Chemical Geology, 112 (1994) 221-245 221

Elsevier Science B.V., Amsterdam

[CA]

Geochemistry of Spanish sepiolite-palygorskite deposits:

Genetic considerations based on trace elements and isotopes

J. Torres-Ruiz', A. L6pez-Galindo a, J.M. Gonz,'tlez-L6pezb a n d A. Delgado c

°Departamento de Mineralogia y Petrologla and IAGM, Facultad de Ciencias, Universidadde Granada-CSIC, Granada, Spain
bDepartamento de Ciencias de La Tierra, Facultad de Ciencias, Universidadde Zaragoza, Zaragoza, Spain
CEstacidn Experimental del Zaidin, CSIC, Granada, Spain
(Received March 4, 1993; revised and accepted July 14, 1993 )

ABSTRACT

Sepiolite-palygorskite deposits in Spanish Tertiary basins were formed in lacustrine environments. The mineral associ-
ations present in the mineralised intervals are made up of neoformed phyllosilicates (sepiolite, palygorskite, stevensite),
detrital silicates ( quartz, feldspars, illite, interstratified smectite-iUite, Al-smectite and kaolinite) and carbonates (calcite,
dolomite). Opal-A, gypsum and halite may also appear sporadically. Two groups of chemical elements and minerals can
be distinguished according to their origin: A1, Ti, Fe, Mn, K, REE and transition trace elements are almost exclusively
included in the detrital Al-silicates; Mg, Ca, C1, F and Li are concentrated in the minerals formed in the depositional basins.
Si, Na, Sr and Ba are contained in both detrital and neoformed minerals. REE, transition trace elements, F and Li contents
can be used to distinguish between phyllosilicates formed by chemical precipitation in the depositional basins, detrital
phyllosilicates, and those formed by transformation of the latter during early diagenetic processes. These data, together
with those on JtaO isotopic fraetionation indicate the formation of sepiolite and Mg-smectite as chemical precipitates,
whereas palygorskite would derive from diagenetic transformation of other inherited clay minerals. The values calculated
for the at,~pio~ite-,,tcr~and O/(palygorskite_watcr)fractionation factors at 20°C are 1.031 and 1.027, respectively.

1. Introduction sent the principal, most characteristic mineral

Fibrous clay minerals are of great economic
interest because of their multiple industrial ap-
plications. Spain has abundant, large sedimen-
tary deposits of sepiolite and/or palygorskite,
most of which have been studied, particularly
with regard to their mineralogical characteris-
ation and the environments in which they
formed (el. Gal~tn and Castillo, 1984 and ref-
erences therein). However, there is hardly any
information on their geochemistry. This paper
aims to present a geochemical characterisation
of this type of mineral deposit [ including data
on rare-earth elements (REE) and isotopes of
C and O ]. On the basis of existing knowledge,
we therefore selected eighty-eight samples from
eight deposits in the Tajo, Duero, Calatayud-
Teruel and Guadalquivir basins, which repre-
facies present in mineralized intervals of these
deposits. All the deposits studied are Neogene
and were formed in restricted continental or
perimarine lacustrine basins.
2. Geological setting
Fig. 1 shows the location of the four conti-
nental basins in which the deposits studied are
found. The main characteristics of these bas-
ins are as follows:
( 1 ) Tajo Basin. Located in the central part
of the Iberian Peninsula, this basin is charac-
terised by three main types of facies, which are,
from border to centre: marginal arkosic facies,
transitional facies (Vicalvaro, Cerro Batal-
lones and Parla deposits) and evaporitic cen-
tral facies (Gahtn and Castillo, 1984). The

0009-2541/94/$07.00 © 1994 Elsevier Science B.V. All fights reserved.

SSDI 0 0 0 9 - 2 5 4 1 ( 9 3 ) E 0 1 8 6 - W
222
o , ,, , '
. 1989 ). The Almaz,'in Sub-basin is located in the
o
ii_~ ¢- co°
(.
o and gypsum-bearing marls covered by the so-
~ ~ ~ oJ~--~
o _ _ .' ~ / A
~ ~ g ~
2o0Km
Fig. 1. Main Spanish Tertiary basins and location of de-
posits studied in this paper (A.b=Almaz~ln Basin; C-
T.b= Calatayud-Teruel Basin; AB.b= Albacete Basin;
M.b= La Mancha Basin; B.b=Badajoz Basin; P.b= Por-
tuguese Basin; 1 = Vic~varo deposit; 2 = Cerro Batallones
deposit; 3=Parla deposit; 4=Pareja deposit; 5 = Made-
ruelo deposit; 6=Almaz~in deposit; 7=Calatayud de-
posit; 8=El Cuervo deposit),
main sediment supplies are provided by the ig-
neous and metamorphic rocks of the Sierra de
Guadarrama. To the east of this basin, and
separated from it by the Sierra de Altomira, is
the so-called "Eastern Tajo Sub-basin", in the
northern part of which the Pareja deposit is lo-
cared in gypsum-bearing marls of the evapori-
tic facies (Martin-Pozas et al., 1981 ). The
uplift of Sierra de Altomira occurred after the
evaporitic sedimentation, and is therefore not
a source area for this sub-basin. The principal
supplies were provided by the Iberian Cordil-
lera. In the quarry of the Cerro Batallones se-
piolite deposit, located in the upper part of the
Miocene Intermediate Unit south of Madrid,
the recent discovery of vertebrate fossils has
permitted dating of these levels to the Valle-
sian (Morales et al., 1992 ).
(2) Duero Basin. Situated to the north of the
Tajo Basin, this basin includes the Maderuelo
deposit in its southern sector. The terrigenous
facies of this deposit came from the erosion of
the Palaeozoic (slates, quartzites and gneisses)
and Mesozoic materials (variegated clays,
J. TORRES-RUIZET AL.
marls, marly limestones, sandstones and lime-
stones ) of the Sierra de Pradoles (Suarez et al.,
easternmost part of the Duero Basin. The
southern sector of this basin consists of a mar-
ginal facies of sandstones and poorly evolved
conglomerates, and an inner facies of clayey
called " P ~ a m o limestones". Sediment was
supplied from the southern border (varieties
of Jurassic and Cretaceous limestones, to-
gether with sandstones and Triassic marls) and
from the eastern border (the above-mentioned
Palaeozoic materials) (S~lnchez de la Torre,
1963 ).
( 3 ) Guadalquivir Basin. Situated in south-
e a s t e r n Spain, this consists of a lower s e q u e n c e
of marine sediments and an upper sequence
formed in a perimarine brackish lacustrine e n -
vironment (Gahin and Ferrero, 1982 ). The El
Cuervo deposit is located in the second, Upper
Pliocene sequence. Three depositional units
can be distinguished in this lacustrine se-
quence (Casas et al., 1987 ), whose sediments
were supplied by the Keuper gypsum-bearing
marls of Germanic-Andalusian facies and by
Palaeogene clays. The commercially exploited
levels are found in the lower and upper units.
(4) Calatayud Basin. Located in northeast-
ern Spain, adjacent to the Ebro Basin. This is
an elongated depression with NW-SE axis and
represents the morphological unit of the Iber-
ian Cordillera that constitutes the boundary
between the two realms known as the Castilian
and Aragonese Branches. Although smaller,
this basin presents a facies distribution similar
to that of the Tajo Basin, i.e. marginal-detrital,
transitional (including the sepiolite deposits)
and central-evaporitic (Arauzo et al., 1989).
The source area is made up of Palaeozoic ma-
terials (slates, sandstones, quartzites and car-
bonates) from the sierras constituting the Ar-
agonese Branch of the Iberian Cordillera.
The sedimentological characteristics of the
Neogene deposits studied here, and in partic-
ular the associations of the neoformed clay
GEOCHEMISTRY OF SPANISH SEPIOLITE-PALYGORSKITEDEPOSITS
minerals, indicate that the sepiolite a n d / o r
palygorskite deposits were formed in alkaline
continental lacustrine environments during
periods of tectonic calm, in a warm climate
with semi-arid or seasonal arid conditions
(Gal,'tn and Castillo, 1984 ).
3. Methodology
3.1. Mineralogical characterisation
Determination of mineral phases was car-
ried out by X-ray diffraction ( X R D ) , using a
Philips ® PW1710, Cu-K,~ radiation and auto-
matic slit, and by the powder method and ori-
ented aggregates treated with ethylene-glycol,
dimethyl-sulphoxide and heating to 350°C.
The quantitative mineralogical analysis was
carded out using information from chemical
analyses and from XRD, according to the min-
eralogical peculiarities of each sample. The
values obtained by the classic method (area
measurement of peaks and reflective power,
e.g. Schultz, 1964; Biscaye, 1965) were cor-
rected according to the chemical composition
of the rock and taking into account the follow-
ing data: (a) the chemical composition of
mineral phases such as sepiolite, palygorskite
and trioctahedral smectite, calculated from
chemical analyses of practically monomineral
samples; (b) the only phases containing signif-
icant quantities of K in their structure are il-
lite, interstratified illite-smectite and potas-
sium feldspar; (c) Ca is almost exclusively
contained in the carbonates; at times, a very
small proportion is also provided by gypsum;
(d) Cl is provided by halite; and (e)signifi-
cant quantities o f N a are only provided by pla-
gioclase and, in a few deposits, by halite. So,
the amounts of quartz, gypsum and feldspars
were calculated from X-ray data, and halite
from the C1 content. In samples with only one
carbonate, calcite and dolomite were esti-
mated from the CaO content, subtracting the
amount corresponding to gypsum; if both car-
bonates are present, their amounts were esti-
223
mated taking into account the calcite/dolo-
mite ratio in diffractograms. The amounts of
the phyllosilicates were deduced from X-ray
data and the K20, A1EOa, Fe203 and MgO
contents.
3.2. Chemical analyses
All the chemical elements except Si, F, C1 and
REE were analysed by inductively coupled
plasma (ICP), using Thermo Jarrel ® Ash-
Plasma 300 equipment. Silicon was deter-
mined by atomic absorption using IL-257 ®
equipment. F and Cl were analysed using se-
lective electrodes. The analyses were carded
out in the TOLSA S.A. laboratories (Madrid).
REE analyses were carried out at the X-Ray
Assay Laboratories (Ontario, Canada) using
the inductively coupled plasma mass spec-
trometry technique (ICP-MS). The detection
limits of elements are: Ni, Sr, V and Zn - - 5
ppm; Co, Cr, Cu and L i m 10 ppm; Ba and Y
m 1 ppm; F and C1 n 500 ppm; La, Ce, Pr, Nd,
Sm, Gd, Tb, Dy, Er, Tm and Yb m 0.1 ppm;
and Eu, Ho and Lu m 0.05 ppm.
Isotope analyses were carded out at the Sta-
ble Isotope Laboratories of the Estaci6n Ex-
perimental del Zaidin (CSIC, Granada,
Spain). Analysis of the carbonatic samples was
performed using the method of McCrea
( 1950 ), which basically consists in leaching the
carbonate with pure (100%) phosphoric acid
for 12 hr in a thermostatic bath at 25 _+0.1 ° C
(50°C for the dolomites). The silicates were
dissolved in nickel chambers with C1F3 at
650°C for 6 hr, following a process similar to
that described by Borthwick and Harmon
(1982). Isotopic ratios were measured in a
Finnigan ® MAT 251 mass spectrometer. The
experimental error found in carbonates ( ~ a C
and 8~80)was < ___0.05%0,using Carrara and
EEZ-1 as internal standards, previously com-
pared with NBS-18 and NBS-19. For silicates
commercial CO2 was used as internal stan-
dard, compared with the standards of V-
SMOW, SLAP and GIPS water, obtaining a
224 J. T O R R E S - R U J Z ET AL.

