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Applied

Geochemistry
Applied Geochemistry 20 (2005) 2252–2282
www.elsevier.com/locate/apgeochem

Thermochemically induced transformations in Al-smectites:


A Spanish natural analogue of the bentonite barrier behaviour
in a radwaste disposal
L. Pérez del Villar a,*, A. Delgado b, E. Reyes b, M. Pelayo a,
J.M. Fernández-Soler c, J.S. Cózar a, M. Tsige d, A.J. Quejido a
a
CIEMAT/DIAE/CHE/Ed.20, Avda. Complutense 22, 28040 Madrid, Spain
b
Dpto. de Ciencias de la Tierra y Quı́mica Ambiental, Estación Experimental del Zaidı́n (CSIC), Prof. Albareda 1, 18008 Granada, Spain
c
Dpto. de Mineralogı́a y Petrologı́a, Universidad de Granada, Avda. Fuentenueva s/n, 18002 Granada, Spain
d
Dpto. de Geodinámica, Facultad de Ciencias Geológicas, Universidad Complutense, Avda. Complutense s/n, 28040 Madrid, Spain

Received 15 October 2004; accepted 25 July 2005


Editorial handling by M. Gascoyne
Available online 7 November 2005

Abstract

The thermal effect induced by the Morrón de Mateo volcanic dome (Cabo de Gata volcanic region, Spain) on the adjacent
bentonitised tuffaceous beds has been studied as a natural analogue of the thermal behaviour of the bentonite-engineered bar-
rier of a geological radwaste repository. These bentonites consist mainly of Fe-rich smectites and were formed in equilibrium
with seawater at temperatures between 75 and 95 C, according to the d18O and dD values. In contrast, bentonites from other
localities in the region consist mainly of Al-smectites, formed in equilibrium with meteoric water below 25 C.
This investigation is focussed on the detection of the chemical differences between smectites from proximal and distal
zones to the dome, as well as to test whether the temperatures calculated based on the O and H isotopic values correspond
to their formation or transformation. The initial hypothesis was that the chosen smectites could be formed under marine
conditions, being later transformed and isotopically re-equilibrated as a result of the intrusion. To check this hypothesis, a
detailed mineralogical, chemical, geochemical and isotopic study has been performed on the smectitised tuffaceous mate-
rials and the overlaying biocalcarenites outcropping near and far from the dome.
The results show that distal smectites are dioctahedral Al-smectites, similar to those from other deposits in the region, while
proximal smectites are Fe- and Mg-rich smectites, showing two evolutionary trends on a Fe–Mg–Al ternary diagram. Similar
features are observed when their structural formulae are plotted on the muscovite–celadonite–pyrophylite diagram. Thus, they
plot in the smectite domain with interlayer charge less than 1, which is mainly due to octahedral substitution for distal smectites,
while for proximal ones it is caused by both octahedral and tetrahedral substitutions. In this ternary diagram, the domains of
both proximal and distal smectites are partially overlapped. The coexistence of di- and trioctahedral smectites was only detected
in one proximal sample. Further, proximal biocalcarenites are enriched in Fe-rich dolomite in relation to the distal ones.
The 87Sr/86Sr and d13C values in carbonates and dD in smectites indicate equilibrium with seawater. In contrast, d18O
values of carbonates and smectites indicate that they were transformed and re-equilibrated between 40 and 90 C, and
between 55 and 66 C, respectively, independently of their location with respect to the dome.

*
Corresponding author. Fax: +34 1 3466542.
E-mail address: l.pvillar@ciemat.es (L.P. del Villar).

0883-2927/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2005.07.014
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2253

These data suggest that the transformation of calcite into Mg–Fe-carbonates and the occurrence of Fe- and Mg-rich
smectites near to the dome resulted from a chemically induced process at similar temperatures. The compositional differ-
ences among samples suggests that Fe, Mg and minor Mn were supplied by a contaminant plume originated from the
dome, migrating through the sediments and becoming more diluted away from the source. The absence of a well-defined
thermal gradient in the system could be due to the small size, semi-closed and shallow character of the basin, as well as to
its high underlying volcanic activity.
Finally, the results are discussed in terms of analogue processes that can be expected in the bentonite barrier of a rad-
waste geological repository.
 2005 Elsevier Ltd. All rights reserved.

1. Introduction been selected as natural analogue of the thermal ef-


fect expected on the bentonite barrier of a DGRR
The disposal of long-lived radioactive nuclear after closure. This natural analogue is located in
wastes in a geological formation has been consid- the Cabo de Gata volcanic region (SE Spain) and
ered by many countries as the most suitable way close to the Morrón de Mateo bentonite deposit.
to provide protection to the biosphere. Most of This formation fulfils some of the above-mentioned
the national programs plan to isolate the nuclear criteria as explained below.
waste using a system based on multiple barriers, in Regarding the first criterion, bentonites in the
order to retain or delay the harmful long-lived ENRESA conceptual design (Astudillo, 2001) for
radionuclides long enough for substantial radioac- the engineered barrier come from the El Cortijo de
tive decay and/or dilution to occur. The near field Archidona deposit (La Serrata de Nı́jar zone), which
multiple barrier system is composed of: (i) the waste consist mainly of a Wyoming-type montmorillonite
itself; (ii) the canister containing the waste; and (iii) (Linares et al., 1993). Therefore, the entire labora-
the bentonite buffer surrounding and isolating the tory experiments performed at CIEMAT have been
canister from the host rock, or bentonite-engineered carried out on this bentonite (Huertas et al., 2000;
barrier. The far-field natural barrier is the host rock, Villar, 2002; Fernández, 2003). However, bentonites
known as geobarrier. from the Morrón de Mateo deposit, which is located
In terms of the performance assessment of a deep in contact with the volcanic dome, consist mainly of
geological repository of radwastes (DGRR), one of a Tatalia and Chamber-type montmorillonite (Del-
the most important aspects is the evaluation of the gado, 1993), which has the chemical composition
behaviour and durability of the bentonite- of the non-ideal montmorillonites, as defined by
engineered barrier. The extrapolation of the short- Shultz (1969) and Brigatti (1983).
term laboratory data over a longer time scale is a The second criterion is closely related to the ben-
relevant aspect for such evaluation. Hence, natural tonitisation processes, which produced numerous
analogues are the only tools that provide suitable bentonite deposits in the region, among which those
data for the long-term evaluation of the different from the Morrón de Mateo area are highlighted.
parts of a DGRR, such as the bentonite-engineered However, as the region was subjected to hydrother-
barrier. mal, marine and continental conditions from the
For the selection of a bentonite formation as nat- Upper Tertiary to Quaternary periods, several dif-
ural analogue of the bentonite-engineered barrier, ferent models have been proposed to explain the
the following criteria must be accounted (Yusa bentonitisation processes at different localities
et al., 1991): (i) analogies between natural exposure (Reyes, 1977; Linares, 1985, 1987; Caballero et al.,
and candidate clays; (ii) analogies between environ- 1985a,b). All these models involve hydrothermal
mental conditions and those expected under dis- solutions derived either from the volcanic activity
posal conditions after burial; (iii) simplicity and in the region, or from meteoric water reheated at
availability of environmental conditions; and (iv) depth. The interaction between these solutions and
availability of chronological data. the vitrophydic rocks, particularly acid tuffs, gener-
Based on these criteria, a smectitised volcano- ated the bentonite deposits. However, the isotopic
sedimentary series intruded by a dacitic volcanic studies performed on smectites from El Cortijo de
dome, known as the Morrón de Mateo dome, has Archidona and Los Trancos deposits (Delgado,
2254 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

1993; Delgado and Reyes, 1996) suggested that they tively), has been carried out for comparison. The
were formed by the interaction between meteoric initial hypothesis was that smectites from both areas
waters and tuffaceous materials at surface tempera- could be formed from the layered tuffs under marine
ture (<25 C). These interactions are more pro- conditions, and the smectites near the dome were la-
nounced along fracture zones (Delgado, 1993). By ter chemically transformed and isotopically re-equil-
contrast, the Morrón de Mateo deposit was formed ibrated by the volcanic intrusion.
by water/rock interaction involving seawater at
temperatures ranging between 70 and 90 C, in rela- 2. Geological background
tion to the Morrón de Mateo intrusion. The
involvement of seawater has been inferred from The Morrón de Mateo volcanic dome is a massive
the presence of marine biocalcarenites interbedded lava body that gives place to a promontory
with and covering the tuffaceous materials (Delgado (197 masl) in the so-called Escullos Depression
and Reyes, 1993; Delgado, 1993). (Fig. 1(a)). The lava body is composed of biotite-
Concerning the third criterion, the natural system hornblende, quartz-rich dacite, with a characteristic
selected is geologically simple, despite the complex red to ochre tint that links this body to the nearby
geological history of the region. Thus, the outcrops Rodalquilar Caldera Complex (Bordet, 1985; Arri-
investigated show a normal and gradual sedimen- bas, 1993; Fernández-Soler, 1992; Cunningham
tary sequence from partially smectitised tuffaceous et al., 1990; Rytuba et al., 1990; Arribas et al.,
beds, with minor marine carbonates, to biocalcare- 1995). The most conspicuous structure in the volca-
nite beds with some smectitised tuffaceous material. nic dome is a wide and well-developed subvertical
All of these outcrops can be stratigraphically corre- flow foliation, marked by alternating centimetre
lated and only the volcanic intrusion and minor bands with slightly different coloration. The flow
faults perturb the exposures located near the dome. foliation orientations and their relationships with
In relation to the availability of chronological the present contacts and faults suggest that the
data, the biocalcarenite beds have been assigned to dome is really composed of an intricate set of
the Lower Tortonian (Betzler et al., 1997), approx- dyke-like subvertical elements, elongated approxi-
imately 11.6 Ma ago (Hilgen et al., 2003), while mately N-S, and rooted in a plug-like feeder-chan-
the Morrón de Mateo dome has been dated between nel around the Morrón de Mateo peak. Every
11.3 and 10.8 Ma (Di Battistini et al., 1987; Zeck dyke-like element could have been generated in an
et al., 2000; Zeck and Whitehouse, 2002). That individual eruptive pulse, being different pulses
means that the volcanic dome intruded between probably separated by short intervals of inactivity
3 · 105 and 8 · 105 years after the formation of the and cooling (Fernández-Soler, 1992).
volcano-sedimentary series. However, though the The Morrón de Mateo dacite dome intruded
lava temperature has been estimated as approxi- through an older volcano-sedimentary series, which
mately 820 C, by using the Fe–Ti oxides and pla- consist mainly, from the bottom to the top, of: (i) a
gioclase-hornblende geothermometric pairs variety of hard, hornblende-rich andesite rocks; (ii) a
(Fernández-Soler, 2002), the cooling rate of the lava layer of marine calcarenites-calcirudites; (iii) white
and therefore the interaction period between the layered tuffs; (iv) marine sedimentary rocks; and (v)
volcanic dome and the volcano-sedimentary series grey tuffs (Fig. 1(b)). White layered tuffs and marine
is more difficult to evaluate. Nevertheless, the Mor- sedimentary rocks are the most interesting litholo-
rón de Mateo geological system has been considered gies for the aims of this work.
as a natural analogue for the bentonite barrier of a The white layered tuffs are composed of a succes-
DGRR. Thus, the transformation of the smectites sion of several types of pyroclastic layers, quite rec-
as a result of the thermal effect induced by the vol- ognisable in spite of the degree of transformation
canic intrusion has been studied in order to evaluate into bentonite. The most common appearance is a
the variations in their buffering and physicochemi- regular decimetre-scale succession of laterally very
cal properties. extended and white-coloured soft layers of benton-
To achieve this objective a strategic mineralogi- ite-rich tuffs. They were originally composed of
cal, chemical, geochemical and isotopic study of white lapilli pumice (pumice-rich layers), alternating
the smectites from the bentonitised layered tuffs, lo- with slightly harder tabular layers of a sandy or
cated close and far from the volcanic dome (the gritty material (gritty layers). These last layers are
Morrón de Mateo and El Murciano areas, respec- brownish to greenish, poorer in bentonite, and
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2255

