are represented in Table 1.

Fig. 3. (1) Huge plate of muscovite (1) being transformed into illite (2). (2) Albite being gradually transformed
into smectite: the chemical composition in 1, 2, 3, 4, 5 and 6 shows this gradual transformation. (3) First
generation of kaolinite (1) with typical face-to-face stacked-type texture. (4) Patch of pitchblende or sooty
pitchblende (1) on the substratum of the fracture filling. (5) Uranotile (1) aggregate precipitated on a calcitic
substratum. (6) Autunite plates embedded in a Mn oxyhydroxide matrix. (7) Idiomorphic octahedric pyrites,
some of them altered to Fe oxyhydroxides, with U adsorbed. (8) Probable palygorskite coated by Fe
oxyhydroxides with some U adsorbed. (1), (2), (3) and (8) are secondary electron images; (4), (5), (6) and (7)
are backscattered electron images.
Table 1
Chemical composition of the x < 60 b~m fraction. Major elements and oxidation degree (Ox °)

B-16 B-17

DEPTH(m, 49.0 I-~,0~~ ~~.~ ~ iiI:i


~ ..~ ~ ~ iI.~:~..:~I279.6 13.... ] ,,99 j °°2., ,~ili!i
58.8 iii~iiiii~i~i!i!ii:i!i
,iii:iiiii~i~ii:i:i:iiiliiiiii~ii~iii:iliii~iii~i~ii~iiii!iiii ,,.o o,.9
~i 5.1 lS, 22.5 11.3 ,,.0 ~.,
........................ 2 : :::::!::!:; ................

1.40
e~
0.60
g~
.,--,
0.99 L~ 0.72 "x.
Mg0 7.8 : i:¢ 2. . . . . 1.6 ,, o,
M.O ;i o.17 o.o7 0.34
..............::x:::
6.3
0.25 .... o.,2 ~)~i~i:.:::::i
3.7 . 5.2
T,O, ....... ,0.02 .................................................. o . , 02, 0.12 o.oo °.,
,,,o, .... i!i ~i~i~ .... 0,9 0.54 o. . . . . . .
2.22
: ? 2 : : :::::
2.03

IL37
CO,=, {{{:{i~i~'ia{::
i{{:.:~i:~:::::" i i g { 2,.6 ~i~.~i iii~:i~i:::{{{ i{{i:!{i{~!{iii{!!i
:{~:{{~:{:{:~i:i::{g~{:{i:.:{i:: 1.32 0.07 5.~0 b~
0.20

N,D

N.D 4~
94.59 I

ox. I}!i{:,~!i~{i{iili{i{:;~a{{{lF{{{{{{~iii{{{{{:tl
o.,, o,o I o.,, 0.45

HYDRAULICALLYACTWE ZONES (WATER SAMPLING) N.D = NOT DETERMINED


Table 2
Chemical composition of the < 60 txm fraction. Trace elements

BOREIIOLE II ..,3 II B_,, I ~-. .-,, ,11 ..,7


DEPTH (m) ¢u

Li (ppm) !i!:~iii:i~ii:::::iii':.:~!.iii iiiii!:ii~ii~:ii: 55 i i~ i:'ii::ii~ii :i iiiii~iiiii.iil ii:iii::i:'i~:ii !: 165 585 37 "'iiii!iiiili~ij:i::iiiiiiii'iiii~iiiii

,~o ii!i~.i~i~:/):i ::,~:.::: <s.o i::i:.:.~i~'~': i~:.::~!~ii!iii:;~::i~:.:.:.:: ,.~

~ i:~ :.~ ~. .......................


~.0. : : ~ : : :
........................... .
v ...........................................................................

~, :,:::~i~i ::~i~:,i:,i ~, '::i:~ 'ii~:~ii :~ ...........................................................