value oft~lSO= + 5.15 _+0.2%O (V-SMOW) for neoformed* phyUosilicates (sepiolite, palygor-
the international NBS-30 (biotite) standard, skite and trioctahedral smectites); and car-
In some cases chemical treatment was re- bonates (calcite and/or dolomite). Opal-A,
quired to eliminate carbonates before analysis gypsum and/or halite may also appear sporad-
of silicates; calcite was eliminated by using a ically in some samples.
weak acid at pH = 5 and dolomite by using a The composition of the analysed samples, on
1 : 1 HC1 solution for 30 min, leaching taking the basis of the three main groups of minerals
place in both cases at room temperature. These mentioned above (detrital minerals, neo-
chemical treatments do not have a significant formed phyllosilicates and carbonates), is
effect on the isotopic values of the clays (Yeh, shown in Fig. 2. In this figure, these samples
1980; Longstaffe, 1986; Ayalong and Longs- are classified according to Torres-Ruiz et al.
taffe, 1990). (1992 ). The rocks located in the areas identi-
fied as 1 to 5 are named according to the clas-
sification of rocks made up of carbonate-lu-
4. Results ~md interpretation tites (Vatan, 1967 ); in the other fields the rocks
are named according to the content and type
4. I. Mineralogy of neoformed minerals; area 5d takes the name
of the most abundant neoformed phyllosili-
cate, if this represents > 90% of the content,
The mineral composition of the samples otherwise it is given the name of the two main
studied is shown in Table 1. The main mineral neoformed phyllosilicates.
components of the samples from all the depos- The most abundant detrital minerals pres-
its belong to three groups: detrital silicates (il- ent in most of the samples are illite and quartz,
lite, interstratified illite-smectite, quartz, feld- which reach proportions of up to 54% and 15%,
spars, dioctahedral smectite and kaolinite); respectively. The other detrital silicates are
generally minor components, apart from iso-
:a~o~tes lated samples. Moreover, the comparison of
,~ ~0 chemical and X-ray data reveals the existence
~/~ ~ ~ of significant quantities of amorphous silica in
/, some very sepiolite-rich samples from the
Cerro Batallones and Parla deposits.
/3b "~\" "~3~ In some layers, the neoformed phyllosili-
/ '\~.,so.. \ \ cates are the major components of the sam-
~--~'--" / ~.x ~ pies, in some cases reaching percentages of up
. .~ to 97% (sepiolite), 94% (magnesium smec-
/ 4~.~. "4b" \ . 4 o ,~ ~ tite) and 71% (palygorskite). On the whole,
~!/ ~ -- • \ •. . . . . I0
' * ~ / ~ ' ~ - - ~ .-.sb " ~\. ~ a ~ - s ~ either only one of these neoformed phyllosili-
NeoformeO l0 ~'~ *,r, ,r) Detritol cates is present, or the sepiolite-magnesium
phyllosilicates minerals smectite or sepiolite-palygorskite associations
Fig. 2. Composition and classification of analysed rocks
are found. Palygorskite and Mg-smectite do not
( 1 = limestone or dolostone; 2 = marly limestone; 3 = marl; coexist in any of the samples.
4 = limery marl; 5 = lutites; 2a = sepiolite (or palygorskite Scanning electron microscopy ( SEM ) study
or bentonite )-bearing marly limestone; 3a=sepiolite-
bearing marl; 4a = sepiolite-bearing limery marl; 5a = se- *The term neoformed minerals is here used as equivalent
piolite-bearing lutite; 3b=sepiolitic marl; 4b=sepiolitic to minerals formed in a depositional basin by chemical
limery marl; 5b=sepiolitic lutite; 4c=limery marly se- precipitation and/or by solution-solid reactions during
piolite; 5c = lutitic sepiolite; 5d = sepiolite), early diagenesis.
GEOCHEMISTRY OF SPANISH SEPIOLITE-PALYGORSKITEDEPOSITS
of the fibrous phyllosilicates reveals that: (1)
the sepiolites differ greatly in shape and fibre
size from one deposit to another and even in
samples from the same deposit. The more
abundant morphologies correspond to planar
aggregates (often with filamentous borders),
and filamentous-fibrous aggregates with bun-
die-like aspect; (2) sporadically the sepiolite
shows a morphology of wool-ball-like aggre-
gates forming grains up to 20/~m in size, which
correspond to a morphological adaptation
around small crystals of gypsum, calcite and/
or halite; (3) the palygorskite crystals form
planar and fibrous aggregates similar to those
of sepiolite but of larger fibre-size, sometimes
reaching up to 100 #m in length (whisker-like
crystals) (Torres-Ruiz et al., 1992).
The carbonates consist of calcite and dolo-
mite in very variable proportions. Calcite is
present in all the sites, while dolomite is only
present in significant quantities in the samples
from Calatayud and Almaz~ln. There are also
small quantities of gypsum and halite in the
samples taken from the E1 Cuervo deposit,
From the qualitative point of view there are
no significant differences among the detrital
minerals present in the different deposits,
However, there are important differences in the
neoformed minerals, which must correspond to
differences in the predominant physical-
chemical conditions in the basins. The pres-
ence of gypsum and, especially, halite in the E1
Cuervo deposit (Guadalquivir Basin) indi-
cates the existence of higher salinity condi-
tions. Although this is a perimarine basin, the
3C data indicate that there is no significant in-
fluence of seawater, so that this higher salinity
must be the result of a higher contribution of
salts from the source areas (Keuper gypsum-
bearing marls) and/or of higher evaporation
conditions,
4.2. Chemistry
4.2.1. Major and trace elements
The data obtained are presented in Tables 2
225
(major elements), 3 (trace elements) and 4
(REE). Table 5 shows the approximate struc-
tural formulae of the neoformed phyllosili-
cares in the different sites, as calculated on the
basis of the chemical analysis of samples very
rich in each of these phyllosilicates, recalcu-
lated to 100% according to the associated
mineralogy.
The fibrous silicates show some composi-
tional differences from one deposit to another.
The sepiolite from the Tajo Basin deposits
shows little or no tetrahedral substitution,
whereas in that of the Calatayud deposit there
is significant substitution of Si by A1TM(up to
0.46 atoms by unit cell) and/or Fe TM (up to
0.15 atoms ) and the Fe v~ content is higher (up
to 0.45 atoms). As regards palygorskite, there
is no tetrahedral substitution in the Almaz~in
and Pareja deposits, but there is appreciable
substitution of Si by A1TM(up to 0.80 atoms)
and a higher Fe vI content (up to 1.31 atoms)
at Maderuelo. Moreover, it should be pointed
out that the palygorskite in all the deposits is
relatively rich in Al ( 1.13-2.16 atoms).
The trioctahedral smectites from Vic~llvaro
correspond to the stevensite end-member [ fol-
lowing the terminology used by Newman and
Brown ( 1987 ) and Giiven ( 1988 ) ] with or
without significant tetrahedral substitution.
We have effected correlations between
chemical and mineralogical compounds in each
basin and in deposits as a whole. The close
similarity observed in all cases lead us to pres-
ent tables and figures for the whole of samples.
Analysis of the linear correlations between
the mineralogical and chemical components
(Table 6) and comparison of the whole sam-
pie results with those of individual deposits
lead to the following considerations:
The major and trace elements make up two
clearly differentiated groups according to their
source. High positive correlations are obtained
among A1, Fe, Mn, K and Ti, which are mainly
found as part of the detrital fraction of the
samples. On the other hand, Mg, Ca and C1 are
basically found in the neoformed minerals
 &

0 ~ 0 ~ 0 0 0 0 0 0 0 0 0 ~ 0 0 ~ 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ~ ~.
~ o
0

0 0 0 0 0 0 0 ~ 0 ~ 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

~ 0 ~ 1 ~ ' ~ O 0 0 0 0 0 0 0 O ~ O O O O 0 0 0 ~ O O 0 ~ O 0 ' ~ O 0 0 ~ O 0 O O O 0 0 ~ O 0 0 0 0 0 0

N ~ = r

0 0 0 ~ 0 i J O O l ~ l ~ O 0 0 0 0 4 0 ~ 0 ~ 0 0 ~ O ~ O 0 0 0 0 & O 0 0 ~ O 0 0 ~ 0 0 0 0 0 0 ~ 0 ~

ooooo o o ~ o ~ ~ ~ 2 ~ N ~ ~ o ~ o ~ N N ~ E ooooooooo~ooo ~

r
GEOCHEMISTRY OF SPANISHSEP1OLITE-PALYGORSKITEDEPOSITS 227

TABLE 1 (continued)