Fig. 1. (a) Geological map of the studied area, showing the location of sampled profiles (modified after Fernández-Soler, 2002). The cross-
sections A–A 0 , B–B 0 and C–C 0 in (a) and Fig. 2 are also indicated. Key: 1: hornblende andesite breccias and lavas. 2: Tortonian marine
sedimentary rocks (limestones, calcarenites, conglomerates and sandstones). 3: layered tuffs. 4: grey tuffs. 5: white dacitic pyroclastic tuffs.
6: the Morrón de Mateo dacite dome. 7: Rodalquilar Complex (rhyo) dacitic rocks. 8: undifferentiated Quaternary sediments. 9: alluvial
fans. 10: Pleistocene oölitic sandstones (fossil beach). (b) Illustrative cross-sections A–A 0 and B–B 0 through the Morrón de Mateo
sequence, showing the intrusive relation between the Morrón de Mateo dome and the volcano-sedimentary sequence (Fernández-Soler,
2002). See location in (a). Key: 1: hornblende andesite breccias and lavas. 2: layered tuffs. 3: Tortonian marine sedimentary rocks
(limestones, calcarenites, conglomerates and sandstones). 4: grey tuffs. 5: white dacitic pyroclastic tuffs. 6: the Morrón de Mateo dome. 7:
recent alluvial sediments. The approximate position of sampled profiles 1, 2, 3, and 6 is also indicated.
2256 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

composed of a larger proportion of crystals, small reworked by sedimentary processes. The biocal-
lithic fragments, and smaller amounts of lapilli carenite is variably cemented to more dense
pumice. It is easily recognisable since the bentonite limestone.
formation has proceeded more extensively in the
originally glass-rich white pumice layers than in
the crystal-rich gritty layers. The whole sequence 3. Sampling and methods
of layered tuffs are sub-horizontal or dipping at
low angle to the E, but the intrusion of the Morrón For the purposes of this investigation, 6 cross-
de Mateo dacite dome dragged and folded the lay- sections (profiles 1–6) were chosen for sampling.
ered sequence in its proximity. Data from drillholes Four of them (1, 2, 3 and 6) are located near the vol-
and outcrops indicate that this lithological unit may canic dome, while the remaining two (4 and 5) far
reach a thickness of 60–70 m, although with large from the dome, in the so-called El Murciano quarry
lateral variations. This formation shows some sedi- (see Figs. 1(a) and 2). At each cross-section, samples
mentary structures that point to lateral currents as were taken from the upper part of the white layered
main transport and deposition mechanism. These tuffs, lowermost layer of calcarenite, and mixed
features suggest that the white layered tuffs may layer between them (Fig. 3 and Table 1).
have formed as a result of phreatomagmatic activ- Samples were dried in a forced air oven at 30–
ity occurring by magma–water interaction in a 40 C for 48 h and then ground and homogenised
shallow marine environment, probably in a depressed in an agate ball grinder. Afterwards, they were
coastal embayment (Fernández-Soler, 1987, 1992; sieved to a <60 lm grain size, by using a nylon mesh
Fernández-Soler and Muñoz, 1988). ASTM sieve.
The marine sedimentary rocks are placed uncon- The semi-quantitative mineralogical composition
formably on top of the white layered tuffs, giving of the bulk samples was determined by a powder
the most notable lithologies, from the bottom to X-ray diffraction (XRD) method, by using the
the top: reflecting powers proposed by Shultz (1964) and
Barahona (1974), and the calculation method of
• A 5–10 m thick layer of poorly consolidated Bradley and Grim (1961). A ‘‘X’’ Pert-MPD Philips
beach sands and sandstones, commonly with bio- diffractometer, Cu Ka radiation and a scan speed of
turbation marks, occurs in some localities near 1.5 2h/min were used. The mineralogical composi-
the Morrón de Mateo dome. tion of white tuff samples has been referred to the
• A few meters thick layer of carbonate-cemented crystalline fraction, because they contain significant
conglomerates, composed of decimetre-sized amounts of amorphous components.
clasts of volcanic rocks and marine fossils. They Optical polarising and scanning electron micros-
are on top of the beach sands, or more commonly copy (Zeiss DSM 960), coupled to an energy disper-
directly on top of the white layered tuffs. sive X-ray analytical Link eXL system (SEM +
• Bioclastic calcarenite, with massive to layered EDX), were used in the study of thin polished sec-
structure, is the main lithological unit of these tions. Some backscattered electron images were
marine sediments. It is about 20 m thick, com- taken to illustrate the most relevant mineralogical
posed of clast-supported, heterometric clasts of and textural features of the samples.
bryozoa, echinoderms and bivalves. This associ- Clayey fractions (<2 lm) were extracted only from
ation (bryomol) is typical of temperate climate the white tuff samples by the conventional sedimenta-
carbonates, which are widespread through the tion method, using de-ionised water. Only sample
Lower Tortonian basin in the Cabo de Gata MTO-11A was treated with a 5% Na hexa-metha-
region. This unit is laterally very extensive, out- phosphate solution for dispersion purposes. Oriented
cropping in both the Morrón de Mateo and El specimens, previously treated with ethylene glycol
Murciano sites. This biocalcarenite unit is (EG), dimethyl sulphoxide and heated at 550 C for
deposited on the white-layered tuffs, showing a 1 h were systematically analysed by XRD in the
transitional bed formed by a mixture of tuffa- 2–35 2h range for mineral identification. The diocta-
ceous materials and marine carbonates (mixed hedral or trioctahedral character of smectite was
bed). At some places, this mixed bed contains deciphered in the 55–65 2h regions from powder
abundant soft-clayey pebbles, which are sup- XRD patterns of the clayey fractions. XRD patterns
posed to be remnants of former pumice pebbles of the EG-solvated oriented specimens, the reflecting
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2257

Fig. 2. (a) Cross-section in the western slope of the Morrón de Mateo hill, with approximate indication of the sampled profile 1. Key: (A)
Recent alluvial fan conglomerates. (B) Layered tuffs. (C) Calcarenites and carbonate-matrix conglomerates. (D) Grey massive tuffs. (E)
The Morrón de Mateo dacite dome. (b) Cross-section in the SW slope of the Morrón de Mateo hill, with approximate indication of the
sampled profiles 2 and 3. Key: (A) Hornblende dacite breccias and lavas. (B) Layered tuffs. (C) Beach sands and sandstone, pumice-rich
lens. (D) Carbonate-matrix conglomerate and lumaquella. (E) Limestones and calcarenites. (F) Grey tuffs. (G) The Morrón de Mateo
dome. (c) C–C 0 cross-section through the Murciano area, indicating the approximate location of distal sampled profiles 4 and 5 (see
location in Fig. 1(a)). Key: (A) Hornblende andesite breccias and lavas. (B) White foraminifera-rich limestones. (C) Layered tuffs. (D)
Carbonate-matrix conglomerates and calcarenites. (E) Pleistocene oölitic sandstones (fossil beach). (d) Cross-section in the western slope
of the Morrón de Mateo hill, with approximate indication of sampled profile 6 and detailed sketch of the structure in the abandoned
quarry in the western slope of the Morrón de Mateo hill. Key: (A) Hornblende andesite breccias and lavas. (B) Layered tuffs. (C) Beach
deposits (clastic sands and sandstones). (D) Calcarenites and carbonate-matrix conglomerates. (E) Grey massive tuffs. (F) White dacitic
pyroclastic tuffs. (G) Mn-rich coralline limestones. (H) The Morrón de Mateo dacite dome.
2258 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

Fig. 3. Pictures of the six sampled profiles, showing the sampling points along the Lower Tortonian tuffaceous-biocalcarenite series.

powers proposed by Barahona (1974) for clay performed in the Chemistry Division of CIEMAT.
minerals and the Bradley and Grim (1961) calcula- Three replicates of both samples and certified refer-
tion method were used for their semi-quantitative ence materials (SRM 97b and SRM 98b for clay-rich
estimation. samples and SRM 88b for carbonate-rich samples)
Chemical analyses of the smectites were carried were dissolved using a HF–aqua regia mixture in a
out in a JEOL-200Kv JEM 2000 transmission elec- closed PTFE vessel and heated overnight. After
tron microscope coupled to an EDX analytical sys- cooling, HF in excess was removed by addition of
tem (TEM + EDX). The structural formulae were HClO4 and the solution was evaporated under an
calculated from these EDX-chemical data, consider- IR lamp. Finally, the residue was dissolved in dilute
ing that total Mg is in octahedral positions. These HNO3. Major, minor and trace elements (except U)
analyses were carried out in the Electron Micros- were determined by inductively coupled plasma
copy Center ‘‘Luis Brú’’ from the Universidad atomic emission spectrometry (ICP-AES, Jobin
Complutense de Madrid. Yvon JY48 and JY38 instruments) and flame atomic
Chemical analysis of the bulk and <2 lm samples emission spectroscopy (FAES, PE 5000, Perkin–El-
(major, minor and trace elements, except SiO2) was mer). For ICP-AES analysis of major constituents
Table 1
Location, lithology and semi-quantitative mineralogical composition of the bulk samples
Profiles Samples Lithology Location Q (%) Plag. (%) K-Fd. (%) Amph. (%) Zeol. (%) Crist. (%) Cc. (%) Dol. (%) T.Ph. (%)

L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282


1 MTO-1 Clayey (1) Near the dome 5 14 4 0.5 1 12 0 0 64
MTO-2 Mixed (1 + 2) 2 4 2 1 3 6 59 6 17
MTO-3 Limestone (2) 2 7 Tr 1 7 14 55 13 Tr
2 MTO-4 Clayey (1) Near the dome 4 1 6 0.5 1 0 31 0 57
MTO-5 Mixed (1 + 2) 3 8 Tr 1 0 Tr 59 2 27
MTO-6 Limestone (2) 3 6 – – – – 82 2 7
3 MTO-7 Clayey Near the dome 5 15 0 0 1 10 19 0 50
MTO-8 Conglomerate 4 14 Tr 1 18 7 46 0 10
MTO-9 Limestone 7 14 Tr – 5 6 53 6 8
4 MTO-10 Clayey (1) Far from the dome 5 23 0 1 1 6 10 0 55
MTO-11 A Soft pebble 1 2 0 0 0 1 8 0 88
MTO-11 B Mixed (1 + 2) 13 7 8 1 3 1 40 0 26
MTO-12 Limestone (2) 12 12 Tr 2 6 3 38 – 27
MTO-13 Limestone 9 8 – Tr 4 5 60 – 15
5 MTO-14 Clayey (1) Far from the dome 2 5 3 0 1 9 0 0 80
MTO-15 Mixed (1 + 2) Tr 8 Tr 2 7 12 46 0 24
MTO-16 Limestone (2) 2 10 Tr 2 6 16 46 – 15
MTO-17 Limestone 2 13 – 2 22 13 35 – 13
6 MTO-18 Clayey (1) Near the dome 1 12 0 0 1 9 27 16 34
MTO-19 Mixed (1 + 2) 2 7 – 2 – 6 58 – 25
MTO-20 Limestone 13 4 – – 1 10 70 – Tr
Q, quartz; Plag., plagioclases; K-Fd., K-feldspar; Amph., amphiboles; Zeol., zeolites; Crist., cristobalite; Cc., calcite; Dol., dolomite; and T.Ph., total phyllosilicates.