~i~:~... ~.o

.............................. • ...:.::.:~:,k :':::::: : '2: ................. •

Y ::ii:[!ii~::::iii:i
:. iii~.i:~i~iiiiii ii~:~:!;::ii~ii~:.:~i: 9.1 ~ ::: ~z~:!:~ii::.iii~:ii~i~i~:ii! i:i~i::ii!~i~:ii::i:::ii:.:
i~ii:i!!::~i:~i:: :~i::: !:iI 27

, '~:iiii:~i:~i~:':i'.iii~iiii::::::!i~i
iiii~::~ii:.'i ~ iii:i::~::?.~:. ii,,iiii~iiiiii~i~:i:~ii":'~:~!i:.i ~, 4~
- ,.~ ~,i~i::~i!!~.'~!.J~:i':':',!!~::
:: :::.i;i!::~i~ii ii~:~!~::~'~i~i':ii:.i ,.~ - iiii!iii~iii!iiiiiii!!iii.~ I
~, ::ii::ii~i::i ::i~:i::::i~'::~::i ,~o ===================================================
::::::::;:::::::: :~~:~:~:~:~~:~~::~~:~:~:::::::::::::::::::::::::::

HYDRAULICALLY ACTIVE ZONE,S (WATER SAMPLING) N,]),= NOT DETERMINED


54 L. P~rez del Villar et al. / Journal of Contaminant Hydrology 26 (1997) 45-60

The degree of oxidation ( O x ° = Fe203/Fe203 + FeO + MnO) of the samples varies


between 0.19 and 0.92, and no correlation between this parameter and depth can be
established. This fact is explained by considering the physico-chemical characteristics of
the circulating waters along the fractures, which will depend, on one side, on the degree
of connection between the fractures and the surface and, on the other, on the water flow
rate through the fractures. This explanation is consistent with the extremely open system
studied.
In most of the fracture fillings, the content of N a 2 0 indicates their degree of
alteration, because albite is the mineral most easily transformed into clays.
The content of P205 in some samples is higher than in the reference granite.
According to the mineralogy of the fracture fillings, most of this P205 is accounted for
by the phosphate minerals inherited from the granite and, in smaller proportion, the
newly formed UO~ +, UO2+-REE phosphates and U O 2 + - R E E - T h silicophosphates.
The P205 of the latter was supplied by the dissolution of the inherited phosphates,
mainly apatite.
The high concentration of organic CO 2 is, in general, remarkable in all the samples,
reaching values up to 0.76% of the bulk sample. This fact can be explained by the
presence of microorganisms within the fracture fillings a n d / o r by the existence of
organic-clay complexes. The humic and fulvic acids would come from the surface of the
site and would be transported along the fractures by the meteoric waters to a depth of
approximately 600 m.

3.4. Trace elements

Table 2 shows a comparison with those trace elements determined in the reference
granite. However, only the REE, Th and U will be discussed in this work. The average
concentrations of Y, Ce and La in the reference granite are 6, 19 and 8 ppm respectively,
and are mainly controlled by refractory minerals such as xenotime and monazite. The
contents of these elements vary greatly in the fracture fillings, in such a way that Y
ranges between < 5 and 53 ppm, Ce between < 5 and 47 ppm and La between < 5 and
42 ppm. Consequently, there has been a concentration of these three elements with
respect to the reference granite, at least in some samples. Though this phenomenon was
mainly produced by a mechanism of the residual concentration of monazite and
xenotime, newly formed parisite, complex REE phosphates and T h - U - R E E silicophos-
phates were also detected. These last minerals indicate that Y, Ce and La from xenotime
and monazite were partially mobilized by the alteration processes affecting the reference
granite and were concentrated in the fracture fillings.
The U and Th contents of the reference granite are mainly controlled by uraninite,
thorite-auerlite and, to a smaller extent, monazite. The U content in most of the samples
is higher or significantly higher than in the reference granite, whereas Th is higher,
similar or significantly lower. This fact suggests that U was generally concentrated in
the fracture fillings, while Th could have been concentrated or leached depending on the
sample.
In order to understand the observed U concentrations, it is necessary to consider the
nature of the U minerals present. Thus, the presence of both primary (uraninite and
L. P£rez del Villar et al. / Journal of Contaminant Hydrology 26 (1997) 45-60 55