Sample Q A.Si Cal Dol K-Fd Plag Hal Gyp Kaol 1-S Illite A 1 - S m Mg-Sm Sepiol Paly

PAR -I 3 0 9 0 0 0 0 0 0 6 16 0 0 19 46
-2 3 0 24 0 2 0 0 0 0 0 18 l0 0 17 26
-3 7 0 13 0 0 0 0 0 1 4 18 0 0 11 46
-4 3 0 41 0 2 0 0 0 0 10 14 5 0 25 0
-5 2 0 48 0 2 0 0 0 0 5 14 0 0 0 29
-21 3 0 29 0 0 1 0 0 0 3 8 0 0 38 18
-22 3 0 48 0 0 0 0 0 0 2 9 10 0 23 5
-23 2 0 55 0 1 0 0 0 0 0 5 5 0 32 0
-24 2 0 45 0 1 0 0 0 0 2 4 8 0 20 18
-25 3 0 17 0 0 0 0 0 0 2 7 0 0 0 71
-26 4 0 17 0 0 0 0 0 0 3 7 0 0 0 70
-27 1 0 58 0 0 0 0 0 0 5 12 15 0 3 6
-28 5 0 37 7 2 0 0 0 0 5 14 5 0 0 25

PARLA-1 1 7 1 0 0 0 0 0 0 0 0 0 0 91 0
-2 4 0 0 0 5 0 0 0 0 3 7 0 0 81 0

VIC -1 3 0 2 0 3 3 0 0 0 0 10 18 0 61 0
-2 3 0 2 0 3 2 0 0 0 0 9 5 15 61 0
-3 2 0 1 0 0 0 0 0 0 0 3 0 94 0 0
-4 3 0 2 0 0 0 0 0 0 0 4 0 92 0 0
-5 2 0 3 0 1 2 0 0 0 0 15 0 15 62 0
-6 3 0 1 0 3 6 0 0 0 0 26 0 21 40 0
-7 10 0 1 0 2 2 0 0 0 0 0 0 5 80 0
-8 0 0 0 0 0 0 0 0 0 0 3 0 0 97 0
-9 0 0 2 0 0 0 0 0 0 0 4 0 77 18 0
°10 6 0 1 2 2 4 0 0 0 0 6 0 79 0 0
-21 12 0 0 0 11 10 0 0 5 4 27 31 0 0 0
-22 15 0 5 0 7 10 0 0 0 5 5 43 0 10 0
-23 5 0 10 0 2 3 0 0 0 4 20 0 0 56 0
-24 5 0 6 0 3 3 0 0 0 2 15 0 0 62 4
-25 5 0 44 0 0 2 0 0 0 4 8 0 0 37 0
-26 2 0 I 0 0 0 0 0 0 0 27 0 17 53 0
-27 4 0 3 0 3 4 0 0 2 0 36 16 0 32 0
-28 6 0 I 0 5 8 0 0 0 0 5 0 0 75 0
-29 5 0 0 0 2 5 0 0 0 0 0 0 0 88 0
-30 2 0 1 0 0 0 0 0 0 0 2 0 0 95 0
-31 12 0 1 0 3 4 0 0 0 0 4 0 0 76 0
-32 8 0 6 0 3 0 0 0 0 5 8 0 0 70 0
-33 4 0 2 0 8 3 0 0 0 2 35 0 0 46 0

Q = quartz; A.Si = amorphous silica; Cal = calcite; Dol = dolomite; K-Fd = K-feldspar; Hag = plagioclase; Hal = halite; Gyp = gypsum;
Kaol = kaolinite; I-S = interstratified illite-smectite; A1-Sm= Al-smectite; Mg-Sm = stevensite; Sepiol = sepiolite; Paly = palygorskite.

(neoformed phyUosilicates, carbonates, gyp-
sum and halite) and correspond to elements in
solution in the depositional basins. Si and Na
are found in both the detrital fraction and the
neoformed minerals,
Similarly, the trace elements also make up
two groups according to their main source. The
first group consists of elements of the first
transition series (V, Cr, Co, Ni, Cu and Zn)
and REE. In the deposits as a whole, positive
correlations are found among all these ele-
ments and Al-silicates of detrital origin (Fig.
3). In detail, different populations can be es-
tablished which show very small variations of
slopes in the regression lines. Such differences
are more related to regional differences (dif-
ferent basins) than to the existence of miner-
alogical differences in the detrital fraction.
228 J. TORRES-RU][ZET At..

TABLE 2

Chemical composition of the samples

Sample SiO2 A1203 MgO CaO Fe203 Na20 K20 Mn203 TiO2 LOI Total

ALM -1 33.00 6.74 5.47 24.95 2.33 0.08 1.20 0.04 0.37 25.13 99.31
-2 13.00 2.03 17.51 25.98 0.71 0.08 0.46 0.01 0,10 40.11 99.99
-3 18.00 2.93 17.00 23.11 1.05 0.09 0.56 0.01 0,16 37.30 100.20
-4 44.00 10.27 11.38 8.82 3.32 0.14 1.72 0.02 0.55 19.64 99.96
-5 22.00 4.20 16.62 19.98 1.41 0.09 0.84 0.01 0.24 34.58 99.97
-6 5.00 0.78 20.58 27.89 0.39 0.04 0.16 0.01 0.04 44.71 99.60
-22 49.00 10.40 10.66 7.31 3.53 0.12 1.78 0.02 0.47 17.77 101.06
-23 48.00 9.62 11.17 7.47 3.43 0.10 1.57 0.01 0.45 18.05 99.87
-24 37.00 8.75 12.87 12.05 2.62 0.10 1.48 0.01 0.36 23.78 99.02
-25 9.00 1.77 19.19 25.83 0.63 0.06 0.41 0.01 0.09 42.98 99.97
-26 32.00 8.44 11.82 14.80 2.93 0.08 2.19 0.04 0.38 26.52 99.20
-27 29.50 7.97 4.99 25.16 2.72 0.07 1.98 0.03 0.33 27.36 100.11
-30 1.20 0.51 0.55 54.60 0.29 0.06 0.05 0.01 0.02 42.54 99.83

CALA -1 11.00 1.25 20.44 25.48 0.51 0.10 0.39 0.05 0.06 40.51 99.79
-2 56.50 1.19 25.48 2.16 0.93 0.03 0.44 0.02 0.06 12.91 99.71
-3 11.00 2.32 19.94 25.19 0.82 0.13 0.62 0.05 0.11 39.99 100.06
-4 59.50 6.43 19.71 0.66 2.09 0.05 1.37 0.02 0.22 9.96 100.01
45 57.00 10.24 13.69 1.63 3.67 0.10 2.60 0.03 0.37 10.35 99.68
-6 56.50 14.04 12.32 0.52 4.75 0.16 3.83 0.04 0.54 7.34 100.04
-7 58.00 18.35 5.75 0.86 4.64 0.22 4.91 0.02 0.77 6.12 99.64
48 60.00 5.62 20.19 0.33 2.44 0.05 1.38 0.02 0.26 9.52 100.0t
-21 59.50 11.70 11.39 0.62 4.35 0.14 2.83 0.03 0.43 8.68 99.66
-22 58.00 17.76 5.49 1.28 5.71 0.15 4.58 0.03 0.65 6.34 99.99
-23 48.50 15.39 10.95 5.06 4.15 0.18 3.99 0.08 0.64 11.84 100.78
-24 59.00 14.67 9.47 0.65 5.33 0.10 3.37 0.03 0.50 6.97 99.99
-25 59.00 7.74 15.81 1.49 2.71 0.07 1.89 0.02 0.29 10.09 99.11

CB-0 10.00 1.33 0.79 46.75 0.43 0.04 0.16 0.02 0.04 39.33 98.89
-1 62.00 12.59 8.48 1.27 4.29 0.45 1.90 0.05 0.45 8.82 100.30
-2 16.00 2.45 4.10 39.35 0.82 0.04 0.08 0.02 0.07 35.00 97.93
-3 57.00 3.14 14.69 8.39 1.00 0.05 0.41 0.10 0.01 14.72 99.51
-4 63.00 2.29 22.10 1.05 0.64 0.06 0.42 0.02 0.10 10.30 99.98
-5 7.00 0.17 2.80 48.31 0.05 0.01 0.04 0.02 0.01 40.57 98.98
-6 62.00 1.43 22.50 2.04 0.44 0.04 0.30 0.03 I).06 11.13 99.97
-7 64.00 0.86 23.19 0.35 0.21 0.03 0.41 0.01 0.03 10.03 99.12
-8 23.00 6.52 2.00 34.56 2.05 0.16 0.80 0.02 0.21 29.99 99.31

EC -1 27.00 4.99 6.10 29.09 1.83 1.02 0.96 0.02 0.17 28.42 99.49
-2 20.50 1.16 6.43 35.62 0.50 1.57 0.15 0.02 0.06 34.43 100.44
-3 20.50 1.05 4.61 38.76 0.46 0.54 0.10 0.02 0.06 34.42 100.52
-4 28.00 3.35 5.95 28.62 1.54 1.49 0.58 0.02 0.17 30.17 99.89
-5 48.00 10.13 7.51 8.77 3.19 3.11 1.54 0.02 0.31 17.24 99.82
-6 18.00 3.04 3.60 34.40 1.29 3.42 0.46 0.05 0.15 35.20 99.63
-7 40.00 8.97 6.04 12.57 3.30 4.85 1.95 0.04 0.34 21.27 99.33
-8 48.00 12.65 5.71 6.81 4.67 3.02 3.04 0.03 0.49 14.73 99.15
-9 48.50 13.01 3.68 9.98 4.66 1.39 3.50 0.03 0.63 14.09 99.47
-10 14.00 4.01 2.05 40.16 1.67 1.33 0.74 0.10 0.19 35.24 99.49