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2260 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

(Al2O3, Fe2O3, CaO, MgO, MnO, P2O5 and TiO2), ing solutions trough a 10 mL Dowex 50 · 8 cation
the dissolved samples were previously diluted 5 times exchange resin. This isotope ratio was measured in
and 20 mg L1 of Y (as internal standard) were the Geochemistry Laboratories of the University
added, in order to improve instrumental precision. of Granada, by means of a multicollector Finni-
Combined uncertainty (including sample prepara- gan MAT 262 thermal ionisation mass spectrome-
tion uncertainty, calibration uncertainty and long ter (TIMS), by using static detection of the
and short-term reproducibility) of the analytical element positive ions. Samples were loaded on a
data are less than 1% for major elements and less Re filament and mass bias was corrected using
86
than 5% for trace elements. Uranium analyses were Sr/88Sr = 0.1194. Blank values of the procedure
performed by laser induced kinetic phosphorimetry are below 0.6 ng.
(KPA-11, Chemchek Instruments Inc.), by using Isotope measurements of O and H in clay miner-
the sample dissolved as described before. als were carried out in the Stable Isotope Labora-
Elemental analyser (Leco CS-244) was used for tory of the University of Western Ontario
total C and S analyses. A standard reference soil (Canada). Prior to O isotopic analyses, gels and
(Soil #1, EuroVector S.p.A., Milano, Italy) was reg- amorphous materials were removed by chemical at-
ularly measured in order to check accuracy of data. tack. Furthermore, samples were degassed under
Differential thermal and thermogravimetric anal- vacuum at 150 C for 12 h to remove adsorbed
yses were carried out using a TG/DTA 6300 system and interlayer water. The O from smectites was ex-
for determining H2O, H2O+ and inorganic CO2. tracted by reaction with ClF3. Oxygen was then
The instrument was calibrated with a high purity purified and converted to CO2 using a vacuum line
monohydrated calcium oxalate (CaC2O4 Æ H2O, similar to that described by Clayton and Mayeda
Alfa Aesar, Karlsruhe, Germany). (1963). For the H measurements, samples were pre-
Labile SiO2 in tuff bulk samples and <2 lm frac- viously degassed under vacuum at 150 C for 12 h to
tions was extracted by the Ross and Hendrick remove adsorbed and interlayer water. Hydrogen
(1945) method and determined by UV–Vis spectro- was extracted from the remaining sample using the
photometry (Beckman DU-7), following the method U-reduction method of Bigeleisen et al. (1952), as
proposed by the US Environmental Protection modified by Keyser and ONeil (1984) and Venne-
Agency (1983). Labile Al2O3 and Fe2O3 were re- mann and ONeil (1993). The isotope ratio measure-
moved by the method proposed by Quejido et al. ments were performed using a Prism II mass
(1988) and determined by ICP-AES, using matrix- spectrometer. The isotopic results are reported in
matching calibration. the standard delta (d) notation in parts per thou-
The total exchangeable cations (TEC) of both sand (&) relative to Vienna Standard Mean Ocean
bulk and <2 lm samples were extracted by succes- Water (VSMOW) (Coplen, 1994). Reproducibility
sive washing with NH4Cl 1 N at pH 8.2 in a 60% was better than ±0.2& and ±2& for d18O and
v/v ethanol and distilled water solution. Prior to dD, respectively.
the determination of the TEC, the soluble salts were Isotope measurements of C and O in carbonates
removed with a solution containing 70% v/v abso- were carried out at the Stable Isotope Laboratory of
lute ethanol and 30% v/v distilled water. The sam- the ‘‘Estación Experimental del Zaidı́n’’ (Granada,
ples were shaken end-over-end for 2 days. After Spain). Calcite samples were treated with 100%
phase separation by centrifuging, the extracted cat- H3PO4 during 12 h in a thermostatic bath at 25 C
ions were measured by using ICP-AES and FAES. (McCrea, 1950). Samples containing calcite, dolo-
A matrix-matching method was used for calibration mite and siderite as major, minor or trace compo-
of both analytical instruments. Accuracy of the nents were treated according to the Al-Aasam
analyses was checked against SAz-1 reference mate- et al. (1990) method. CO2 was analysed by means
rial, which is a Ca-rich montmorillonite, supplied by of a Finnigan MAT 251 mass spectrometer, and
The Clay Minerals Society. the experimental error found was lower than
Carbonate fractions from both mixed and bio- ±0.15 for d13C and d18O, using Carrara and EEZ-
calcarenite bulk samples were selectively removed 1 internal standards, previously compared with
by twice treating with Morgans solution at pH NBS-18 and NBS-19. All the samples were com-
4.5, in order to determine the Sr contents and pared with a reference CO2 obtained from a stan-
their isotope ratios. Samples for 87Sr/86Sr ratios dard calcite prepared simultaneously. Thus, O
determination were prepared by passing the result- isotope ratios for carbonates were recalculated tak-
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2261

ing into account the fractionation factor for acid Samples from the first group contain two genera-
decomposition: 1.01065 for dolomite at 50 C tions of calcite. The first generation consists of
(Rosembaum and Sheppard, 1986) and 1.01044 rounded-shaped, fine-grained xenomorphic calcite
for calcite at 25 C (Kim and ONeil, 1997). with minor Mn or Mn and Fe (Fig. 4(a)). This gen-
The specific surface area of both smectitised eration is mixed with fossil clasts, mainly bryozoa.
pyroclastic bulk samples and <2 lm fractions was These features are typical of marine bioclastic cal-
determined by a BET Flowsorb II 2300 (Micromer- carenites. The second generation consists of large
itics) equipment. The calculations were carried out xenomorphic to idiomorphic plates or crystals of
by the BET method of the single point. calcite either almost totally pure or with minor
Mn or Mn and Fe (Fig. 4(a) and (b)). The latter
4. Results and discussion occasionally replaces other minerals, fills their fis-
sures and replaces bryozoa remains. Both genera-
4.1. Mineralogy tions act as cement of the partially altered
pyroclastic fraction, which, in turn, is later cemen-
The semi-quantitative mineralogical composition ted by zeolites and microcrystalline silica.
of the bulk samples from the smectitised tuffaceous, Samples from the second group do not contain
mixed and biocalcarenite materials is listed in Table detrital primary calcite except in sample MTO-9,
1. In all the samples, plagioclase, K-feldspar, amphi- in which the original bioclastic texture is preserved.
bole, undetermined phyllosilicates, cristobalite and In contrast, large plates of pure calcite and plates of
undetermined zeolites represent the original mineral Mn-calcite, showing a close textural relationship
assemblage of the tuffaceous fraction and its alter- between them, predominate in all the samples
ation products. The carbonate fraction in the (Fig. 4(c)). Furthermore, hypidiomorphic to idio-
samples consists mainly of calcite with probably sec- morphic dolomite crystals and dolomite with minor
ondary dolomite in some samples, particularly in Mn and Fe are relatively frequent in the samples
those from the proximal profiles. (Fig. 4(d)). In addition, a Fe (Mn) carbonate, with
The SEM observations and EDX analyses per- botryoidal texture and a chemical composition sim-
formed on the mixed and biocalcarenite samples al- ilar to that of spherosiderite, is occasionally found
low one to state that the tuffaceous fraction has a in some samples (MTO-3). This Fe (Mn) carbonate
complex mineralogy, mainly due to the large num- is closely associated with ankerite and replaces large
ber of minor and trace minerals identified. Among plates of pure calcite (Fig. 4(e)). As in samples of
them, some hydrothermal and/or diagenetic miner- the first group, the bryozoa clasts are filled and
als must be highlighted as indicators of physico- mineralised by carbonates and colloidal or micro-
chemical environmental conditions under which crystalline silica (Fig. 4(f)).
they were formed. These minerals are zeolites The textural and mineralogical differences ob-
(thomsonite, mordenite, phillipsite, heulandite, cly- served between carbonates from proximal and distal
noptilolite, and probable ferrierite), spherulitic, con- samples seem to indicate the existence of two differ-
centric and fibrous-radiating criptocrystalline silica, ent geochemical environments, probably developed
framboidal pyrite, sphalerite, Sr-rich barite, celes- after sedimentation, as a result of the Morrón de
tine, and primary Mn-oxyhydroxides. Other sec- Mateo intrusion. This intrusion could be the source
ondary minerals related to meteoric diagenesis, of Mg, Fe and Mn that metasomatised the original
such as gypsum, and As rich Fe-oxyhydroxides calcite of bioclastic calcarenite. It could operate as
from the oxidation of pyrite are also present in all the source of a contaminant front migrating
the samples. Unidentified clay minerals, probable through the sediments undergoing dilution away
smectite, coated by Fe-oxyhydroxide or closely from the source. This may be the reason why neither
associated with Mn-oxyhydroxides, are present in dolomite nor ankerite and spherosiderite could be
some samples, as a result of the total alteration of formed in the distal samples.
obsidian and/or pumice rounded pebbles. Samples from both biocalcarenite and mixed beds
For the description of the carbonate fraction, the contain minor pyrite regardless of their location with
samples have been classified in two groups: the first respect to the subvolcanic dome. This sulphide is
consists of samples located far from the volcanic usually included in carbonates and currently almost
dome and the second group of samples near the totally transformed into As-rich Fe-oxyhydroxides,
dome. preserving its original framboidal texture. Though
2262 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2263

Table 2
Semi-quantitative mineralogical composition of the clayey fractions (<2 lm) from the smectitised tuffaceous samples
Profiles Samples Location Smectite Crist. Plagioclase Calcite Zeolites Di/trioctahedral Crystallinityc
(%) (%) (%) (%) (%)
1 MTO-1 Proximal 94 4 1  1 Dioctahedral 0.91
2 MTO-4 Proximal 95 – 5 – – Di- and trioctahedral 0.97
3 MTO-7 Proximal 97 – – 3 – Dioctahedral 0.95
4 MTO-10 Distal 95 – 5 – – Dioctahedral 0.92
MTO-11Aa Distal 98 – 2 – – Dioctahedral 1.00
MTO-11Bb Distal 86 6 8 – – Dioctahedral 0.96
5 MTO-14 Distal 89 11 – – – Dioctahedral 0.94
6 MTO-18 Proximal 76 5 8 11cal + dol – Dioctahedral 0.97
NB: % is referred to crystalline fraction. Crist: Cristobalite. 11 cal + dol: calcite (7%) + dolomite (4%). All the samples contain spinel
(MgAl2O4), which was detected in the powder XRD patterns.
a
Soft pebble from the mixed bed.
b
Clay fraction from bulk sample taken in the mixed bed.
c
Biscaye (1965) crystallinity index.

the paragenetic position of pyrite is problematic, its tocrystalline silica from the submarine alteration of
textural relationships with carbonates, as well as its obsidian and pumice pebbles into smectites and
textural feature itself, suggest that it could be con- zeolites. Weathering is the last process affecting the
temporary with the recrystallisation and metaso- system. It formed As-rich Fe-oxyhydroxides, a sec-
matic-diagenetic processes affecting carbonates. ond generation of Mn-oxyhydroxides and, locally,
The presence of As in the Fe-oxyhydroxides suggests gypsum.
that the original pyrite was an As-rich pyrite. From The semi-quantitative mineralogical composi-
these data, it can be inferred that reducing condi- tion of the clayey fractions (<2 lm) obtained from
tions prevailed during the aforementioned metaso- the white tuff samples, including representative
matic-diagenetic process. Thus, the substitution of samples of the soft clayey pebbles (MTO-11A)
Ca by Fe(II) and Mn(II) in carbonates was facili- and their host mixed bed (MTO-11B), is listed in
tated. Another diagenetic mineralogenetic event ob- Table 2. Data indicate that samples consist mainly
served in the samples is a silicification process that of a high-crystalline dioctahedral smectite, with
resulted in the precipitation of colloidal and/or cryp- minor cristobalite, plagioclase, calcite and zeolites.
The coexistence of both dioctahedral and triocta-
hedral smectite has been observed only in one
proximal sample. From their structural formulae,
b
Fig. 4. Backscattered electron images showing: (a) Two genera-
two groups of smectites have been distinguished.
tions of calcite with minor Mn (1). Notice the different textural The first group (Appendix A) contains the smec-
features of primary fine-grained detrital calcite and the large tites from proximal samples (MTO-1, MTO-4
plates of secondary calcite. 3: secondary zeolites and 2: colloidal and MTO-18) and the second (Appendix B) by
silica (Distal sample MTO-13). (b) Large plate of carbonate smectites from distal samples (MTO-10, MTO-
showing the two generations of calcite: in the inner part of the
plate, partially re-crystallised primary pure calcite (1) is present,
11A and MTO-14). Smectites from sample MTO-
preserving some detrital features. This calcite is coated by the 7 can be considered as intermediate terms (see
second generation of Mn-bearing calcite (2). 3: colloidal silica Appendix A).
(Distal sample MTO-13). (c) Re-crystallised Mn-bearing calcite Smectites from the first group usually show struc-
(1), calcite (4) and neoformed ankerite (3) and dolomite (2). tural formulae similar to Fe–Mg or Mg–Fe rich
(Proximal sample MTO-20). (d) Re-crystallised calcite (2),
idiomorphic dolomite + ankerite (1), Fe–Mn-bearing dolomite
smectites, while smectites from the second group
(4) and Mg-bearing calcite (5) cemented by colloidal silica in dark are similar to montmorillonite. Smectites from this
grey. 3: partially substituted muscovite plate (Proximal sample second group usually have approximately 8Si4+ in
MTO-3). (e) Spherosiderite (3) and ankerite (2) substituting the tetrahedral sheet and Al3+ > Mg2+ > Fe3+ in
secondary calcite (1). 5: void in the rock. 4: neoformed dolomite. the octahedral positions, in an approximate propor-
6: probable muscovite. 7: Fe–Mn oxyhydroxides. 8: hornblende.
9: ilmenite. 10: colloidal silica (Proximal sample MTO-3). (f)
tion of 4Al3+:2Mg2+:Fe3+. Nevertheless, it is rele-
Bryozoa remains firstly mineralised by colloidal silica (1) and vant that octahedral occupancy in all the structural
secondly by calcite (2) (Proximal sample MTO-6). formulae significantly exceed 4 cations per O20
2264 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