pitchblende) and secondary U minerals suggests that the latter were formed by oxidation
and dissolution of the former and that the U(VI) was concentrated by precipitation under
supergenic oxidizing conditions as silicates, phosphates and silicophosphates. Coprecipi-
tation a n d / o r adsorption of U onto Fe oxyhydroxides have also been detected.
The Th minerals can account for the Th contents of the samples; most of them are
inherited from the granite and preserved, due to their high stability, from hot and cold
waters that have circulated and are currently circulating along the fractures. However,
the presence of Th, U - T h and U - T h - R E E silicophosphates, together with the fact that
the content of Th in some samples is three times that of the reference granite, suggests
that this element was also partially mobilized and concentrated in the fracture fillings.
The low or null mobility of Th at ambient temperature, however, implies that these
processes took place under hydrothermal conditions.
In short, the concentration of U and Th in the fracture fillings seems to be the result
of different remobilization and precipitation processes throughout the geological history
of the fractures.

3.5. E n v i r o n m e n t a l isotopes

Using the 6180 values of the clay minerals (Table 3a), considering that these clay
minerals were formed in equilibrium with the current meteoric water at the E1 Berrocal
site, with an annual average 6180 value of -7.4%o, and applying Eqs. (2)-(4), the
formation temperatures of these minerals are between 68 and 104 °C for illite; between
100 and 124 °C for the first generation of kaolinite; 18 °C for the second generation of
kaolinite; between 16 and 30 °C for smectite, and 39 °C for palygorskite (Fig. 4).
The 6180 values determined in quartz from the UQV range between 12.7%o and
15.4%o, for the six samples analyzed. According to Eq. (1), the temperature of formation
of this quartz varies between 85 and 106 °C (Fig. 4).
The 613C and 6180 values in carbonates were determined in 123 samples from
boreholes B-13 to 17, and the results obtained, summarized in Table 3b, show that both
613C and 3180 values are very variable, and that the influence of edaphic CO 2 in the
formation of carbonates is generally greater than the atmospheric CO 2. This suggests
that the CO 2 of these carbonates comes mainly from the plant cover of the site,
essentially constituted by C3-type plants, with a 613C value of -26%o.
The geothermometric study of these carbonates was carried out based on the
aforementioned 6180 values, on Eq. (5) and on the annual average 6180 value of the
current meteoric water at the site. The results obtained demonstrate that most of these
minerals (80%) were formed at a temperature range between 25 and at least 65 °C, while
the remaining 20% was formed at ambient temperature. This suggests that these
carbonates are mixtures, in different proportions, of those formed at ambient conditions
and others formed at temperatures higher than those calculated. Consequently, at least
two overlapping generations of carbonates exist in the system.
Based on the temperature of formation of the main minerals, the fracture fillings are
the result of the overlapping of several hydrothermal and weathering processes on the
granitic gouge faults originated during the fracturing processes that affect the E1
Berrocal granite. After the fracturing of the granite, quartz, illite and the first generation
56 L. Pdrez del Villar et al. / Journal of Contaminant Hydrology 26 (1997) 45-60