MAD-/ 57.00 18.99 2.87 0.86 7.23 0.47 4.64 0.09 0.75 6.42 99.32
-2 58.00 17.81 4.63 1.01 7.41 0.34 2.56 0.07 0.63 8.17 100.63
-3 57.00 16.50 5.16 2.01 7.03 0.30 2.30 0.06 0.56 9.09 100.03
-4 38.50 7.50 6.36 20.73 3.04 0.10 0.83 0.02 0.30 22.59 99.97
-5 26.00 4.83 4.34 31.43 1.98 0.07 0.58 0.01 0.18 29.82 99.24
GEOCHEMISTRYOF SPANISH SEPIOLITE-PALYGORSKITE DEPOSITS 229

TABLE 2 (continued)

Sample SiO2 A1203 MgO CaO Fe203 Na20 K20 Mn203 TiO2 LOI Total

PAR -1 55.00 10.35 9.55 4.99 3.37 0.11 1.77 0.03 0.5a 13.13 98.88
-2 44.00 10.10 6.15 13.52 3.66 0.09 1.74 0.03 0.51 18.27 98.09
-3 55.00 9.20 8.05 7.68 2.90 0.11 1.71 0.02 0.60 14.05 99.32
-4 34.50 8.25 6.00 22.93 2.50 0.11 1.41 0.02 0.45 22.94 99.11
-5 30.00 8.20 3.65 26.61 2.50 0.08 1.38 0.02 0.30 25.71 98.86
-2l 42.00 8.06 9.00 16.59 2.75 0.15 0.97 0.02 0.46 19.49 99.49
-22 31.00 6.75 5.75 26.62 2.16 0.10 0.85 0.01 0.20 24.79 98.43
-23 28.00 4.63 5.07 30.54 1.44 0.08 0.62 0.02 0.20 28.95 99.55
-24 33.00 6.23 6.15 25.01 1.96 0.08 0.65 0.02 0.30 24.76 98.20
-25 53.00 8.60 8.75 9.54 2.88 0.07 0.83 0.01 0.45 16.79 100.92
-26 50.00 7.65 8.70 9.97 2.53 0.08 0.86 0.02 0.42 17.87 98.10
-27 23.00 7.63 2.41 32.47 2.60 0.07 1.17 0.03 0.32 28.75 98.45
-28 33.00 7.90 5.75 22.88 2.45 0.08 1.62 0.02 0.32 24.17 98.19

PARLA-1 63.00 0.52 25.00 0.45 0.13 0.03 0.23 0.01 0.03 10.34 99.74
-2 60.00 5.27 20.42 0.25 1.62 0.25 2.10 0.03 0.26 8.63 98.83

VIC -1 60.00 6.33 19.66 1.34 1.94 0.24 1.46 0.03 0.21 7.87 99.08
-2 58.00 6.40 22.61 1.31 2.11 0.28 1.32 0.04 0.21 7.21 99.49
-3 62.00 2.10 26.00 1.00 0.76 0.10 0.43 0.01 0.10 7.85 100.35
-4 60.00 3.21 25.00 0.99 0.95 0.10 0.50 0.02 0.10 8.25 99.12
-5 56.00 7.10 22.65 1.57 2.10 0.34 1.41 0.04 0.31 7.47 98.99
-6 59.00 10.23 16.23 1.08 3.11 0.78 2.48 0.05 0.42 6.71 100.09
-7 61.50 2.36 25.74 0.72 0.67 0.15 0.53 0.01 0.12 8.61 100.41
-8 61.50 1.16 26.53 0.26 0.36 0.10 0.43 0.01 0.06 9.83 100.24
-9 60.00 1.85 27.03 1.34 0.51 0.15 0.50 0.01 0.10 7.85 99.34
-10 60.00 5.40 22.67 1.32 1.55 0.37 0.96 0.03 0.22 7.48 100.00
-21 63.00 17.32 2.62 1.21 4.21 1.86 4.02 0.16 0.64 4.09 99.13
-22 60.00 16.60 6.39 2.64 4.43 0.40 2.59 0.15 0.49 6.40 100.09
-23 56.50 6.64 15.40 5.49 1.78 0.34 1.67 0.03 0.24 12.04 100.13
-24 57.00 5.84 17.12 3.60 1.39 0.39 1.87 0.02 0.28 11.47 98.98
-25 34.00 2.75 11.18 24.40 0.63 0.24 0.86 0.02 0.13 25.07 99.28
-26 59.00 8.77 17.01 0.89 2.43 0.49 2.14 0.04 0.35 8.01 99.19
-27 58.50 15.39 8.47 1.74 4.77 0.82 3.16 0.06 0.57 6.42 89.90
-28 61.50 5.01 20.56 0.43 1.17 0.36 1.34 0.02 0.24 9.07 99.70
-29 62.00 2.21 23.52 0.23 0.49 0.21 0.77 0.01 0.11 9.50 99.05
-30 62.00 0.95 25.07 0.13 0.24 0.06 0.36 0.02 0.05 10.13 99.01
-31 64.00 3.21 20.79 0.33 0.82 0.23 1.09 0.02 0.14 9.36 99.98
-32 60.00 3.80 19.26 3.43 1.02 0.25 0.97 0.03 0.14 11.25 100.15
-33 58.00 12.82 10.15 1.67 5.02 0.32 4.03 0.09 0.43 7.41 99.94

The second group of trace elements consists
of F and Li, which are mainly found in associ-
ation with the neoformed phyllosilicates. F
shows a high positive linear correlation coeffi-
cient for the Mg and neoformed phyllosilicates
as a whole (Fig. 3 ). However, sepiolite and Mg-
smectite contain more F than palygorskite,
This fact produces a negative correlation be-
tween palygorskite and F in the deposits as a
whole. However, this correlation is positive for
deposit or samples where palygorskite is the
only neoformed silicate. Li is preferentially
concentrated in the Mg-smectite phase (stev-
ensite). This selective concentration of Li in
the Mg-smectites as against that of other neo-
formed phyllosilicates is a well-documented
fact (Tardyetal., 1972 ) . As these authors point
out, for similar Mg contents in the silicates, Li
is retained more readily in laminar than in fi-
brous minerals, and so palygorskites can be
= ,..,~_ ^ _ .Z 8
g
N
A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A
o ~

AA AA AA A A AA A AAAA A

A A A AAAA A AA A A

~ ~ - ~ o ~ ,~ ~ Y ~ ~ ~d ~- ~ ~ ~ d ~ ~ & ~

A A A A A A A A A A A A A A A A A A A A A A A A A E ~ N Z A A A A A A A A A A A A A A A a ~
NNNNNNNN~NNNN N~ NNNNN N ~ N~NN NNN~ ~N~NNE NN~N~a m
GEOCHEMISTRY OF SPANISH SEPIOLITE-PALYGORSKITE DEPOSITS
found in contrast to saponites and sepiolites to
stevensites. The reason for this is that Li is fixed
preferentially in those minerals that allow in-
terlaminar compensation of charge deficit in
the octahedral layer, which is characteristic of
laminar minerals, whereas interlaminar corn-
pensation does not occur in fibrous minerals,
Sr and Ba are positively correlated at the
level of individual deposits. Neither element
shows highly significant correlations as re-
gards the rest of the chemical components and/
or the different mineral phases. However, on
considering the deposits as a whole, correla-
tion between both elements is not significant.
On the other hand, although in most samples
the C1 content is below the detection limit, from
Table 3 it can be observed that the greatest Sr
content correspond to E1Cuervo deposit, where
halite is a neoformed phase that is frequently
present,
Fig. 4 represents a factor analysis of princi-
pal components and a cluster analysis of the
most significant mineralogical and chemical
variables or groups of variables. In the factor
analysis, the three factors chosen explain 87%
of the total variance. Factor 1 characterises and
contrasts the detrital minerals and associated
chemical elements (variables with high posi-
tive ponderations) and the neoformed phyl-
losilicates and associated elements. Factor 2
characterises and groups together the Mg-
smectite and Li (high negative ponderations),
and factor 3 characterises and separates paly-
gorskite from the other neoformed phyllosili-
cates, in particular from sepiolite,
The distribution patterns of REE normal-
ised to North American Shale Composite
(NASC) for each deposit are shown in Fig. 5.
In all the deposits the chondrite-normalised
REE patterns show a trend with a negative
anomaly in Eu, similar to those of the NASC.
However, REE contents range from 1 to 0.05
times the NASC values, according to the rain-
eralogy of the samples. Furthermore, in corn-
parison with the NASC pattern, most of these
samples show a noticeable progressive deple-
231
tion in heavy REE (HREE). The REE are
mainly supplied by detrital minerals. From
practically monomineralic samples and multi-
ple regression calculations among REE and
mineral components, we have obtained that
REE contents of the main minerals are or-
tiered as follows:
illite > interstratified illite-smectite
>palygorskite
> Mg-smectite ~ sepiolite ~ carbonate
Moreover, some differences are observed in the
REE patterns for the clayey samples of the dif-
ferent deposits. The Madrid Basin deposits
(Vicalvaro, Parla and Cerro Batallones ) show
a negative anomaly in Eu as regards NASC, this
anomaly is less noticeable in the Pareja deposit
and is either not present or slightly positive in
the other deposits. There is no relationship be-
tween the feldspars and Eu contents. Similarly,
the Madrid Basin deposits have a slightly in-
creasing general trend from Ce to Gd, whereas
the trend in the other deposits is flat or slightly
decreasing. According to the geological con-
text of these deposits, the impoverishment in
HREE could be related to the pH of the alter-
ation solutions, as the light REE (LREE) ac-
cumulate preferentially in profiles during al-
kali alteration states (Nesbitt, 1979). The
differences found among deposits with a simi-
lar mineralogy must be related only with dif-
ferences in source areas. Furthermore, the dif-
ferences in patterns between deposits is a
characteristic inherited from the source areas,
as the behaviour of the REE throughout con-
tinental weathering is governed by the phe-
nomenon of inheritance, so that the detrital
clays transported to the sedimentation basins
maintain their continental memory, without
important variations according to the detrital
clay mineralogy (Bonnot-Courtois, 1981;
Fleet, 1984).
REE-TRTE (transition trace elements) and
(REE + TRTE)-F correlation diagrams for
neoformed phyllosilicates are shown in Fig. 6.
TABLE 4