(OH)4 group, particularly in those from the first tionary trend that points to vertex Mg. Smectites
sample group. They have a chemical composition from sample MTO-7 represent the intermediate
between beidellite and saponite, showing an octahe- members, while smectites from sample MTO-4 rep-
dral occupancy ranging from 4.22 (sample MTO-1, resent the Mg-rich end-members. All of the inter-
8) to 5.25 (sample MTO-18, 4). Smectites of samples mediate and end-members are represented in
from the second group or distal samples also exhibit sample MTO-18.
more than 4 cations in the octahedral sheet, ranging When the structural formulae are represented
between 4.08 (sample MTO-11A, 5) and 4.42 (sam- on the muscovite–celadonite–pyrophyllite ternary
ple MTO-10, 4), but with a chemical composition diagram (Fig. 5(b)), all of them plot in the smectite
that generally corresponds to an anomalous Mg-rich domain, with total interlayer charge below 1. How-
montmorillonite. This anomalous chemical compo- ever, net negative charge in distal smectites is
sition and structural formulae suggest the possibility mainly due to the octahedral substitutions, while
that different stacking of minor trioctahedral and in proximal smectites it is caused by both octahe-
dominant montmorillonitic layers constitute the dral and tetrahedral substitutions but in different
analysed particles. Similar anomalous chemical for- proportions. Smectites plotted outside of the dia-
mulae for smectites have been described in previous gram are those containing more than 4 trivalent
works (i.e., Paquet et al., 1982, 1987; Duplay, 1984; cations in octahedral sites (more than 12 positive
Kodoma et al., 1988; Mayayo et al., 2000), question- charges). Though this fact could suggest impurities
ing the assumed compositional gap between di- and in the samples, irregularities in the structure or the
trioctahedral smectites (Weaver and Pollard, 1973). presence of hydroxide-like interlayers, such as bru-
However, Grauby et al. (1993) demonstrated that cite (Mg(OH)2) and/or Fe oxyhydroxides Fe(OH)3
complete solid-solution between di- and trioctahe- layers (Newman and Brown, 1987), it can be ex-
dral smectites does not exist, but rather, on the basis plained as an advanced stage in the transition from
of XRD, TEM and IR analyses, these intermediate di- to trioctahedral smectites, as Mayayo et al.
compositions seem to correspond to physical mix- (2000) suggested. In this sense, it is relevant that
tures, in different proportions, of di- and trioctahe- the proximal smectite domain overlaps that of
dral smectites stacked together in the same particle. the distal ones. Consequently, all of these data sug-
This fact has been interpreted as the result of the gest that a secondary geochemical process affected
alteration of dioctahedral smectites in environments the system, transforming Al-rich smectites into Fe-
with a high rock/water ratio and a significant solute rich and Mg-rich smectites. This process was prob-
content (Mayayo et al., 2000). According to this, the ably similar to that responsible for the presence of
coexistence of both di- and trioctahedral smectites in Mg–Fe-rich carbonates in the proximal mixed and
the proximal sample MTO-4, as detected by XRD, biocalcarenite samples, since in both cases the
can be explained. same elements (Fe and Mg) are involved.
The octahedral cations have also been repre-
sented on an Al–Fe–Mg ternary diagram in order 4.2. Elemental geochemistry
to check the smectite evolution from distal to
proximal samples (Fig. 5(a)). This diagram shows The major and trace elements of bulk samples
that distal smectites, with structural formulae sim- are listed in Tables 3 and 4. No significant chemi-
ilar to all of the other bentonite deposits in the re- cal differences exist between proximal and distal
gion (Reyes, 1977; Reyes et al., 1987; Linares samples from the smectitised tuffaceous material,
et al., 1993; Delgado, 1993), plot close to vertex except for MnO contents, which are higher in
Al, determining the initial point of two evolution- proximal MTO-1 and MTO-18 samples than in
ary trends. The first trend points towards vertex the remaining ones. These Mn-rich samples are
Fe and is formed by smectites from samples also enriched in As, while sample MTO-1 is also
MTO-10, MTO-11A, MTO-14 and MTO-1. In this enriched in Ba. The differences observed among
trend, smectites from the distal MTO-10 sample the CO2 and CaO are related to the carbonate con-
represent the intermediate members, while smec- tents in the samples (see Table 1) and they are not
tites from the proximal MTO-1 sample represent related to their location with respect to the dome.
the Fe-rich end-members. The same initial point Similarly, scarce chemical differences exist among
and the smectites from proximal MTO-7, MTO-4 the mixed samples. Nevertheless, variations in the
and MTO-18 samples determine the second evolu- MgO contents, partially associated with dolomite,
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2265

Fe
0.1 0.9

0.3 0.7
Legend
Proximal samples
0.5 0.5 Distal samples

0.7 0.3

0.9 0.1

Mg Al
a 0.1 0.3 0.5 0.7 0.9
3+
K (Al, Fe )4 Si Al2 K (Al, Fe3+) (Mg, Fe2+)2 Si8

Muscovite Celadonite

b Pyrophyllite 3+
(Al, Fe )4 Si8

Fig. 5. (a) Fe–Mg–Al ternary diagram showing the octahedral cations of the smectites. Notice the two evolutionary trends defined by the
distal (Al-rich members) and proximal smectites (Mg-rich and Fe-rich end-members). (b) Pyrophyllite–celadonite–muscovite ternary
diagram on which smectites are represented according to the octahedral, tetrahedral and interlayer charges. Note that all the smectites plot
in the smectite domain and that the proximal smectite area overlaps the distal smectite one.

are related to the location of the samples. Thus, MgO contents, are also related to the mineralogical
samples near the dome (MTO-2, MTO-5 and composition of the samples (see Table 1), which
MTO-19) contain the highest concentrations of are dolomite-enriched in the proximal ones. As in
MgO. Among them, sample MTO-2 is also richest mixed samples, some proximal biocalcarenite sam-
in MnO. Finally, all the chemical variations ob- ples (MTO-3 and MTO-20) are Mn-enriched with
served in biocalcarenite samples, mainly in the respect to the other samples.
2266
Table 3
Chemical composition of the bulk samples (Major elements)
Oxides (%) SiO2L Al2O3 Al2O3L Fe2O3 FeO Fe2O3L MgO MnO CaO Na2O K2O TiO2 P2O5 H2OT CO2T SO2T
SRM-97b Certified – 39.23 ± 28 – 1.19 ± 1 – 0.187 ± 3 0.0061 ± 6 0.035 ± 4 0. 066 ± 3 0.066 ± 3 2.39 ± 7 (0.046) – – –
Obtained – 39.51 ± 63 – 1.16 ± 3 – 0.191 ± 5 0.010 ± 1 0.042 ± 8 0.069 ± 5 0.063 ± 6 2.34 ± 9 0.049 ± 8 – – –
SRM-98b Certified – 27.03 ± 38 – 1.69 ± 1 – 0.59 ± 2 0.0150 ± 6 0.106 ± 5 0.202 ± 9 0.066 ± 3 1.35 ± 2 (0.069) – – –
Obtained – 27.21 ± 58 – 1.68 ± 3 – 0.61 ± 3 0.017 ± 2 0.110 ± 8 0.210 ± 12 0.068 ± 5 1.38 ± 6 0.073 ± 9 – – –

L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282


SRM-88b Certified – 0.336 ± 13 – 0.277 ± 2 – 21.03 ± 7 0.0160 ± 12 29.95 ± 5 0.0290 ± 7 0.1030 ± 24 2.39 ± 7 0.066 ± 3 – – –
Obtained – 0.352 ± 26 – 0.285 ± 9 – 21.10 ± 9 0.017 ± 2 30.0 ± 1 0.030 ± 1 0.105 ± 6 2.44 ± 9 0.071 ± 7 – – –

Samples Smectitised tuffaceous samples


MTO-1 0.50 11.63 0.27 5.64 0.14 0.70 3.30 1.00 3.20 2.40 1.40 0.55 0.03 9.08 0.62 0.10
MTO-4 0.38 11.85 0.25 4.42 0.30 0.45 4.40 0.07 17.4 1.30 1.90 0.47 0.11 6.39 11.73 0.08
MTO-7 0.49 15.46 0.24 4.12 0.27 0.38 3.90 0.14 12.3 1.90 0.96 0.49 0.13 5.84 6.60 0.06
MTO-10 0.84 17.42 0.28 5.11 0.24 0.52 4.00 0.04 8.60 2.20 1.10 0.69 0.14 6.80 3.34 0.06
MTO-11A 0.48 14.12 0.28 6.91 0.17 1.10 5.40 0.04 8.20 1.60 0.60 0.42 0.09 8.98 5.14 0.08
MTO-14 0.93 16.70 0.10 4.53 0.11 0.15 5.20 0.04 2.70 2.00 0.66 0.52 0.14 10.37 0.37 0.06
MTO-18 0.36 10.91 0.29 3.66 0.25 0.46 4.80 0.25 20.3 1.70 0.99 0.41 0.11 5.99 16.13 0.04
Mixed samples
MTO-2 n.d. 6.30 n.d. 3.00 n.d. n.d. 2.60 0.82 37.7 1.20 n.d. 0.21 0.08 n.d. 28.0 n.d.
MTO-5 n.d. 9.70 n.d. 3.40 n.d. n.d. 2.60 0.20 36.7 1.30 n.d. 0.23 0.09 n.d. 23.0 n.d.
MTO-8 n.d. 10.50 n.d. 3.00 n.d. n.d. 1.20 0.56 29.4 2.00 n.d. 0.52 0.13 n.d. 19.0 n.d.
MTO-11B n.d. 10.90 n.d. 3.20 n.d. n.d. 1.50 0.42 24.6 2.20 n.d. 0.56 0.15 n.d. 17.0 n.d.
MTO-15 n.d. 8.80 n.d. 4.30 n.d. n.d. 1.90 0.51 29.2 2.00 n.d. 0.59 0.16 n.d. 19.0 n.d.
MTO-19 n.d. 7.00 n.d. 3.40 n.d. n.d. 2.50 0.49 36.6 2.20 n.d. 0.26 0.08 n.d. 23.0 n.d.
Biocalcarenite samples
MTO-3 n.d. 9.60 n.d. 3.60 n.d. n.d. 2.80 0.85 32.4 2.20 n.d. 0.36 0.10 n.d. 22.0 n.d.
MTO-6 n.d. 4.30 n.d. 2.30 n.d. n.d. 1.30 0.24 45.6 0.30 n.d. 0.17 0.07 n.d. 33.0 n.d.
MTO-9 n.d. 12.2 n.d. 4.60 n.d. n.d. 2.20 0.35 29.2 1.90 n.d. 0.65 0.16 n.d. 19.0 n.d.
MTO-12 n.d. 11.8 n.d. 3.20 n.d. n.d. 1.40 0.33 22.8 2.00 n.d. 0.63 0.13 n.d. 14.0 n.d.
MTO-13 n.d. 6.90 n.d. 3.30 n.d. n.d. 0.93 0.62 32.1 1.20 n.d. 0.32 0.14 n.d. 24.0 n.d.
MTO-16 n.d. 10.4 n.d. 6.00 n.d. n.d. 2.70 0.40 26.0 2.20 n.d. 0.62 0.14 n.d. 17.0 n.d.
MTO-17 n.d. 11.5 n.d. 4.00 n.d. n.d. 1.60 0.56 24.0 2.40 n.d. 0.49 0.15 n.d. 14.0 n.d.
MTO-20 n.d. 1.50 n.d. 1.20 n.d. n.d. 1.50 1.70 41.1 0.40 n.d. 0.06 0.06 n.d. 30.0 n.d.