Table 3

(a) ~lSO ESTIMATED VALUES FOR PURE CLAY MINERALS I


6~sO~ I L L I T E ~180°~¢~oKAOLINITE 6~sO%oSMECTITE b~aO%oPALYGORSKITE

8.2 5.9 17.5 15.2

7.1 5.4 16.5

6.2 7.5 17.8

4.7 19.1 17.9

5,9 18.0

5.2 18.1

6.3 18.0

5.7 19.3

8.6

(b) ~PsO AND 6~3C VALUES OF CARBONATES FROM FRACTURE


FILLINGS

BOREHOLES B-13 B-14 B-15 B-16 B-17

N ° SAMPLES 21 10 16 54 22

~3C average -11.2 -13.0 -11.4 -13,2 -12,8

~5x3C max. -6.6 -10.9 -8.3 -8.4 -11.4

~5~3C min. -13.1 -15.3 -13.0 -16.4 -13.9

~'*O average -12.8 -10.4 -10.7 -11.5 -10,5

~SO max. -9.4 -7,5 -8.2 -7,5 8.2

61So rain. -15.8 -13.6 -14.7 -15.6 -12,5

of kaolinite were formed at approximately 100 °C. Later, after the fracturing of quartz
veins, the formation of the U orebody in the main Q vein, composed of pitchblende,
pyrite (melnikovite), barite and ankeritic carbonates, took place at < 100 °C. During the
ancient, recent past and current weathering processes, oxidation of sulfides and pitch-
blende, dissolution of the first generation of carbonates and apatite, and new formation
of Fe oxyhydroxides, jarosite and a second generation of kaolinite took place under acid
conditions in the UQV. In these conditions, U(VI) migrated downward in the vein until
neutralization of the solutions was reached, precipitating uranyl phosphates and forming
smectite from illite and feldspars. In weakly alkaline environments, outside the UQV,
smectite, a second generation of Mn-rich carbonates and uranyl silicates and phosphates
were formed. Occasionally, in an even more alkaline environment in the system,
palygorskite was also formed.
L. P£rez del Villar et al./ Journal of Contaminant Hydrology 26 (1997) 45-60 57

30 250

o•.
uJ
200

150

100
&.
0 Z;
~_ 50

-10, o
i i
0
i
o
+
0 8
i
o
i i
0
i
0
_
o 8
, i
o 0
i i
0
i
o ~
I
3 4 5 6 7 8 9 10
TEMPERATURE(°C) K A O L I N I T E ~'BO
60 1 oo

G" 8o
~ +° -7
~ 6o
I---
~ +°
~ 20 n
lO ~9.~ ~ ~ ~ 2o

0 ~ ~ ' ~ o
15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5 21 lO 12 14 16 18 20 22 24
KAOLINITE ~1~0 SMECTITE ~180
120
300

~..10{3 ~.. 250

200

,~ 150

40 ~. 100

20 50

i , J 0
0 11 12 13 14 15 16 17 18 19 20 8 9 10 11 12 1 3 14 15 16 17 18 19

PALYGORSKITE ~180 QUARTZ ~180


Fig. 4. 6 £80-temperatureplots for the different clay minerals and quartzpresent in the fracture fillings from
the El Berrocal site.

3.6. U and Th series disequilibrium

Thirteen bulk samples from different locations in the fracture system have been
analyzed for U and Th series disequilibrium. The results obtained (Table 4) also show
that all the samples have U concentrations higher than the reference granite, while the
Th concentration is more variable, but generally higher too.
At least two types of fracture infill material may be recognised from the listed
isotopic data in Table 4. The first group (B-1-48.52, B-7-45.45, B-14-35.95 and
B-15-110.0) has all three activity ratios equal to unity. The second group of samples has
at least one activity ratio different from unity by at least 2 and 3 standard deviations
quoted. In this group, the samples can be further distinguished in terms of recent U and
Ra gain or loss. Thus, with respect to U, six samples (B-13-53.80, B-13-67.92,
58 L. P£rez del Villar et al. / Journal of Contaminant Hydrology 26 (1997) 4 5 - 6 0

Table 4
U and Th contentsand isotopic activity ratios of some samples of the infill materials