Rare-earth element contents of the samples

Sample La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Y

ALM -1 14.50 34.60 4.00 14.90 2.70 0.40 1.80 0.20 1.20 0.22 0.60 <0.10 0.70 0.08 5.00
-4 26.30 50.60 6.90 26.90 4.80 0.82 3.90 0.50 2.50 0.46 1.20 0.20 1.30 0.17 11.00
-22 23.30 46.80 5.20 19.40 3.70 0.76 2.50 0.30 1.90 0.37 0.90 <0.10 1.00 0.13 9.00
-23 20.40 41.00 4.80 18.60 3.20 0.70 2.50 0.30 1.80 0.31 0.90 0.10 0.90 0.11 7.00
-24 17.50 34.20 4.40 16.90 2.90 0.70 2.70 0.20 1.40 0.26 0.70 <0.10 0.80 0.10 6.00
-30 1.90 2.60 0.50 1.70 0.80 0.26 0.60 0.10 0.30 0.07 0.40 <0.10 0.20 0.09 < 1.00

CALA -2 2.50 4.80 0.60 2.40 0.60 0.08 0.20 <0.10 0.30 <0.05 0.10 <0.10 0.10 <0.05 0.50
-5 18.90 37.30 4.30 16.60 3.00 0.78 2.00 0.20 1.50 0.27 0.80 <0.10 0.80 0.11 7.00
-7 36.90 79.60 9.00 34.10 6.20 1.41 5.20 0.60 3.20 0.57 1.70 0.20 1.60 0.22 15.00
-8 10.50 21.30 2.30 9.30 1.90 0.38 1.10 0.20 0.80 0.16 0.40 <0.10 0.50 0.05 4.00
-21 22.90 47.10 5.60 22.40 3.80 1.01 3.40 0.40 2.50 0.48 1.30 0.20 1.30 0.17 12.00
-23 37.00 74.30 8.40 34.00 5.90 1.08 4.20 0.50 2.60 0.47 1.20 0.20 1.30 0.20 12.00
-25 16.00 32.80 4.00 14.20 2.60 0.58 1.80 0.20 1.30 0.25 0.70 <0.10 0.80 0.12 6.00

CB-I 23.10 55.90 6.60 27.00 5.50 0.70 4.70 0.80 3.70 0.69 1.80 0.30 1.80 0.22 18.00
-2 11.10 15.30 2.40 9.80 2.10 0.27 2.40 0.30 1.80 0.36 0.90 <0.10 0.90 0.11 10.00
-4 7.60 15.20 1.90 7.20 1.70 0.21 1.50 0.20 1.50 0.22 0.70 <0.10 0.70 0.08 8.00 ,,..d
~5 2.20 2.80 0.60 2.00 0.90 0.17 0.50 0.10 0.30 0.12 0.40 <0.10 0.40 0.09 2.00
-7 1.80 4.40 0.40 1.70 0.40 <0.05 0.10 <0.10 0.20 <0.05 0.10 <0.10 0.10 <0.05 1.00 :~

EC-4 9.50 18.40 2.20 7.70 1.70 0.38 1.50 0.20 1.00 0.22 0.70 <0.10 0.50 0.06 6.00
N
-5 15.60 27.00 3.30 12.70 2.20 0.53 1.90 0.20 1.40 0.28 0.80 <0.10 0.80 0.10 7.00
,.-]
-8 23.90 43.70 5.10 21.00 3.60 1.06 3.70 0.50 2.30 0.41 1.20 0. t0 1.30 0.18 11.00
-9 29.00 54.30 6.40 25.60 4.60 1.06 4.20 0.50 2.90 0.57 1.50 0.20 1.60 0.24 15.00 r"
MAD-/ 44.90 80.60 10.70 42.10 7.20 1.70 6.70 0.90 5.20 0.87 2.40 0.40 2.20 0.34 22.00 ¢~
-2 34.10 68.10 6.80 26.80 5.30 1.36 4.90 0.70 4.00 0.77 2.00 0.30 2.10 0.32 22.00
-3 27.60 53.10 7.30 27.10 5.10 1.24 5.30 0.70 3.80 0.68 2.00 0.20 2.00 0.24 18.00 r~
-5 12.50 25.90 2.80 10.60 2.20 0.54 1.80 0.30 1.70 0.26 0.90 <0.10 0.70 0.10 8.00

PAR -1 24.10 48.90 5.40 21.60 4.10 0.71 3.50 0.50 2.10 0.38 1.00 0.20 1.10 0.15 9.00
-3 34.50 71.30 7.80 29.00 5.70 0.86 4.10 0.60 2.90 0.52 1.50 0.20 1.40 0.22 13.00 o
-21 18.10 41.20 4.10 15.50 3.00 0.49 2.50 0.30 1.70 0.26 0.70 <0.10 0.80 0.11 8.00
-25 21.40 52.90 5.10 19.20 3.60 0.66 2.90 0.40 2.20 0.39 1.00 0.10 1.00 0.11 10.00
-26 20.70 45.50 5.00 19.10 4.10 0.60 3.10 0.40 2.10 0.36 1.00 0.10 1.00 0.13 9.00

PARLA-I 3.30 6.60 0.90 3.40 0.80 0.08 0.60 <0.10 0.50 0.07 0.20 <0.10 0.20 <0.05 2.00 '~
-2 9.50 18.70 2.20 8.30 1.80 0.24 1.20 0.10 1.00 0.16 0.50 <0.10 0.40 0.06 4.00
,--I

VIC -2 11.50 29.80 3.00 11.50 2.90 0.30 2.60 0.40 2.50 0.43 1.30 0.20 1.20 0.15 12.00
-3 5.50 10.60 1.40 5.80 1.10 0.11 0.70 0.10 0.70 0.12 0.30 <0.10 0.30 <0.05 3.00
-4 7.60 14.30 1.90 8.00 2.00 0.38 1.50 0.30 1.40 0.32 1.00 0.20 0.80 0.17 5.00
-5 19.30 37.20 5.10 21.90 4.80 0.68 4.40 0.60 3.30 0.55 1.50 0.10 1.30 0.17 15.00
-6 24.60 50.80 6.10 24.80 6.40 0.66 4.80 0.80 4.40 0.77 2.10 0.30 2.00 0.25 22.00
-8
-8 3.80 7.50 0.80 3.40 0.80 0.09 0.50 <0.10 0.40 0.05 0.20 <0.10 0.20 <0.05 2.00 r~
-9 6.10 ll.90 1.40 4.80 1.00 0.15 1.00 0.10 0.70 0.14 0.30 <0.10 0.30 <0.05 4.00
-21 46.70 94.20 11.90 49.40 10.30 1.10 9.10 1.40 7.40 1.33 3.70 0.50 3.90 0.49 37.00 ~D
-23 16.90 42.20 4.40 17.20 3.50 0.46 3.30 0.50 2.70 0.47 1.40 0.20 1.10 0.15 13.00
-24 ll.70 30.10 2.80 ll.20 2.60 0.38 2.00 0.30 1.80 0.29 0.80 <0.10 0.80 0.07 7.00
-26 20.50 39.00 5.00 19.70 4.50 0.56 3.60 0.60 3.30 0.61 1.70 0.20 1.50 0.21 18.00
-27 37.10 76.50 9.30 38.40 8.90 0.95 7.60 1.20 6.90 1.23 3.40 0.40 2.90 0.36 33.00
-29 8.20 17.40 1.90 8.00 1.80 0.29 1.50 0.30 1.00 0.21 0.70 0.10 0.60 0.11 4.00
-30 6.40 12.50 1.40 6.30 1.20 0.28 0.90 0.10 1.00 0.12 0.30 <0.10 0.40 0.07 3.00
-33 19.20 34.50 4.70 19.00 4.50 0.51 3.80 0.70 3.90 0.75 2.50 0.30 2.30 0.28 22.00

I,o
234 J. TORRES-RUIZET AL.

TABLE 5

Structural formulae of sepiolites, palygorskites and stevensites

Mineral Sample Si TM AITM Fe w AIvt Mgvl Fe vI Ti Mn K Na Ca

Sepiolite CALA-2 11.76 0.09 0.15 8.00 0.01 0.01 0.002 0.07 0.01
CALA-4 11.42 0.46 0.12 7.67 0.31 0.05 0.002 0.06 0.03
CALA-8 11.60 0.40 0.01 7.29 0.45 0.05 0.002 0.08 0.02
CB-4 12.00 0.41 7.09 0.10 0.02 0.002 0.07 0.03
CB-6 12.00 0.08 7.83 0.08 0.01 0.003 0.05 0.02
CB-7 12.00 0.06 7.82 0.04 0.001 0.07 0.01
PARLA-1 12.00 0.13 7.71 0.02 0.001 0.06 0.01
VIC-8 11.91 0.09 0.02 7.80 0.05 0.01 0.001 0.06 0.04 0.05
VIC-29 11.76 0.21 0.03 7.88 0.05 0.02 0.001 0.13 0.09
VIC-30 12.00 0.12 7.60 0.04 0.01 0.002 0.06 0.02

Palygorskite ALM-22 8.00 1.22 1.75 0.66 0.09 0.05 0.05

ALM-23 8.00 1.13 1.98 0.63 0.08 0.06 0.05 0.03
MAD-2 7.20 0.80 1.36 1.07 1.31 0.11 0.006 0.07 0.15
MAD-3 7.37 0.63 1.12 1.43 1.16 0.09 0.005 0.06 0.13 0.19
PAR-25 8.00 1.29 2.24 0.38 0.06 0.001 0.05 0.02
PAR-20 8.00 1.16 2.43 0.37 0.06 0.001 0.05 0.03 0.08