Total SiO2: non-determined; L: labile oxides; n.d.: non-determined. Uncertainties of the reference materials are referred to the last significant digits.
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2267

Table 4
Chemical composition of the bulk samples (Trace elements)
Elements (ppm) As Ba Ce Co Cr Cu La Ni Sn Sr V W Y Zn Zr U
SRM-97b Certified – (180) – (3.8) 227 ± 12 – – – – 84 ± 2 – – – (87) (500) –
Obtained – 172 ± 12 – <5 230 ± 18 – – – – 86 ± 4 – – – 89 ± 6 468 ± 16 –
SRM-98b Certified – (700) – (16.3) 119 ± 5 – – – – 189 ± 8 – – – (110) (220) –
Obtained – 735 ± 28 – 19 ± 4 123 ± 8 – – – – 192 ± 10 – – – 119 ± 9 175 ± 18 –
SRM-88b Certified – – (3.8) (1.0) (2.3) – – – – 64 ± 3 – – – – – –
Obtained – – <10 <5 <5 – – – – 67 ± 5 – – – – – –

Samples Smectitised tuffaceous samples


MTO-1 274 535 23 21 19 9.6 12 24 <10 208 166 <25 <5 60 n.d. 3.1
MTO-4 <25 128 14 11 23 12 21 12 44 280 94 <25 6.8 37 n.d. 3.0
MTO-7 <25 108 21 17 14 14 22 21 44 268 91 <25 10 46 n.d. 1.4
MTO-10 <25 84 24 19 11 12 21 14 44 208 155 <25 16 50 n.d. 3.1
MTO-11A <25 155 <10 18 <5 14 14 17 44 140 158 <25 <5 90 n.d. 7.8
MTO-14 <25 32 36 9.1 6 10 23 13 <10 178 93 <25 10 54 n.d. 3.5
MTO-18 239 67 13 9.4 23 13 22 13 <10 225 69 <25 7.4 24 n.d. 3.2
Mixed samples
MTO-2 <25 200 <10 <5 13 9.3 19 12 <10 374 79 <25 <5 12 19 n.d.
MTO-5 <25 80 <10 <5 20 14 18 7.7 <10 265 63 <25 <5 16 22 n.d.
MTO-8 <25 251 <10 <5 26 12 20 23 <10 422 121 <25 6.5 6.2 33 n.d.
MTO-11B <25 150 <10 <5 25 22 22 26 <10 286 122 <25 12 11 40 n.d.
MTO-15 <25 122 <10 6.3 6.6 9 23 13 <10 291 123 <25 9.8 12 47 n.d.
MTO-19 <25 45 <10 <5 7.5 9.8 18 6.2 <10 266 49 <25 <5 9.1 25 n.d.
Biocalcarenite samples
MTO-3 <25 286 <10 <5 17 13 21 18 <10 285 175 <25 6.6 12 22 n.d.
MTO-6 <25 71 <10 <5 12 12 17 5.5 <10 325 50 <25 <5 7.4 13 n.d.
MTO-9 <25 133 <10 10 38 12 19 13 <10 374 131 <25 <5 17 31 n.d.
MTO-12 <25 126 <10 6 13 11 21 15 <10 290 130 <25 6.5 20 51 n.d.
MTO-13 <25 310 <10 <5 9.5 9.1 18 13 <10 312 66 <25 <5 5.4 25 n.d.
MTO-16 <25 239 <10 10 6.4 8.4 20 11 <10 285 114 <25 <5 17 39 n.d.
MTO-17 <25 192 <10 8.4 <5 7.4 20 5.1 <10 327 93 <25 <5 10 41 n.d.
MTO-20 <25 34 <10 <5 <5 11 22 19 <10 151 17 <25 7.1 <5 <5 n.d.

Major and trace elements of clayey fractions 4.3. Isotopic geochemistry


from the smectitised tuffaceous samples are listed
in Table 5. Considering both analytical and miner- 4.3.1. 87Sr/86Sr ratio in carbonate fraction from
alogical results (see Table 2), it can be stated that: mixed and biocalcarenite samples
(i) proximal samples are richer in Fe than distal The 87Sr/86Sr values of carbonates extracted
samples, for a similar smectite content; (ii) some from mixed and biocalcarenite samples (Table 6)
proximal samples (MTO-4, MTO-7 and MTO-18) range from 0.709219 (mixed sample MTO-5) to
are also richer in Mg than distal specimens; and 0.709902 (biocalcarenite sample MTO-3). The
(iii) only two proximal samples (MTO-1 and lower values are close to those for the Lower Tor-
MTO-18) are Mn-enriched with respect to distal tonian seawater (Veizer et al., 1999), approximately
ones. Given that the main mineral in these samples 11.6 Ma ago (Fig. 6(b)). This means that some
is smectite (approximately 93% as average value), samples almost totally preserve their original
87
the chemical composition of the clayey fractions, Sr/86Sr ratio, which represents that of marine
particularly major elements, seems to indicate that water at that time. However, the higher values
proximal smectites are richer in ferromagnesian must be explained considering the interaction be-
elements than distal ones. Nevertheless, trace ele- tween seawater and acid volcanic rocks, which ex-
ments are not useful to differentiate proximal to hibit high 87Sr/86Sr ratios. Since the volcanic
distal samples. activity in the region was of approximately 7 Ma
As a consequence, these geochemical features (see Fig 6(b)) and the volcanic rocks have 87Sr/86Sr
seem to support the secondary process deduced in values generally higher than 0.7105 (Fig. 6(a))
the previous section from the mineralogical features (Toscani et al., 1990; Arribas et al., 1995; Benito
of the proximal and distal samples. et al., 1999; Turner et al., 1999; Fernández-Soler,
2268 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

Table 5
Chemical composition of the clayey fractions from the smectitised tuffaceous samples
Oxides (%) MTO-1 (Pr) MTO-4 (Pr) MTO-7 (Pr) MTO-10 (D) MTO-11A (D) MTO-14 (D) MTO-18 (Pr)
Al2O3 10.9 12.7 11.3 14.7 13.3 12.9 10.2
Al2O3L 0.29 0.25 0.23 0.22 0.23 0.18 0.22
Fe2O3 8.10 6.28 5.33 4.87 3.58 3.05 7.89
FeO 0.18 0.28 0.24 0.20 0.11 0.13 0.10
Fe2O3L 0.79 0.56 0.27 0.36 0.65 0.16 0.37
MgO 5.5 8.0 7.0 6.6 5.8 5.7 7.1
MnO 0.5 0.03 0.03 0.03 0.03 0.03 0.15
CaO 0.94 2.0 2.70 1.80 1.60 0.80 7.9
Na2O 0.44 0.24 0.20 0.50 0.57 1.3 0.75
K2O 0.67 0.58 0.37 0.80 0.54 0.41 0.58
TiO2 0.26 0.16 0.27 0.18 0.15 0.21 0.31
P2O5 0.03 0.06 0.13 0.07 0.04 0.06 0.40
H2O 10.6 12.7 13.3 12.2 9.70 8.6 13.4
H2O+ 5.94 6.69 5.68 5.87 6.12 5.39 7.61
CO2 total 1.32 0.99 1.58 1.39 0.77 0.95 5.87
SO2 0.04 0.02 0.04 0.04 0.01 0.06 0.02
SiO2L n.d. 0.40 0.51 0.58 0.56 0.76 0.49
Total 46.5 51.94 49.18 50.41 43.76 40.69 63.34
Trace elements (ppm)
As 98 71 39 38 38 51 <25
Ba 229 51 28 52 115 11 30
Ce 15 <10 25 26 <10 33 14
Co 11 12 <5 18 6.8 11 11
Cr 36 37 31 21 <5 6.4 46
Cu 32 36 40 37 32 33 19
La 12 9.3 22 19 11 21 18
Ni 16 15 13 13 10 8 19
Sr 99 108 88 127 123 76 115
V 202 109 100 126 126 92 99
Y <5 <5 7.9 7.3 <5 9.2 <5
Zn 110 128 126 137 81 71 72
Zr 119 63 157 124 140 183 n.d
Li 150 180 290 240 230 230 200
U 2.3 1.5 1.6 2.3 2.5 2.8 2.4
(Pr): Proximal. (D): distal.

unpublished data), the diagenetic processes involv- those carbonates with d13C values more positive
ing 87Sr-enriched fluids could cover a period of than 2.5& (formed or transformed in equilibrium
approximately 4 Ma. That is, until approximately with marine waters) show a high dispersion in the
the end of the volcanic activity in the region (see d18O values (STD = 2.28), which is probably related
Fig. 6(b)). However, it cannot be stated that there to a wide temperature range (Fig. 7). However, car-
is any relationship between the 87Sr/86Sr values and bonates with d13C values more negatives than
the location of samples with respect to the volcanic 2.5& (formed or transformed under the influence
dome. of meteoric water) present a narrower range of d18O
values (STD = 0.45) that is typical of meteoric dia-
4.3.2. d18O and d13C in carbonate fractions from genesis under a narrow interval of temperatures (see
mixed and biocalcarenite samples Fig. 7). In fact, these last samples approximately
The isotopic signatures of carbonates extracted plot on the Meteoric Calcite Line (MCL) for the
from mixed and biocalcarenite samples (Table 7) site, which is located on the vertical of the d18O 
display a relatively high dispersion for both d18O 5& vs. PDB (Delgado, 1993), though slightly dis-
and d13C values, which range from 8.40& to placed toward more positive d18O values (4.5& vs.
+1.14& (PDB) and from 7.80& to +1.58& PDB as average value) (Fig. 8). Consequently, only
(PDB), respectively. It should be pointed out that these calcites originated at 15 C in equilibrium with
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2269

Table 6
87
Strontium contents and Sr/86Sr ratios of carbonate fraction from mixed and biocalcarenite bulk samples removed with Morgans
solution (pH 4.5)
87
Standard Sr/86Sr 87
Sr/86Sr measured External reproducibility (n)
NBS-987 0.71024 ± 2 0.710252 0.000004 (106)
Dolerite WS-E 0.706583 0.706596 0.000014 (39)

87
Sample Sr (ppm) Sr/86Sr Internal reproducibility
Biocalcarenite samples
MTO-3 285 0.709902 0.000014
MTO-6 325 0.709257 0.000014
MTO-9 360 0.709385 0.000021
MTO-12 290 0.709666 0.000043
MTO-13 315 0.709521 0.000021
MTO-16 300 0.709634 0.000100
MTO-17 355 0.709567 0.000014
MTO-20 155 0.709731 0.000050
Mixed samples
MTO-2 385 0.709308 0.000021
MTO-2R 265 0.709477 0.000014
MTO-5 265 0.709219 0.000014
MTO-8 405 0.709465 0.000014
MTO-11B 285 0.709797 0.000024
MTO-15 300 0.709681 0.000021
MTO-19 300 0.709241 0.000021

meteoric water, with an d18O value of 4.7& (V- tion for siderite has not yet been established.
SMOW). However, these temperatures do not show correla-
The high variability of d18O values in carbonates tion with mineralogy and neither with the location
with d13C values more positive than 2.5& is due to of samples, as mentioned for Sr isotopes (see
the presence of calcite formed under marine condi- Fig. 7).
tions, preserving its original d18O signature close Consequently, these isotopic data allow one to
to 0& (Anderson and Arthur, 1983), together with state that the carbonates found in the studied bio-
other secondary carbonates (calcite, dolomite and calcarenites clearly resulted from hydrothermal
siderite) neoformed under different conditions, such transformation processes that affected to marine-
as reheated marine waters. Thus, some of the more bioclastic materials, originally consisting of calcite
negative carbonates, such as calcite with d18O = and probably aragonite. After emersion, a new gen-
8.4& (PDB) and dolomite with d18O = 8.3& eration of meteoric calcite was formed as a result of
(PDB), indicate neoformation temperatures close the meteoric diagenesis.
to 60 and 90 C, respectively, if equilibrium with
seawater is assumed. 4.3.3. d18O and d2H in smectites from the smectitised
Summarising, only two samples preserves their tuffaceous samples
original isotopic signature in equilibrium with cold Proximal and distal smectites show relatively uni-
seawater, while a half of them were transformed in form d18O values, ranging from +18.5& to +20.1&
equilibrium with reheated seawater, in a tempera- (Table 8), the average value being +19.3& (V-
ture range from approximately 28 C to around SMOW). These isotopic signatures are relatively
60 C. The remaining samples were neoformed un- high and could be assigned to edaphic clays (Savin
der meteoric conditions. In contrast, dolomite is al- and Epstein, 1970; Savin and Lee, 1988; Lawrence
ways a secondary carbonate neoformed at a and Taylor, 1971, 1972). However, carbonates
temperature range from approximately 40 C to mixed with the smectitised layered tuffs have a mar-
around 90 C, also in equilibrium with reheated ine origin and were later affected by diagenetic pro-
seawater. Something similar occurs for siderite, if cesses involving reheated seawater (Delgado and
the fractionation equation for dolomite is extrapo- Reyes, 1993). Consequently, in order to estimate
lated to siderite, since a specific experimental equa- the most probable physicochemical conditions un-
2270 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