BOREHOLE DEPTH [U] ~U/z3SU 231~Ph/2~qLI


[Thl l zZS'Fhl~ZTh MINERALOGY
(m) (ppm) {ppm)
1 48,52 105 1 38+0 03 0 96±006 1149 0.86±0 16 Not determined
7 4545 114 0.88±0.02 1021006 137 116±0.16 Not determined
13 4 3 14 70 0.86A(1 01 1 2 2 ± 0 05 bib 124±0.20 Not determined
13 5380 327 I 67±0.01 086±003 1235 0 92±007 18% T.Phy. 67%carbonates
13 67.97 409 10 0 ± 0 01 0.71 + 0 0 3 212 184±0.08 71% T.Phy No carbonates
14 3508 90 0.94+002 1 14±0,05 9 75 1.41±015 44% T.Phy No carbonates
14 35 63 289 098+_002 0 74±003 15 13 264±053 61% T.Phy No carbonates
14 3595 1446 0.99±0.02 1 07±0 05 1283 1 0 8 ! 0 16 Not deletTnined
14 21620 404 61 I 32±0.02 088__+006 968 0 95 ± 0 2 0 46% T.Phy. No carbonates
14 216.24 20905 1 14±003 0.92+0 08 716 0 60±0.34 33% TPhy. No carbonates
14 21634 15420 1.20±0.03 086±006 529 1 17±0.42 36% T,Phy No carbonates
15 1100 46.5 1.09±0.01 10 4 ± 0 , 0 4 I6.3 10 1 ± 0 0 5 67% TPby. No carbonates
15 110.66 50.9 1.53 ±0.01 1.00±0 04 8.8 129=[_0.09 25% T.Phy. 9%carbonates

T Phy.: Total Phyllosilicates

B-14-35.63, B-14-216.20, B-14-216.34 and B-15-110.66) have 234U/238U activity


ratios (AR) greater than unity, which is interpreted as a recent U gain from fracture
waters (Osmond and Ivanovich, 1992). Another two samples (B-13-43.14 and B - 1 4 -
35.08) h a v e 234U/238U AR less than unity and the corresponding 23°Th/234U AR
greater than unity, which is considered as a recent U loss with preferential removal of
the more mobile 2 3 4 U isotope from the leached solid (Osmond and Ivanovich, 1992). In
contrast, eight samples in Table 4 have 228Th/232Th AR equal to unity indicating
secular equilibrium in the top part of the Th decay series and no apparent mobility of
228Ra, the intermediate radionuclide between the two Th isotopes in the decay chain.
From the remaining five samples, four have recently gained 228Ra ( < 20 years), and one
sample (B-14-216.24) has lost 228Ra (AR < 1). These results indicate no apparent
correlation between the observed disequilibrium and the mineralogical composition of
the samples. This observation is consistent with the extremely open character of the El
Berrocal site.

4. S u m m a r y and conclusions

1. The samples studied represent all the fracture families identified in the system, as
well as the hydraulically and non-hydraulically conductive fractures.
2. The mineralogical characteristics of the fracture fillings and the stable isotopic data
establish that these infill materials are the result of the overlapping of two low-tem-
perature hydrothermai alteration processes and the ancient, recent past and present-day
weathering processes on the granitic gouge faults.
L. Pdrez del Villar et al. / Journal of Contaminant Hydrology 26 (1997) 45-60 59

3. A m o n g the major elements, the content of Na in the samples represents the degree of
alteration reached by the fracture fillings, and the high organic CO 2 content indicates
either the presence of organic activity in the fracture fillings or the fixation in the
clay minerals of organic acids coming from the surface.
4. In relation to the reference granite, all the trace elements are concentrated in the
fracture fillings, Y, Ce, La, Th and U being particularly concentrated.
5. The detailed study of the mineralogy of the fracture fillings shows that these
elements, mainly U, are basically retained by precipitation and, in smaller propor-
tions, by co-precipitation or adsorption onto Fe oxyhydroxides.
6. The variability of U and Th series disequilibrium indicates that the infill materials
can be recently or currently releasing or gaining U to or from the groundwaters,
consistent with the extremely open character of the system. The samples in disequi-
librium with respect to U isotopes generally function as a closed system for the
228Ra(228Th)/232Th pair.

Acknowledgements

Financial support for this work was provided by ENRESA and CEC. We are grateful
to Drs. M.L. Munuera, A. Quejido, A. Bay6n, F. Floriano and M. S~nchez of the
Chemical Department of C I E M A T for the chemical analyses. We also thank F. SAnchez
and J. Navea from the Geology Department for preparation of the samples.