Mg-smectite VIC-3 4.00 0.11 2.65 0.04 0.01 0.02 0.01 0.03
VIC-4 3.96 0.04 0.15 2.66 0.05 0.01 0.02 0.01 0.01

We present TRTE and REE grouped because
the elements belonging to each group behave
similarly. The values were calculated on the
basis of the chemical and mineralogical anal-
yses of samples very rich in each of these rain-
erals, recalculated to 100% of phyllosilicate.
The values for the detrital aluminosilicates and
carbonates are also shown. It can be seen that
palygorskite presents higher sumREE and
sumTREE and minor F values than those of
Mg-smectite and sepiolite, which do not seem
consistent with a origin of palygorskite by
chemical precipitation,
4.2.2. Isotope data
Table 7 and Fig. 7 present the isotopic com-
positions of ~3C in carbonates and ~80 in silica,
neoformed phyllosilicates and carbonates.
microcrystalline quartz, whereas that from El
Cuervo is opal-A.
The silica from the Viclllvaro and Cerro Ba-
tallones sites (Madrid Basin) presents c~~ao-
values of + 23.62 to + 25.61%00, whereas at the
E1 Cuervo site (Guadalquivir Basin) its c~180-
value is + 30.4%0. According to the equation
by Clayton et al. ( 1972)* and for environmen-
taltemperatures between 15 ° and 25°C (the
interval including the predominant climatic
conditions during formation of these depos-
its), the water from which the silica precipi-
tated would have had J laO-values between
- 1 3 and -9%0 for the Vic~tlvaro and Cerro
Batallones sites (Fig. 7 ). These c~80-values are
slightly more negative (by ~ 2%o) than those
*Clayton et al. experimentally deduce the equation:
1000 lnc~= 3.38 ( 106X T -2 ) - 3 . 4

4.2.2.1. Isotopic composition of silica. Four
samples of silica nodules were analysed from
the Viclilvaro (VIC), Cerro BataUones (CB-a
and CB-b) a n d El Cuervo (EC)deposits.
samples from the first two deposits consist of
For silica-water fractionation in the 200-500°C range.
However its extrapolation to lower temperatures seems to
be valid, since the data coincide with those of Kita et al.
(1985) for amorphous silica and Labeyrie (1974) for
The biogenic silica for the 34-93 ° and 0 - 3 0 ° C ranges,
respectively.
 m

TAnLE6 'e
O
Pearson correlation coefficients of mineralogical and chemical data ,~
m
AI2Os Fe203 MgO SiO2 K20 Na20 CaO TiO2 Mn203 Sr Ba F Li REE TRTE ALSIDET SEPIOL STEVE SEP+STE PALY NEOPHY
U~

A1203 1.00
cD
Fe203 0.96 1.00 ~o
MgO -0.58 -0.59 1.00 b~e
Si02 0.24 0.20 0.57 1.00 ,.~
K20 0.90 0.82 -0.42 0.31 1.00 r~
Na20 0.33 0.29 -0.32 0.04 0.33 1.00
CaO -0.32 -0.28 -0.54 -0.98 -0.39 -0.04 1.00 ©
TiO2 0.95 0.89 -0.58 0.20 0.84 0.25 -0.28 1.00 m
Mn20~ 0.67 0.61 -0.35 0.22 0.69 0.29 -0.23 0.55 1.00
Sr 0.30 0.29 -0.33 -0.16 0.28 0.70 0.07 0.32 0.02 1.00
Ba 0.28 0.25 -0.35 -0.13 0.37 0.33 0.11 0.32 0.t6 0.42 1.00
F -0.58 -0.60 0.89 0.52 --0.43 -0.34 --0.46 -0.66 -0.33 -0.39 --0.32 1.00
Li -0.15 -0.19 0.52 0.34 -0.05 -0.06 -0.32 - 0 . 1 9 -0.01 -0.09 -0.16 0.46 1.00
REE 0.93 0.83 -0.55 0.24 0.83 0.27 -0.29 0.94 0.71 0.22 0.25 -0.51 -0.13 1.00
TRTE 0.95 0.93 -0.57 0.22 0.83 0.31 -0.30 0.95 0.54 0.36 0.28 -0.55 -0.19 0.88 1.00
ALSIDET 0.89 0.79 -0.47 0.26 0.96 0.36 -0.32 0.83 0.78 0.25 0.36 -0.45 -0.06 0.89 0.80 1.00
SEPIOL -0.48 -0.47 0.71 0.43 -0.27 -0.17 -0.39 -0.52 -0.22 -0.32 -0.21 0.65 0.02 -0.48 -0.48 -0.32 1.00
STEVE -0.24 -0.25 0.45 0.19 -0.20 -0.10 -0.18 -0.26 -0.11 -0.09 -0.14 0.43 0.82 -0.21 -0.23 -0.20 -0.19 1.00
SEP+STE -0.59 -0.59 0.93 0.52 -0.37 -0.23 -0.46 -0.63 -0.27 -0.35 -0.27 0.86 0.51 -0.58 -0.58 -0.42 0.81 0.42 1.00
PALY 0.34 0.42 -0.48 -0.12 0.05 0.03 0.09 0.45 -0.08 0.18 -0.02 -0.44 -0.38 0.31 0.42 -0.02 -0.58 -0.25 -0.68 1.00
NEOPHY -0.52 -0.46 0.88 0.61 -0.50 -0.28 -0.56 -0.50 -0.44 -0.33 -0.39 0.82 0.39 -0.53 -0.46 -0.59 0.63 0.36 0.81 - 0 . 1 2 1.00

REE = ~ elements; TRTE = transition trace elements ( V, Cr, Co, Ni, Co, Zn ); ALSIDET = detrital M-silicates; Sepiol = sepiolite; Steve = stevensite; Paly = palygorskite; NEOPHY = neoformed
phyHosilicates. Bold face values are the most significant correlation coefficients.

t,o
236 J TORRES-RUIZ ET AL.

20 ; , 20 ~. . . . . r- ~ ........!. . . . . . . . . .

,~ ,l,

15 15

zx

8 lo
Cq
o %0o. 0
8 lo
C'~
o *6
o
o

0
o
!
0 0 ~ 0 I
o I

•° ," I
, 5 q

, **% I
I / I t I
0 100 200 300 0 100 200 300 400 500

REE (ppm) TRTE (ppm)

t05 ; ;

~, . . ~ o Almazan
"104 ** * -P
,,,, ,~ ~ ,~ C a l a t a y u d

. o ~ Cerr0 Batallones
Oo
z~ ~ ~ o El C u e r v o

10 ~
o * Maderuelo
,9

o Pareja

, Parla

102 * Vicalvaro
0 1'0 ,2to 30

MgO (%)
Fig. 3. Variations of REE and transition trace elements (TRTE) as regards the A l 2 0 3 contents and of MgO as regards the
F contents in the different deposits,

of present-day meteoric water and recent pa- meteoric water and seawater would presum-
laeowater for each of these latitudes (in the ably have been ~ 1-2%o lighter, because of the
Madrid Basin the isotopic compositions range much smaller area of the polar ice-caps, which
from - 10 to -7%0; L6pez Vera and Araguas, retain lighter water, the g'SO-values for water
1986). If we consider that during the Miocene in equilibrium with silica would correspond to
G E O C H E M I S T R Y O F SPANISH S E P I O L I T E - P A L Y G O R S K I T E D E P O S I T S 237

1
FACTOR ANALYSIS P~x
Factor Factor Factor 0 6 TIO2/~J293
I 2 3 r,zo.~ ~_
mTE~
0 2 RE£
1<70 0,966 0,074 0,099 ~ Az-s~,-9
AJ-Sll 0,955 0,074 0,069 ~<- 0 2 LI

AI;O a 0,937 0,081 0,297

REE 0,902 0,057 0,283 -o 6
MgO
llO; 0,886 0,088 0,354 .1 . . ,
-1 -0, 6 -0, 2 O. 2 0.'6
TRTE 0,882 0,086 0,323 fACTOR I
Fe?O~ 0,859 0,107 0,344
Stev -0,152 -0,959 -0,041 CLUSTER DIST~CES
0.000
U 0,012 -0,901 -0,266 sepiol
F
Seplol -0,261 0,264 -0,913 Mgo ~l__
M@O -0,360 -0,403 -0,785 Neophy l 2. 000
Li ]
F -0,370 -0,380 -0,737 Stev - -

Paly 0,058 0,131 0,709 K2O

Al-Sil
Neophy -0,405 -0,341 -0,609 REE
E~=~.d~,o~. 45,45 16,35 24,72 TRTE
TiO2
A1203
Fe203
Faly

Fig. 4. Factor analysis of principal components and cluster of main mineralogical and chemical variables. Legend as in
Table 6.

those of meteoric water during that period. In environments and strongly affected by sup-
contrast, the E1 Cuervo deposit, of a younger plies of highly negative carbon ( - 2 5 to
age (Upper Pliocene), is in equilibrium with - 10%o), which must have originated in the
waters having J lSO-values between - 7 to decomposition of the plant cover and in the
- 5%0, similar to those of recent meteoric breathing of plant roots (Salomons and Monk,
waters from SE Spain (IAEA, 1981; Delgado 1976; Salomons et al., 1978; Deines, 1980).
et al., 1991 ). Such negative 613C-values discount the possi-
bility of a marine origin for the carbonates.
4.2.2.2. lsotopic composition of carbonates. The most negative values are found in the
The calcite samples analysed correspond to the calcites ( - 11.15 to - 8.12%o) and are consis-
Cerro Batallones, E1 Cuervo and Pareja depos- tent with an edaphic origin, under the majority
its, while the dolomite samples are from the presence of C3 plants. In fact, this type of
Almaz~tn and Calatayud deposits, plants, which follow the Calvin-Benson pho-
tosynthesis cycle, have t~13C isotopic values of
4.2.2.2.1. Carbon. The 6~3C-values have a around -26°/o0 (Ceding, 1991 ). Sincethe car-
wide range ( - 11.15 to - 4.28%o) and are typ- bonates are ~ 10% heavier in 6 ~3C in compar-
ical of carbonates originating in continental ison with the isotopic composition of the CO2
238 J. TORRES-RU|Z ET AL.