Fig. 6. (a) Frequency diagram showing the commonest 87Sr/86Sr values for the volcanic rocks in the Cabo de Gata region (values from
Toscani et al., 1990; Arribas et al., 1995; Benito et al., 1999; Turner et al., 1999; Fernández-Soler unpublished data). (b) Diagram showing
the 87Sr/86Sr values from biocalcarenite samples and volcanic rocks in relation to the secular variation of seawater 87Sr/86Sr of Veizer et al.
(1999), indicating the probable span of the water/rock interaction processes affecting carbonates.

der which the formation or transformation of these with an isotopic signature from 5.5& to 2.9&
smectites took place two approaches have been V-SMOW. These values were calculated from the
attempted. average d18O value of meteoric calcites (5& vs.
The first considers that these smectites were PDB) from the site (Delgado, 1993). In this manner,
formed or transformed in equilibrium with seawa- a temperature range from 22 C to approximately
ter, with d18O and dD values close to 0&. Following 46 C is obtained for the studied smectites (see
this hypothesis, the d18O values of the smectites Fig. 9). Though this range is narrower (between 26
indicate that they could be formed or transformed and 41 C) when the curve for the d18O average va-
at a temperature between 55 and 66 C (Fig. 9). lue (19.3&) is considered (see Fig. 9), these temper-
Slightly higher temperatures (between 75 and atures are higher than those expected for surficial
95 C) were obtained for the smectites from the processes and therefore this hypothesis must be
Morrón de Mateo bentonite deposit (Delgado and rejected.
Reyes, 1993; Delgado, 1993), which is located just The dD values of the smectites (from 83.6& to
in contact with the volcanic dome (see Fig. 9). 64.2& V-SMOW, see Table 8) show a larger
The second approach envisages that smectites dispersion than the d18O values. This fact has been
were formed or transformed as a result of weather- related to post-formational processes, mainly
ing processes, in equilibrium with meteoric water, weathering processes, involving isotopic exchanges
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2271

Table 7
Isotopic composition of carbonates (d & vs. PDB)
Extracted CO2
3 Calcite Dolomite Siderite
Profiles Samples d13C d18O d13C d18O d13C d18O
1 MTO-2 4.28 4.26 2.60 4.44 1.90 4.93
1 MTO-2R 4.25 3.87 2.87 4.28 2.33 4.52
1 MTO-3 7.80 4.20 – – – –
2 MTO-5 0.60 1.00 0.69 1.56 1.58 1.14
2 MTO-6 0.70 4.05 0.91 4.25 1.04 4.39
3 MTO-8 1.80 4.85 – – – –
3 MTO-9 0.70 5.90 0.30 6.75 – –
4 MTO-11B 5.98 5.10 – – – –
4 MTO-12 3.35 5.16 – – – –
4 MTO-13 2.10 8.40 0.98 8.30 – –
5 MTO-15 1.95 2.90 1.66 4.15 – –
5 MTO-16 0.85 3.30 0.10 2.96 1.21 6.60
5 MTO-17 0.20 1.25 – – – –
6 MTO-18 5.90 4.30 – – – –
6 MTO-19 0.71 5.03 0.00 4.50 – –
6 MTO-20 0.52 5.40 0.80 6.12 – –

of H (Delgado and Reyes, 1993; Delgado, 1993). plot on the curve corresponding to a meteoric
Furthermore, this hypothesis is in good agreement water, with a d18O value of 4& (Fig. 11). How-
with the theoretical calculations performed by Key- ever, when dD values are plotted ‘‘versus’’ these
ser and Kerrich (1991), who indicated that the temperatures, they fit well to a straight line that
clayey minerals can exchange H isotopes at 25 C, intersects almost all of the possible dD curves for
though the equilibrium is reached after approxi- meteoric water. Among them, the curve with a
mately 2 Ma. dD value of 22&, which corresponds to the
Taking into account both d18O and dD values of d18O value of 4&, is also intersected. Further-
the smectites, and given that theoretical smectite in more, this straight line shows two tendencies. The
equilibrium with seawater would have isotopic sig- first toward the curve corresponding to seawater,
natures (dD/d18O) of (64/+27); (59/+25); with dD of 0&, at a temperature slightly higher
(45/+21); (41/+19) and (35/+17), at 15, 25, than 60 C, and the second toward curves corre-
50, 60 and 75 C, respectively (Fig. 10), the dD val- sponding to very negative dD values, at tempera-
ues of the analysed smectites are not compatible tures lower than 20 C.
with seawater (see Fig. 10). These dD values would These two tendencies can be explained by con-
be either compatible with a genesis in equilibrium sidering that the smectites were probably formed
with meteoric waters or in equilibrium with seawa- or transformed in equilibrium with seawater at a
ter, if post-formational isotopic exchanges of only temperature around 60 C (55–65 C), as previ-
H occurred. ously deduced only from the d18O values (see
In order to test this last hypothesis, the geother- Fig. 9). At a later stage, weathering processes af-
mometric equation proposed by Delgado and Reyes fected these smectites involving only H isotopic ex-
(1996) has been applied, taking into account that it changes. The large dispersion of dD values is
is restricted to a temperature range from 0 to 150 explained by the variability in the extent of isoto-
and to smectites unaffected by post-formational ex- pic exchange between these smectites and meteoric
changes for H isotopes waters.
3:54  106 T 2 ¼ d18 Osm  0:125dDsm þ 8:95 Finally, though the temperature range calcu-
lated for the smectites is narrower than that calcu-
ðsm : smectiteÞ. lated for the carbonates, the former approximately
Thus, the d18O values measured on the smectites should correspond to the average temperature of
formed at temperatures ranging from 26 to 41 C the latter.
2272 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

Fig. 8. d13C (PDB)/d18O (PDB) diagram showing the composi-


tion of carbonates from the mixed and biocalcarenite samples.
Note that calcites with d13C values more negatives than 2.5&
plot close to the Meteoric Calcite Line (MCL) obtained from
regional calcites (Delgado, 1993).

bed (Table 9), as well as in their corresponding


clayey fractions (Table 10).
Based on the data from bulk samples, it can be
stated that the TEC is directly related to the phyl-
losilicate content in the samples and, in all of
them, the order of abundance of the exchangeable
cations is Mg2+ P Na+ > Ca2+ > K+  Sr2+. No
differences between proximal (MTO-1, 4, 7 and
18) and distal samples (MTO-10, 11A, 11B and
14) can be established. The TEC values of the
clayey fractions is closely related to the smectite
Fig. 7. Isotopic composition of the marine and meteoric
carbonates in relation to: (A) mineralogy, (B) distance from the content in the samples, if we take into account
Morrón de Mateo dome and (C) sampled profiles. Temperatures the uncertainties in both the semi-quantitative
were calculated using the Anderson and Arthur (1983) equation mineralogical composition and TEC measure-
and marine water (d18O = 0& vs. V-SMOW). ments. No differences between proximal and distal
samples are observed. However, the order of
abundance of exchangeable cations depends on
4.4. Physicochemical properties the samples, particularly regarding Ca2+, Mg2+
and Na+. It is noticeable that the amount of K+
Both total exchangeable cations (TECs) and BET in the clayey fractions is significantly lower than
specific surface area have been determined in bulk in the bulk samples, as well as the high content
samples from the smectitised pyroclastic bed, of Mg as an exchangeable cation in almost all
including samples MTO-11 A and B from the mixed the samples. The first feature could be explained

Table 8
Isotopic signature (d18O V-SMOW) of the <2 lm fractions from the smectitised tuffaceous samples
Profiles Samples Mineralogy d18O (V-SMOW) dD (V-SMOW) Location
1 MTO-1 94% smectite 19.6 77.2 Near the dome
2 MTO-4 95% smectite 18.9 74.4 Near the dome
3 MTO-7 99% smectite 19.1 83.6 Near the dome
4 MTO-10 95% smectite 18.8 64.2 Far from the dome
MTO-11 A 98% smectite 19.7 75.5
MTO-11 B 86% smectite 20.1 82.3
5 MTO-14 89% smectite 18.5 70.4 Far from the dome
6 MTO-18 90% smectite 19.8 87.6 Near the dome
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2273

Fig. 9. Diagram showing temperature and d18O (V-SMOW) values of waters. The curves represent the theoretical temperature of
formation of smectites and calcites in equilibrium with marine and meteoric waters. Surficial temperature (15–25 C) and meteoric calcites
(d18O = 5& vs. PDB) were used to calculate the isotopic composition of the meteoric waters. The Savin and Lee (1988) and Anderson
and Arthur (1983) equations were used for calculation. The dotted line represents the most common isotopic composition of smectites
from the Morrón de Mateo bentonite deposit.

by the absence of zeolites in the clayey fractions, without any apparent difference between proximal
given that these minerals can contain K as an and distal ones.
exchangeable cation. Regarding the second charac- As a consequence, it seems that no significant dif-
teristic, some of this Mg can be present as brucite ferences in the TEC and specific surface area values
either as impurities in the clayey fractions or as are observed in relation to the crystallochemical dif-
hydroxide-like layers in the smectite structure, as ferences observed between proximal and distal
explained before. In any case, brucite can be easily smectites.
dissolved during treatment for cation exchangeable
extraction, since it is soluble in ammonium salts. 5. Conclusions, analogies and implications for the
The specific surface area has been measured on performance assessment of the bentonite-engineered
bulk samples (see Table 9) and on 3 clayey frac- barrier
tions (see Table 10). As for TEC, the specific sur-
face area seems to be closely related to the The textural, mineralogical and chemical differ-
phyllosilicate and smectite contents in the samples, ences observed between carbonates from proximal

Fig. 10. Theoretical isotopic composition of smectites in equilibrium with seawaters (white squares) and in equilibrium with meteoric
waters (black-oblique rights) at different temperatures. Studied smectites are shown in black squares. The Savin and Lee (1988) and
Capuano (1992) equations were used for calculation of d18O and dD theoretical values, respectively.
2274 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