References

Anderson, T.F. and Arthur, M.A., 1983. Stable isotopes of oxygen and carbon and their application to
sedimentologic and paleoenvironmentalproblems. In: Stable Isotopes in Sedimentary Geology (M.A.
Arthur, T.F. Anderson,I.R. Kaplan,J. Veizer and L.S. Land, eds.). Soc. Econ. Paleont.Min., Short Course
10, Dallas.
Arribas, A., 1965. Mineralogiay Metalogeniade los yacimientosespafioles de uranio. 'El Berrocal', Escalona
(Toledo). Not. Com. Inst. Geol. Min. Espafia, 77: 67-92.
Borthwick, J. and Harmon, R., 1982. A note regarding chlorine trifluornro as an alternative to bromine
pentafluoride for oxygen isotopes analyses. Geochim. Cosmochim. Acta, 46: 1665.
Clayton, R.N., O'Neil, J.R. and Mayeda, T.K., 1972. Oxygen isotope exchange between quartz and water. J.
Geophys. Res., 77: 3057.
Eslinger, E.V. and Savin, S.M., 1973. Mineralogy and oxygen isotope geochemistry of the hydrothermally
altered rocks of the Ohaki-Broadlands,New Zealand geothermal area. Am. J. Sci., 273: 240.
Julivert, M., Fontbotr, J.M., Ribero, D. and Conde, L., 1972. Mapa Tect6nico de la Penfnsula Ib&ica y
Baleares. E. 1:10 6. Inst. Geol. Min. de Espafia, Madrid.
Land, L.S. and Dutton, S.P., 1978. Cementation of a Pennsylvanian deltaic sandstone: Isotopic data. J.
Sediment. Petrol., 48:1167.
McCrea, J.M., 1950. On the isotopic chemistry of carbonated and a paleotemperature scale. J. Chem. Phys.,
18: 849.
Osmond, J.K. and lvanovich,M., 1992. Uranium-seriesmobilizationand surface hydrology. In: Uranium-Series
Disequilibrium: Applications to Earth, Marine and Environmental Sciences (M. Ivanovich and R.S.
Harmon, eds.). Clarendon,Oxford, 259-289.
60 L. Pgrez del Villar et al./ Journal of Contaminant Hydrology 26 (1997) 45-60

Prrez del Villar, L., De la Cruz, B., Pardillo, J., Pelayo, M., Riva, P. and Astudillo, J., 1993a. El sistema
granito-mineralizaci6n de uranio de el Berrocal como an~logo natural de un almacenamiento de residuos
radiactivos. Estudios Geol., 49: 187.
Prrez del Villar, L., De la Cruz, B., C6zar, J.S., Pardillo, J., G6mez, P., Turrero, M.J., Rivas, P., Reyes, E.,
Delgado, A. and Caballero, E., 1993b. The clayey fissural fillings associated with NI00°-110°E fractures
at the El Berrocal uranium mine (Sierra de Gredos, Spain): Characterization, genesis and retention capacity
of radioactive and other elements. Estudios Geol., 49: 199-222.
P~rez del Villar, L., De la Cruz, B., Pardillo, J., C6zar, J.S, and Mrnager, M.T., 1994. U distribution in
relation to the mineralogical and geochemical characteristics of the granite from the El Berrocal uranium
mine (Spain). In: Proc. 4th Int. Conf. on the Chemistry and Migration Behaviour of Actinides and Fission
Products in the Geosphere, Charleston, SC, USA. R. Oldenbourg, Miinchen, 363-375.
Savin, S.M. and Lee, M., 1988. Isotopic studies of phyllosilicates. Rev. Mineral., 19: 189.
Vennemann, T.W. and Smith, H.S., 1990. The rate and temperature of reaction of C1F3 with silicate minerals,
and their relevance to oxygen isotope analysis. Chem. Geol., 86: 83.

Вам также может понравиться