101 , , , , , , , , , , , , , , Io ~ , . . . . . , , , , , , , =-- lO 1 ~ _ = _ ~ _ = _ . = _ = ~ . . . . . .

Q)

x 'N2g ~. * Pa26
+ ~,c27 o P~25
:s .,- ~c26 o Par21
< 10-1 o ~2_4 10-t / " Pa,'3
• '¢1C23 • 10-11 h . . . . ~_ . . . . . . . . o Par 1
o ~c,21 La Ce Pr NdSmEuGd Ib D/HoBTm~Lu

~ o pa~1 -.--,= t, . . . . . . . . ,-
•~ Vie6 . Oh7 Maderuel0
., Vlc6 .066
sFIc4 . =Oh4
o Vr-.3 ..Oh2
10-2 , , , , , , , , , , , t , ,
La Ce B"~SmEuGdlb DyHoEfTrn'YbLu
- Ft.2 10-2 , i , , , ~ J , ~ , k , ~
La Ce R NdSmEuGdTo D/HoEr fmYb Lu
o Oh;
.of
Calatayud Almazan o Mad6
o Mad3
10_.I
~ . , ~ , ~, o~ Mad2
Madl
I~ Ca R I~8mEu Gd Tb D,/I-bErlm~ lu

~<~01401 t I' ~~ " ~~ z - ~' ] ~ \~ 10010

' ~i ~. . .~. . . . . . .". . . . . . . 1111i- : '--=- ' . .El
. . . .Ouervo
.... -!

• 0aI321 ,,, Aim24

o C~8 o Aim23 o Ec9
o Cala7 o klm22 a Ec8
,, ~ Ec5
10-2l . . . . . . j ~ ...... | o Cala2 10-2 , , ~ , , ~ ~ , i , ~ ~ ~ ~ o Aim1 10 L _ ~ . . . ~ , , , , , , , , , , o Ec4
La Ce PrNLI~Eu~1 ro DyHoBTmYbLu la Ce R Nd 8mEu~ To DyHo 6" lm~ Lu L~ Ce R N(I~Eu Gd Tb DyHo Erlrn~ Lu

Fig. 5. NASC-normalisedREE patterns of the analysedsamples.

supplied by the carbon reservoir (Emrich et al., - 24%0, thus indicating a source of C3 plants
1970; Friedman and O'Neil, 1977) to which with a very scarce atmospheric CO2 contribu-
another 4°/00 is added by the oxidation of or- tion. The slightly higher values ( - 9 . 5 to
ganic matter in the plant cover (Ceding, 1984; - 8%o) found in the Pareja and E1 Cuervo de-
Ceding and Hay, 1986; Quade et al., 1989), posits indicate a higher atmospheric CO2
the composition of the resultant edaphic car- contribution.
bonates would bc around - 12°/00. The contri- The dolomites present heavier J13C-values
bution of atmospheric CO2 would have pro- ( - 5.74 to - 4.28%o) and must therefore have
duced deviations in this value towards higher been more affected by atmospheric CO2. The
jl3C-values. Consequently, the Cerro Batal- higher fractionation in the dolomite (in com-
lones (CB) samples, with J~3C-values of - 11 parison with the calcite) as regards the CO2
and - 10%oo, would have been provided by a which formed it may also have contributed, al-
reservoir with isotopic compositions o f - 2 5 to though only slightly, to these heavier carbon
GEOCHEMISTRY OF SPANISHSEPIOLITE-PALYGORSKITEDEPOSITS 239

lO6 . . . . . . . TABLE 7
Seololites (*)
Stevons~tes(-) Isotopic data of carbonates (PDB), silica, sepiolite, palygor-
'/~i~'-~ skite and stevensite (V-SMOW)
104 ~ r s k i t e 8
Sample j 180 j 13C
"~ . J ~ Averaoe detrltl (0/00 VS. (o/~ VS.
~ ~ PDB) PDB)
103
Averagee Shales Calcite CB-2 - 6.54 - 9.96
(Tur~,den& Wedepoht19~1)
• CB-5 -6.39 - 11.15
Carbonates
EC-3 - 1.52 - 9.40
102 I I J = I ~ I EC-9 - 1.06 -8.58
100 200 300 400 500 600 700 80o PAR-25 - 6.40 - 8.12
REE + TRTE (ppm)
Dolomite ALM-6 - 2.25 - 5.43
ALM-23 -2.38 -5.74
500 ' Averagedetritlc AI-Silicatesf CALA-I + 1.31 -4.53
AverageShales • ~ CALA-2 + 1.94 -4.29
400 ,,~ ~w ~ , ~ , , ~ CALA-3 + 1.07 - 5.02

Sample j is0
~300 (%0 vs.
v
LU V-SMOW)
F-
or 200 (= j ) i=alygorskites
F- Silica CB-a + 24.1
100 ~ CB-b +25.6
,~""~'~ Sepiolites (*) EC + 30.4
0 ~ ~ta°r~t~°s?~) ~ VIC +23.6
0 100 200 300 Sepiolite PARLA-I + 18.2
REE (ppm) CB-7 + 18.8
VIC-8 + 18.0
Fig. 6. REE, TRTE and F contents of sepiolites, palygor-
skites, stevensites, detrital Al-silicates and carbonates in Palygorskite PAR-25 + 22.0
the studied deposits. The REE, TRTE and F contents of PAR-26 +21.0
carbonates correspond to sample ALM-30 (98% calcite).
The average content of REE and TRTE of the Al-silicates Stevensite VIC-3 + 16.0
were calculated from their regression lines. The average F VIC-9 + 17.0
content of M-silicates was deduced from sample VIC-21
(88% M-silicates and 12% quartz). The samples of se-
piolite (CALA-2, -8, CB-4, -7, PARLA-1, -2, VIC-8, -29, t h a t at t h e e n d o f t h e T e r t i a r y t h e Pco2 in t h e
-3o), palygorskite (ALM-22, -23, -24, MAD-5, PAR-25, a t m o s p h e r e c o u l d h a v e b e e n b e t w e e n 600 a n d
-26) and stevensite (VIC-3, -4) included in this figure 1000 ppmV (Berner, 1990), only an arid eli-
correspond to those very rich in only one of these phyllos-
ilicates. Their REE, TRTE and F contents were obtained mate would have contributed to a n apprecia-
from equations of this type: ble i n f l u e n c e o f a t m o s p h e r i c c a r b o n , w h i c h is
m u c h h e a v i e r ( - 6.5%0) t h a n t h a t p r o v i d e d b y
REEsepiol = REEsample -- REEAt.snicates-- REEcarboaates
p l a n t d e c o m p o s i t i o n ( - 25%o), t h u s p r o d u c -
ing h i g h e r J~ 3C-values.
v a l u e s ( ,,, 1 - 2 % o ) ( F o n t e s et al., 1970; S h e p -
pard and Schwarcz, 1970). 4.2.2.2.2. Oxygen. T h e J~sO in t h e s a m p l e s
T h e h i g h e r c o n t r i b u t i o n o f a t m o s p h e r i c CO2 r a n g e s f r o m - 6 . 5 4 to + 1.94%o ( P D B ) , the
is e n c o u r a g e d b y t h e i n c r e a s e in a r i d i t y c o i n - m o r e n e g a t i v e v a l u e s c o r r e s p o n d i n g to calcites.
cident with lower development of the plant T h e a(~¢~t,-w=,~) i s o t o p i c f r a c t i o n a t i o n is
c o v e r . I n d e e d , i f w e t a k e i n t o a c c o u n t t h e fact well k n o w n f o r a w i d e r a n g e o f t e m p e r a t u r e s
240 J. TORRES-RU|Z ET AL.

(A) (B)

~- eo

0 1 ~ 2

(~la0 OF THE CALCITE

~ 20

20 21 22 23 24 25 26 27 28 29 30 31 32 35 12 14. 16 18 20 22 24 26 28 30
~'a0 OF THE SILICA (~'80 OF THE SMECTITE
Fig. 7. A. T ( °C)-&180 (°/oovs. PDB) diagram for calcites according to the equation of Anderson and Arthur ( 1983 )
B. T ( °C)-c~ 180 (%o vs. PDB) diagrams for dolomites according to the equation of Irwin et al. ( 1977 ).
C. T ( °C )-8~aO (%o vs. SMOW) diagrams for silica based on a low-temperature extrapolation of the equation by Clayton
et al. (1972)
D. T ( °C)-c~sO (%o vs. SMOW) for Mg-smectites according to the equation by Savin and Lee ( 1988 ).
Curves represent the theoretic values of ~ s O of minerals in equilibrium with waters of different isotopic composition.
Thick lines represent the 8~SO-values of the different minerals analysed and the solutions in equilibrium with them for a
15-25 ° C temperature range.