32 geochemical environments in the site. These differ-


30 ent geochemical environments were probably
28 developed after sedimentation of the volcano-
26 sedimentary series, as a result of the intrusion of
24 the Morrón de Mateo dome. Thus, this volcanic
22 intrusion could be the thermal agent and, particu-
20
larly, the source of Mg, Fe and Mn for the transfor-
18
18

mation of calcite into Mg–Fe–Mn-carbonates and


16
of Al-rich smectites into of Fe-rich and Mg-rich
14 -12 -10 -8 -6 -4 -2 0
12
smectites.
0
The geothermometric study of carbonates al-
-40 -6
-22 lowed the distinguishing of a generation of second-
-50
-60 -38
ary carbonates (calcite, dolomite and minor
-70 siderite) neoformed and isotopically re-equilibrated
-54 with re-heated seawater at a temperature range be-
-80
-90 -70 tween 28 C and approximately 90 C. Something
-100 similar occurs in smectites, since they were formed
-110 -86
D

or transformed at a temperature range between 55


-120
-130
and 66 C, which approximately agrees with the
-140 average temperature for the secondary carbonates.
0 20 40 60 80 100 120 However, no relationship between the tempera-
Temperature(˚C) tures of formation or neoformation for each sam-
Fig. 11. Graphic representation of the geothermometric equation
ple and its location with respect to the volcanic
proposed by Delgado and Reyes (1996). Fractionation of oxygen dome is observed. As a consequence, a clear ther-
(above) and hydrogen (below) in the smectite–water (marine and mal gradient from proximal to distal samples can-
meteoric) system are represented as a function of temperature. not be established. This means that the geological
The curves indicate the theoretical isotope values of smectites environment where the transformation processes
formed in equilibrium with different meteoric waters, as well as in
equilibrium with seawaters. The d18O/dD pairs that lie on the
affecting carbonates and smectites reached a rela-
Meteoric Water Line (MWL) are 2/4; 4/22; 6/38; 8/ tively similar temperature in the whole studied
54; 10/70 and 12/86, while the pair 0/0 correspond to area. This was likely due to the small size, shallow
seawaters. Note how for temperatures other than 26–41 C the and semi-closed character of the marine basin, as
isotopic composition of the original water is not compatible with well as the contemporary and intense geothermal
the MWL. However, temperatures plotted on the lower diagram
fit well to a straight line that suggests a post-formational
activity in the site, of which the Morrón de Mateo
exchange for hydrogen isotopes. dome was the main, but not unique, volcanic
manifestation.
and distal samples, as well as the crystallochemical Regarding the ENRESA design for a deep geo-
differences detected between distal and proximal logical repository (Astudillo, 2001), the candidate
smectites suggest the existence of two different bentonite to build the bentonite-engineered barrier

Table 9
Total exchangeable cations (meq/100 g) and Bet specific surface area (m2/g) of bulk samples from the tuffaceous and mixed beds
Profiles Samples Location Phy (%) Na+ K+ Ca2+ Mg2+ Sr2+ Total CEC  (m2/g)
A
1 MTO-1 Proximal 64 22.3 6.6 12.1 28.1 0.1 69.2 45.08
2 MTO-4 Proximal 57 17.5 5.4 20.6 27.4 0.1 71 32.91
3 MTO-7 Proximal 50 23.9 6.0 7.0 18.9 0.1 55.9 40.70
4 MTO-10 Distal 55 19.6 5.0 14.2 21.8 0.1 60.7 40.79
4a MTO-11A Distal 88 35.4 6.7 27.9 39.2 0.2 109.4 68.66
4a MTO-11B Distal 26 16.1 3.6 5.5 15.6 0.0 40.8 29.27
5 MTO-14 Distal 80 46.6 5.3 17.7 38.6 0.1 108.3 54.82
6 MTO-18 Proximal 34 0.1 2.5 8.1 15.4 0.1 26.2 18.52
a
Samples from the mixed bed. Sample MTO-11A was previously treated with Na-hexamethaphosphate for dispersion. Phy:
phyllosilicates.
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2275

Table 10
Total exchangeable cations (meq/100 g) and Bet specific surface area (m2/g) of <2 lm fractions from the tuffaceous samples
Profiles Samples Location Sm. (%) Na+ K+ Ca2+ Mg2+ Sr2+ Total CEC  (m2/g)
A
1 MTO-1 Proximal 94 25.2 3.2 22.8 56.5 0.1 107.8 n.d.
2 MTO-4 Proximal 95 39.9 3.7 45.7 33.3 0.2 122.8 n.d.
3 MTO-7 Proximal 97 49.6 3.8 28.5 23.5 0.1 105.5 n.d.
4 MTO-10 Distal 95 39.6 4.2 19.3 32.9 0.1 96.1 98.37
5 MTO-14 Distal 89 30.1 2.7 24.4 54.5 0.2 111.9 n.d.
6 MTO-18 Proximal 76 0.3 2.0 51.1 38.0 0.2 91.6 90.21
Sm., smectite; n.d., non-determined.

is an Al-smectite similar to that from the distal zone Based on these analogies, the neoformation of Fe
(El Murciano area) of the Morrón de Mateo volca- (Mg)-rich smectites observed in the proximal zones
nic dome. Furthermore, the thermal peak induced of the natural system would be expected in the ben-
by radioactive decay of the nuclear spent fuel after tonite barrier of the repository, in which an en-
burial, estimated to reach some 100 C, is another hanced Fe concentration close to the container
important physical variable of the man-made sys- can be induced as a result of its oxidation under
tem, since this parameter will have a large influence intermediate redox conditions. In this scenario, no
on the hydrated bentonite barrier. This temperature variations in the physicochemical properties, i.e.,
is also similar to that calculated for the natural sys- TEC and BET specific surface area, of the bentonite
tem studied. barrier will occur, as this study has demonstrated.
After sealing of a deep geological repository, it is However, under a stronger or longer interaction,
expected that the steel container will be affected by the neoformation of trioctahedral smectites such
two corrosion phases. The first will occur immedi- as saponite-stevensite, Fe(II)-rich saponite or dioc-
ately post-closure, under aerobic conditions, and tahedral nontronite (as a function of the Mg and
as a result of the oxidation by the air occluded in Fe(II)/Fe(III) activities in the environment, respec-
the bentonite barrier. These effects will be weak tively), corrensite and Fe–Mg-rich chlorite may oc-
and restrictive in space. In contrast, during the sec- cur as recorded in some active geothermal and
ond phase, which will start when the barrier is to- diagenetic systems (Yamada and Nakasawa, 1993;
tally saturated (approximately 103–104 a), the Beaufort et al., 1995, 2001; Bril et al., 1996; Robin-
oxidation of the steel container will occur, resulting son and Santana de Zamora, 1999; Mayayo et al.,
in the formation of both magnetite (Fe3O4) and Fe- 2000; Hover and Ashley, 2003). In these circum-
oxyhydroxides or siderite (FeCO3), depending on stances, significant variations in the physicochemi-
the physicochemical conditions in the system, and cal and physicomechanical properties of the
the production of hydrogen. In any case, the prob- bentonite-engineered barrier of a deep geological
able coexistence of Fe(II) and Fe(III) indicates that repository of radwastes could be expected.
transitional redox conditions can prevail in the
man-made system. Acknowledgements
With respect to the natural system all these
physicochemical conditions were met as a result Financial support for this work has been pro-
of the volcanic dome intrusion. So, relatively high vided by ENRESA (Spain). We are grateful to
temperature, Fe(II)–Fe(III) concentration, total M.D. Sánchez de Ledesma M. Sánchez and Dr.
hydration of the smectitised tuffaceous bed and M. Fernández from the Chemistry Division of CIE-
transitional redox conditions worked all together MAT for the chemical analyses, and Dr. A.M.
close to the Morrón de Mateo volcanic dome. Fernández for the cation exchangeable determina-
Consequently, among the main processes expected tions. We also thank to L. Gutiérrez-Nevot for the
in the bentonite-engineered barrier, the transforma- XRD diagrams and J.M. Durán for the BET spe-
tion of Al-smectites into other phyllosilicates is the cific surface area measurements. Dr. R. Pusch and
most relevant, as a result of the interaction be- an anonymous reviewer are also thanked for their
tween smectite, temperature and geochemical useful criticisms, comments and suggestions that im-
conditions. proved the manuscript.
2276 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

Appendix A

Chemical composition and structural formulae of proximal smectites (Sample MTO-1)


Oxides (%) 1 2 3 4 5 6 7 8 9 10
SiO2 65.74 65.58 65.71 63.69 65.44 65.37 63.85 66.11 65.91 65.28
Al2O3 13.24 24.39 15.04 16.14 15.79 16.18 14.94 15.68 19.41 14.31
Fe2O3 13.57 4.33 9.37 10.40 9.41 9.61 10.96 8.87 4.87 11.34
MgO 5.91 4.16 6.97 7.05 6.93 7.00 6.90 6.72 6.76 6.67
K2O 0.11 0.35 0.83 0.79 0.77 0.35 0.79 0.50 0.83 0.20
CaO 0.79 0.73 0.99 0.88 0.67 0.83 1.05 0.87 0.85 1.10
Na2O 0.63 0.45 1.09 1.04 0.98 0.67 1.51 1.25 1.36 1.10
Total 100.0 99.9 100.0 99.9 99.9 100.0 100.0 100.0 99.9 100.0
Tetrahedral cations Numbers of cations on the basis of O20(OH)4
Si 7.97 7.71 7.93 7.76 7.88 7.85 7.77 7.94 7.85 7.94
Al
P 0.03 0.29 0.07 0.24 0.12 0.15 0.23 0.06 0.15 0.06
Tetrahedral 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00
Octahedral cations
Al 1.86 3.09 2.07 2.07 2.13 2.14 1.92 2.16 2.57 1.99
Fe3+ 1.32 0.41 0.91 0.95 0.91 0.93 1.07 0.86 0.47 1.04
Mg
P 1.07 0.73 1.25 1.28 1.24 1.25 1.25 1.20 1.20 1.21
Octahedral 4.24 4.23 4.23 4.31 4.28 4.33 4.24 4.22 4.23 4.23
Interlayer cations
Ca 0.10 0.09 0.13 0.11 0.09 0.11 0.14 0.11 0.11 0.14
Na 0.15 0.10 0.25 0.25 0.23 0.16 0.36 0.29 0.31 0.26
K 0.02 0.05 0.13 0.12 0.12 0.05 0.12 0.08 0.13 0.03
Interlayer charge 0.37 0.34 0.64 0.60 0.52 0.42 0.75 0.59 0.66 0.57
Tetrahedral charge (%) 9.25 85.34 11.13 40.39 22.35 34.77 30.10 9.60 23.47 11.30

(Sample MTO-4)
Oxides (%) 1 2 3 4 5 6 7 8 9 10 11
SiO2 59.68 59.89 60.86 62.68 63.44 61.17 66.36 63.95 63.85 60.25 60.5
Al2O3 18.89 17.93 17.18 16.57 9.8 17.67 19.2 15.91 14.94 17.64 14.38
Fe2O3 7.76 8.95 7.49 8.73 7.4 8.54 4.35 10.96 10.96 8.35 10.73
MgO 9.85 9.77 10.25 9.96 18.1 10.17 7.69 6.64 6.90 12.66 12.0
K2O 0.59 0.5 0.42 0.24 0.05 0.22 0.44 0.49 0.79 0.16 0.20
CaO 1.6 1.51 2.21 1.72 0.97 1.03 0.76 0.78 1.05 1.92 1.01
Na2O 1.64 1.44 1.58 0.1  1.21 1.19 1.27 1.51 0.00 1.27
Total 100 99.99 99.99 100.0 99.67 100.0 99.99 100.0 100.0 100.98 100.1
Tetrahedral cations Numbers of cations on the basis of O20(OH)4
Si 7.28 7.31 7.42 7.57 7.70 7.44 7.88 7.79 7.77 7.25 7.41
Al
P 0.72 0.69 0.58 0.43 0.30 0.56 0.12 0.21 0.23 0.75 0.59
Tetrahedral 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00
Octahedral cations
Al 1.99 1.89 1.88 1.93 1.11 1.98 2.57 2.07 1.92 1.75 1.48
Fe3+ 0.76 0.88 0.73 0.85 0.72 0.79 0.39 1.00 1.07 0.81 1.05
Mg 1.79 1.78 1.86 1.79 3.28 1.84 1.36 1.21 1.25 2.27 2.19
P
Octahedral 4.54 4.55 4.48 4.57 5.10 4.60 4.32 4.28 4.24 4.83 4.73
Interlayer cations
Ca 0.21 0.20 0.29 0.22 0.13 0.13 0.10 0.10 0.14 0.25 0.13
Na 0.39 0.34 0.37 0.02 0.00 0.29 0.27 0.30 0.36 0.00 0.30
K 0.09 0.08 0.07 0.04 0.01 0.03 0.07 0.08 0.12 0.02 0.03
Interlayer charge 0.83 0.90 1.02 0.51 0.25 0.59 0.53 0.58 0.75 0.52 0.60
Tetrahedral charge (%) 87.27 76.24 57.30 83.84 118.46 94.60 22.77 36.72 30.10 143.78 98.66
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2277

Appendix A (continued)
(Sample MTO-7)
Oxides (%) 1 2 3 4 5 6 7 8 9 10
SiO2 65.61 65.58 66.39 60.65 65.52 64.45 65.12 60.65 64.95 66.50
Al2O3 15.27 15.88 15.45 18.72 16.03 15.51 14.89 18.72 15.14 15.61
Fe2O3 7.79 7.80 8.38 8.45 6.80 8.34 7.26 8.45 8.07 7.53
MgO 8.28 8.14 7.88 8.10 8.29 9.23 9.76 8.13 9.71 8.24
K2O 0.24 0.31 0.24 0.00 0.00 0.00 2.20 0.00 0.00 0.00
CaO 1.64 1.92 1.66 2.23 1.75 2.47 0.00 2.23 2.13 2.12
Na2O 0.00 0.37 0.00 1.80 1.33 0.00 0.78 1.82 0.00 0.00
Total 98.83 100.0 100.0 99.95 99.72 100.0 100.0 100.0 100.0 100.0

Tetrahedral cations Numbers of cations on the basis of O20(OH)4


Si 7.75 7.87 7.94 7.38 7.87 7.76 7.87 7.38 7.80 7.94
Al
P 0.25 0.13 0.06 0.62 0.13 0.24 0.13 0.62 0.20 0.06
Tetrahedral 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00

Octahedral cations
Al 1.96 2.11 2.12 2.07 2.14 1.96 1.99 2.06 1.95 2.14
Fe3+ 0.75 0.75 0.80 0.83 0.66 0.81 0.70 0.82 0.78 0.72
Mg
P 1.50 1.46 1.41 1.47 1.48 1.66 1.76 1.47 1.74 1.47
Octahedral 4.20 4.32 4.33 4.36 4.28 4.42 4.46 4.36 4.46 4.33

Interlayer cations
Ca 0.31 0.25 0.00 0.29 0.23 0.32 0.00 0.00 0.27 0.27
Na 0.41 0.09 0.21 0.42 0.31 0.00 0.18 0.29 0.00 0.00
K 0.10 0.05 0.00 0.00 0.00 0.00 0.34 0.43 0.00 0.00
Interlayer charge 1.13 0.63 0.46 1.06 0.76 0.64 0.52 1.02 0.55 0.54

Tetrahedral charge (%) 22.17 21.06 12.16 58.39 16.71 38.00 24.68 60.92 36.07 10.74

(Sample MTO-18)
Oxides (%) 1 2 3 4 5 6 7 8 9
SiO2 61.48 63.02 64.23 55.45 63.74 64.86 63.94 62.86 65.45
Al2O3 14.69 14.02 15.71 10.06 14.96 15.15 14.97 14.86 16.90
Fe2O3 9.46 8.87 8.57 13.09 7.95 8.63 8.81 9.28 6.45
MgO 10.49 10.74 8.07 18.47 11.34 9.11 8.99 9.50 8.13
K2O 0.42 0.30 0.13 0.16 0.73 0.25 0.90 0.95 0.58
CaO 1.97 3.04 2.18 1.78 1.28 1.59 1.95 1.94 2.16
Na2O 1.48 0.00 1.11 0.98 0.00 0.41 0.45 0.63 0.34
Total 99.99 99.99 100.00 99.99 100.00 100.00 100.01 100.02 100.01

Tetrahedral cations Numbers of cations on the basis of O20(OH)4


Si 7.52 7.66 7.76 6.97 7.69 7.81 7.75 7.66 7.84
Al 0.48 0.34 0.24 1.03 0.31 0.19 0.25 0.34 0.16
P
Tetrahedral 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00

Octahedral cations
Al 1.64 1.67 2.00 0.46 1.82 1.96 1.89 1.79 2.23
Fe3+ 0.93 0.87 0.83 1.32 0.77 0.83 0.86 0.91 0.62
Mg 1.91 1.95 1.45 3.46 2.04 1.63 1.62 1.73 1.45
P
Octahedral 4.49 4.48 4.28 5.25 4.63 4.43 4.37 4.42 4.30

Interlayer cations
Ca 0.26 0.40 0.28 0.24 0.17 0.21 0.25 0.25 0.28
Na 0.35 0.00 0.26 0.24 0.00 0.10 0.10 0.14 0.08
K 0.07 0.05 0.02 0.03 0.11 0.04 0.14 0.15 0.09
(continued on next page)
2278 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

Appendix A (continued)
Oxides (%) 1 2 3 4 5 6 7 8 9
Interlayer charge 0.93 0.83 0.84 0.74 0.44 0.54 0.74 0.79 0.72

Tetrahedral charge (%) 51.20 40.79 28.47 138.73 68.91 35.42 33.17 43.54 22.27

Appendix B

Chemical composition and structural formulae of distal smectites (Sample MTO-10)


Oxides (%) 1 2 3 4 5 6 7 8 9
SiO2 66.90 65.97 65.15 64.03 65.85 66.26 67.00 67.22 62.18
Al2O3 18.70 19.45 19.34 17.78 18.86 18.98 16.50 18.00 19.46
Fe2O3 5.65 5.39 5.42 7.44 5.97 6.09 5.80 5.65 6.76
MgO 7.61 7.27 7.99 8.36 7.73 7.30 7.61 7.61 8.22
K2O 0.85 0.33 0.33 0.75 0.33 0.37 0.35 1.04 0.51
CaO 0.20 1.46 1.78 1.43 1.18 1.34 2.41 0.49 1.17
Na2O 0.10 0.13 0.00 0.21 0.08 0.00. 0.33 0.00 1.70
Total 100.0 100.0 100.0 100.0 100.0 100.3 100.0 100.0 100.0

Tetrahedral cations Numbers of cations on the basis of O20(OH)4


Si 7.92 7.82 7.75 7.69 7.82 7.85 7.98 7.97 7.50
Al
P 0.08 0.18 0.25 0.31 0.18 0.15 0.02 0.03 0.50
Tetrahedral 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00

Octahedral cations
Al 2.51 2.54 2.46 2.21 2.46 2.51 2.30 2.48 2.27
Fe3+ 0.53 0.51 0.52 0.72 0.57 0.58 0.55 0.54 0.65
Mg 1.33 1.28 1.42 1.50 1.37 1.29 1.35 1.34 1.48
P
Octahedral 4.37 4.34 4.39 4.42 4.39 4.38 4.21 4.36 4.40

Interlayer cations
Ca 0.05 0.19 0.23 0.18 0.15 0.13 0.31 0.06 0.15
Na 0.05 0.03 0.00 0.05 0.02 0.00 0.08 0.00 0.40
K 0.16 0.05 0.04 0.12 0.05 0.08 0.05 0.16 0.08

Interlayer charge 0.30 0.45 0.50 0.53 0.37 0.31 0.74 0.28 0.78

Tetrahedral charge (%) 27.66 39.60 50.84 58.05 49.19 46.99 2.16 11.40 64.25

(Sample MTO-11A)a
Oxides (%) 1 2 3 4 5 6 7 8 9 10
SiO2 64.50 64.82 66.68 66.76 67.20 66.01 65.78 66.42 65.87 67.13
Al2O3 19.83 19.44 17.23 19.09 18.25 18.51 18.41 16.65 18.47 17.29
Fe2O3 4.71 5.38 5.73 4.59 4.41 4.88 4.98 6.17 4.87 5.31
MgO 6.88 6.68 7.09 6.65 6.31 6.80 7.25 7.00 6.79 6.86
K2O 0.56 0.54 0.61 0.71 0.55 0.66 0.86 0.45 0.66 0.82
CaO 0.92 0.79 1.08 1.09 1.19 0.98 0.56 1.11 0.98 1.35
Na2O 2.50 2.35 1.58 1.11 2.14 2.15 2.15 2.19 2.35 1.23
Total 99.99 100.0 100.0 100.0 100.0 99.99 99.99 99.99 99.99 99.99
L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282 2279

Appendix B (continued)
Oxides (%) 1 2 3 4 5 6 7 8 9 10
Tetrahedral cations Numbers of cations on the basis of O20(OH)4
Si 7.72 7.75 7.96 7.92 7.99 7.88 7.86 7.95 7.87 8.00
Al
P 0.28 0.25 0.04 0.08 0.01 0.12 0.14 0.05 0.13 0.00
Tetrahedral 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00

Octahedral cations
Al 2.52 2.49 2.38 2.59 2.54 2.48 2.45 2.30 2.47 2.43
Fe3+ 0.45 0.52 0.55 0.44 0.42 0.47 0.48 0.59 0.47 0.51
Mg
P 1.23 1.19 1.26 1.18 1.12 1.21 1.29 1.25 1.21 1.22
Octahedral 4.20 4.20 4.19 4.21 4.08 4.16 4.22 4.15 4.15 4.16

Interlayer cations
Ca 0.12 0.10 0.14 0.14 0.15 0.13 0.07 0.14 0.13 0.17
Na 0.58 0.54 0.37 0.25 0.49 0.50 0.50 0.51 0.54 0.29
K 0.09 0.08 0.09 0.11 0.08 0.10 0.13 0.07 0.10 0.13

Interlayer charge 0.90 0.83 0.75 0.64 0.88 0.85 0.77 0.86 0.90 0.75

Tetrahedral charge (%) 30.83 29.70 5.72 12.30 1.41 14.31 18.26 5.55 14.42 0.07
a
Sample treated with Na-hexamethaphosphate for dispersion (the amount of exchangeable Na is higher than in smectites of the other
samples).

(Sample MTO-14)
Oxides (%) 1 2 3 4 5 6 7 8 9 10
SiO2 66.77 67.15 67.09 66.21 65.92 66.36 66.83 67.29 68.00 67.75
Al2O3 18.20 18.90 17.97 19.20 19.96 18.79 18.38 19.06 18.80 20.36
Fe2O3 4.66 4.37 4.81 4.59 4.47 4.36 4.40 4.66 5.04 4.40
MgO 8.08 6.80 7.35 7.75 7.04 7.20 7.17 7.59 7.26 6.98
K2O 0.42 0.35 0.18 0.18 0.48 0.00 0.54 1.16 0.00 0.51
CaO 0.00 2.00 0.74 0.59 1.01 0.95 0.72 0.24 0.46 0.00
Na2O 1.87 0.52 1.85 1.47 1.12 2.34 1.96 0.00 0.44 0.00
Total 100.00 100.09 99.99 99.99 100.0 100.0 100.0 100.0 100.0 100.0

Tetrahedral cations Numbers of cations on the basis of O20(OH)4


Si 7.92 7.94 7.96 7.85 7.82 7.88 7.94 7.95 8.00 7.95
Al 0.08 0.06 0.04 0.15 0.18 0.12 0.06 0.05 0.00 0.05
P
Tetrahedral 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00 8.00

Octahedral cations
Al 2.47 2.58 2.47 2.53 2.61 2.51 2.51 2.60 2.60 2.76
Fe3+ 0.44 0.41 0.46 0.44 0.43 0.42 0.42 0.44 0.48 0.41
Mg
P 1.43 1.20 1.30 1.37 1.24 1.27 1.27 1.34 1.27 1.22
Octahedral 4.34 4.19 4.23 4.34 4.28 4.20 4.20 4.38 4.35 4.40

Interlayer cations
Ca 0.00 0.25 0.09 0.07 0.13 0.12 0.09 0.03 0.06 0.00
Na 0.43 0.12 0.43 0.34 0.26 0.54 0.45 0.00 0.10 0.00
K 0.06 0.05 0.03 0.03 0.07 0.00 0.08 0.17 0.00 0.08

Interlayer charge 0.49 0.68 0.64 0.51 0.58 0.78 0.72 0.24 0.21 0.07

Tetrahedral charge (%) 16.03 8.35 6.06 29.87 31.31 15.04 8.27 20.91 0.90 73.59
2280 L.P. del Villar et al. / Applied Geochemistry 20 (2005) 2252–2282

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