(Epstein et al., 1953; Craig, 1965; O'Neil et al., T ( °C ) =

1969; Friedman and O'Neil, 1977 ). Anderson
and Arthur (1983) proposed the following 31"9--5"55(C~d--C~w)+0"17(C~d--fiw)2
equation:
T (°C)= In both equations ~c and c~d are the 6180
(PDB) of calcite and dolomite, respectively,
16-4.14(~c -C~w) +0.13 (c~c-6w) 2 and C~wis the ~ 8 0 (SMOW) of the water with
For the less well-known fractionation of do- which the carbonate was in equilibrium.
lomite-water, Garlick (1974) proposed the The calcites of the Cerro Batallones and
equation: Parla sites have c~180-values of - 6 . 4 + 0.1%o,
GEOCHEMISTRY OF SPANISH SEPIOLITE-PALYGORSKITE DEPOSITS
which are similar to those of other meteoric
calcites precipitated at similar latitudes (Hays
and Grossman, 1991 ). For the range of envi-
ronmental temperatures between 15 ° and
25°C these calcites were in equilibrium with
water whose isotopic composition ranged from
- 7 to -5%0 (Fig. 7). The calcites from the E1
Cuervo site show values of - 1 and + 1.5%.
Comparison of these values with those ob-
tained for meteoric water on the basis of the
J~SO-values in silica indicate that the calcites
precipitated from highly evaporated water
(J~sO enriched to ~ 4-60/00).
The isotopic ratios in oxygen for dolomites
are grouped around -2.3%0 in the Almaz~tn
site and would have been in equilibrium with
water of - 6 to -4%o for the 15-25°C range
of environmental temperature, whereas the
dolomites in the Calatayud deposit, with corn-
positions between + 1 and + 2%o, correspond
to water of - 2 to 0%o composition (see Fig.
7). As in the case of the calcites, these data in-
dicate that the dolomites precipitated from
highly evaporated water, and the Calatayud
deposit presents the highest evaporation ratio,
4.2.2.3. Isotopic composition of the neoformed
silicates. The isotopic fractionations of the clay
minerals are as yet not particularly well known.
Of the clay minerals present in the sites stud-
ied here, only the isotopic fractionation of
smectite is well known in a wide range of tern-
peratures. Data on sepiolite and palygorskite
are scarce in the literature. For sepiolite we
have only found one approximate value of
a(~pioate-water)= 1.033 (at 0°C at the bottom of
the Atlantic; Savin, 1973). For palygorskite,
Church and Velde (1979) obtained values
which are somewhat confused as regards both
the units employed (PDB or SMOW?) and the
genesis. The isotopic analyses of the samples
of sepiolite ( > 97% pure) and palygorskite
(enriched by chemical treatment to >90%)
permitted us to make an approximate evalua-
tion of the isotopic fractionation of oxygen in
the sepiolite-water and palygorskite-water
241
systems at environmental temperatures.
The samples richest in smectite from the Vi-
calvaro site present values of + 16 to + 17%0.
The values from VIC-3 (94% pure) indicate
equilibrium with meteoric water with j~so-
values of - 11 to - 9%0 at temperatures be-
tween 15 ° and 25°C (see Fig. 7). Sample VIC-
9, with a more positive J~SO-value probably
due to its mixture with a high percentage of se-
piolite (18%), also agrees with this type of
water. These values, which are somewhat
lighter than those of present-day water, coin-
cide with the values obtained for water on the
basis of the isotopic fractionation of silica.
If we consider that sepiolite is a chemical
precipitate and that it precipitates from the
same type of water as Mg-smectite and silica,
on the basis of the known a(sttiea_water)fraction-
ation at environmental temperatures and the
j lSO.values obtained for silica and sepiolite in
the Vicftlvaro, Cerro Batallones and Parla sites,
we obtain an isotopic fractionation od(sepiolite-
water)= 1.031 in all cases, for a temperature of
20 ° C. The validity of the method used to cal-
culate the O/(sepiolite_water) can be tested by using
the same method to calculate the fractionation
of Mg-smectite. By this procedure, also on the
basis of the j~SO-values of silica and smectite
(sample VIC-3 with 94% smectite ), we obtain
a O~(smectite_water)-ValUe of 1.029, which is simi-
lar to that given by Lawrence and Taylor
( 1972 ) for smectite with < 4.5% Fe and also
to that given by Savin and Lee ( 1988 ).
The isotopic compositions of the palygor-
skites present higher glSO-values ( + 2 1 to
+22%0) than the other neoformed silicates
mentioned above, which indicates formation
in environments undergoing higher evapora-
tion and, therefore, in equilibrium with heav-
ier water than that considered for the forma-
tion of silica, sepiolite and smectite. On the
contrary, the palygorskite could be more read-
ily associated with the water from which the
carbonates precipitated. If we accept this fact
(supported by the constant association of pal-
ygorskite with carbonates), on the basis of the
242
known a(calcite_water) fractionation and the
dlaO-values of palygorskite and associated
carbonates, we obtain a C~(palysorskite-water)-Value
of 1.027 at 20°C.
5. Genetic considerations
The conditions of formation of magnesian
clay minerals in sedimentary environments
continues to be the subject of considerable de-
bate. The main question is to determine
whether these minerals formed by direct pre-
cipitation, from the solutions in the deposi-
tional basins or diagenetic solutions, or whether
they are the result of diagenetic reactions be-
tween solutions and solids and, therefore,
products of the transformation of preexisting
material (see Yelde, 1985 and Jones, 1986).
According to Jones (1986), evidence from
both ancient and present lacustrine deposits
indicates that the second case is the most com-
mon cause of the authigenic formation of clay
minerals in lake environments. The transfor-
mation of preexisting clays seems particularly
encouraged where the proportion of sediment
to water is high and where there is an impor-
rant solute content (beaches and typical salt
lakes). This type of diagenesis produces the
same proximal-distal compositional trend
(increase of Si and Mg towards the centre of
the basin) as that of direct precipitation, ac-
cording to the model proposed by Millot
(1977). Textural evidence (Khoury, 1979)
and laboratory experiment (Siffert and Wey,
1962; Wollast et al., 1968) indicate that se-
piolite can nucleate directly from natural water
rich in Si and Mg. Jones (1986) pointed out
that the only silicate phases that nucleate di-
rectly from natural surface water rich in Si seem
to be sepiolite and magadiite, the latter at con-
siderably higher salinity than the former. Velde
(1985) indicated t h a t s t e v e n s i t e m u s t e s s e n -
tially be a chemical precipitate, and that Li is
a component necessary for its crystaUisation,
As regards palygorskite, Gal~tn et al. ( 1975 ),
Callen (1978), Singer (1979) and Estroule-
J. TORRES-RUIZ ET AL.
Choux (1984), among others, indicated the
formation of palygorskite mainly by precipi-
tation and not by diagenetic reaction. How-
ever, other authors such as Couture (1977),
Kastner ( 1981 ), Gal~ln and Ferrero ( 1982 ),
Weaver (1984) and Tazaki et al. (1987) up-
hold the formation of palygorskite by transfor-
mation of other clay minerals, especially from
dioctahedral smectites.
In most cases, the evidence on which work-
ers base their attempts to discover the origin of
magnesian phyllosilicates in the sediments of
continental or marine basins derives from ex-
perimental work and electronic microscope
observation of certain mineral transforma-
tions (Weaver, 1984; Tazaki et al., 1987; Ab-
del-Samad et al., 1989). In this paper we use
the amounts of certain trace elements (F, Li,
REE and transition elements) and isotopic
fractionation data as discriminating parame-
ters. Clay minerals produced by weathering
and/or transformation, tend to inherit and
level out the distributions of residual trace ele-
ments (REE and transition elements) of their
source rocks or minerals. On the other hand,
directly precipitated clay minerals show very
low REE content and distributions according
with those of the solutions in the depositional
basin, where the amount in solution is very
small in comparison to that transported by
particles (in fresh water sumREE is ~ 1 0 - 4
ppm). Furthermore, as against detrital min-
erals, neoformed clay minerals in evaporitic
basins could retain higher quantities of migra-
tory elements (such as F and Li) during con-
tinental weathering.
The study undertaken by us shows that, on
the one hand, the REE and first-series TRTE,
and, on the other, the F contents clearly distin-
guish and separate the inherited aluminosili-
cates from sepiolite and Mg-smectite. More-
over, the contents of these elements in
palygorskite are intermediate between those of
both mineral groups. This suggests a genesis of
this mineral other than by direct chemical pre-
cipitation from the solutions in the deposi-
GEOCHEMISTRYOF SPANISHSEPIOLITE-PALYGORSKITEDEPOSITS
tional basins. Indeed, such proportions, and
those of A1, would rather suggest palygorskite
genesis bytransformationofdetritalphyllosil-
icates. These genetic considerations are sup-
ported by the results of the analysis of isotopic
fractionation. The data obtained indicate that
sepiolite, stevensite and silica are in equilib-
rium with waters of similar isotopic composi-
tion (~lSo) and that they are different to the
solutions in equilibrium with palygorskite,
which have heavier values similar to those of
water in equilibrium with carbonates.
6. Conclusions
6.1. Trace elements
( 1 ) REE and first-series TRTE on the one
hand, and F and Li contents on the other can
be used to distinguish between inherited phyl-
losilicates and phyllosilicates formed by chem-
ical precipitation in the depositional basins,
The former present high sumREE and sum-
TRTE values and very low values of F and Li,
whereas the latter have low sumREE and
sumTRTE values and high F values. The latter
also have high Li values in laminar minerals,
as is the case of Mg-smectite, which distin-
guishes it clearly from inherited dioctahedral
smectites,
(2) The REE, TRTE, F and Li contents of
sepiolite and Mg-smectite (stevensite) indi-
cate the formation of these minerals by chem-
ical precipitation from natural surface water.
On the other hand, the contents of these ele-
ments in palygorskite rather indicate an origin
by transformation of other inherited clay
minerals.
6.2. C and 0 isotopes
( 1 ) The main source of C in the carbonates
was edaphic, mainly provided by decomposi-
tion of C3 plants.
(2) Sepiolite, Mg-smectite and silica (either
cryptocrystalline or opal-A) formed in equi-
243
librium with surface solutions of similar iso-
topic fractionation (c~lSO), which are differ-
ent to the solutions in equilibrium with
palygorskite and carbonates (isotopically
heavier solutions, related to more evaporated
solutions).
(3) The values calculated for the fractiona-
tion factors of the sepiolite-water and palygor-
skite-water systems at 20°C are:
Og(sepiolite_water)
= 1.03 1
Og(palygorskite_water)
= 1.027
Acknowledgements
We thank A. Alvarez and J. Casas (TOLSA
S.A., Madrid) for their collaboration in the
field work, and Dr. E. Reyes (Estaci6n Exper-
imental del Zaidin) for his help in the results
and discussion of isotope data. We also thank
TOLSA S.A. for the analytical data of major
and trace elements. This research has been
partially financed by groups 4065 and 4028 of
the Autonomous Government of Andalucia.
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