Applied Clay Science, 6 (1992) 265-276 265

Elsevier Science Publishers B.V., Amsterdam

The formation of bentonite: mass balance effects

E. Caballero, E. Reyes, A. Delgado, F. Huertas and J. Linares

Estacion Experimental de Zaidln (e.S. I.C), Profesor Albareda 1. 18008-Granada. Spain
(Received April 23, 1991; accepted after revision August 30, 1991)

ABSTRACT

Caballero, E., Reyes, E., Delgado, A., Huertas, F. and Linares, J., 1992. The formation of bentonite:
mass balance effects. Appl. Clay ScL, 6: 265-276.

The alteration of volcanic material into bentonite produces an important loss of mass originated by
the hydrolytic action of a large amount of hydrothermal solutions. The latter solutions also provide
essential elements for the formation of these materials. Mass balance gains and losses in 52 samples
from several bentonite deposits show that the greatest element losses correspond to Si, and to a lesser
extent to Na and K. There are some gains in Fe, Ca, Mg and H 20. On the other hand, there is a good
correlation (1'=0.87) between the amount of matter lost and the amount of smectite formed. In ad-
dition, the relationship between matter loss and the chemical composition ofthe neoformed smectite
has been studied, and it has been observed that the chemical composition of smectite varies with
increasing matter loss. The initial smectite contains less A I, and more Fe and Mg in comparison to
the final smectite.

INTRODUCTION

The fundamental process that takes place during the formation of hydro-
thermal bentonites is the hydrolysis of volcanic materials. This process re-
quires the existence of important accumulations of porous and vitreous rocks
and large quantities of aqueous solutions above room temperature (Caballero
et al., 1985; Linares, 1985).
Leone et al. (1983) determined the formation temperatures for bentonites
samples taken from the Cabo de Gata region (southeastern Spain); they av-
erage between 40 and 70°C.
From the relationship between the chemical composition and density of
rock and bentonite, it can be inferred that large losses of matter take place
during the alteration process. There is some natural evidence that supports
this conclusion. Thus, at some points in the volcanic region of Cabo de Gata
(Almeria, Spain) there are bentonite dikes, extruded through fractures, which
may derive from the collapse of the deposit overburden caused by matter loss
during bentonite formation. In other cases, small geomorphological read-

0169-1317/92/$05.00 © 1992 Elsevier Science Publishers B.V. All rights reserved.

266 E. CABALLERO ET AL.

justements, also due to reductions in volume, can be observed in some ben-

tonite deposits (Reyes et al., 1979a, b; Caballero et al., 1985).
The purpose of this work was to calculate the loss of matter in a series of
bentonite deposits in the Cabo de Gata region, starting from the chemical
composition of the parent rock, which was deduced theoretically. In addition,
we have tried to analyze the variations in the chemical composition of the
smectites, depending on the different amounts of material lost.

MATERIAL AND EXPERIMENTAL METHODS

Fifty-two bentonite samples, displaying different degrees of alteration and

belonging to bentonite deposits of small outcrops in Cabo de Gata were se-
lected (Fig. 1). The transformation is total and, therefore, no parent rocks
are present. The selection of these samples was made strictly on the basis of
geological criteria, the sample being taken from those points where the parent
rock was probably a rhyolite.
Mineralogical analysis (Table I) was carried out by XRD, following a
methodology similar to that of Tatlock (1966). The chemical composition of
bentonites (bulk sample) and smectites ( < 2 ,um fraction) was determined
by the wet method (Table II) (Huertas and Linares, 1974).

RESULTS AND DISCUSSION

Inferring the theoretical parent rock

As already mentioned, the transformation into bentonite was so complete,

that no parent rock remained. In order to determine the composition of the
parent rock, a series of calculations were made starting from the chemical
analysis of bentonites and based on Barth's geological balance (1948), so as
to normalize all the data. Because all the bentonites showed different degrees
of alteration (different smectite percentages), Barth's parameter was re-
gressed against the smectite content. In this way, by extrapolation to a zero
smectite content, the composition of the parent rock or a rock very similar to
it, is derived. The regression equations obtained are given in Table III. From
extrapolation to zero smectite, the following parent rock composition is ob-
tained: Si0 2=78.95 %, A1 20 3=8.18 %, Fe203=5.81 %; Ti0 2=0.44 %,
Na 20=2.51 % and K20=3.92 %.
The values for MgO, CaO and H 20+, which are negative in this extrapola-
tion, are considered to be zero. When comparing these data with values avail-
able for rocks in the region (L6pez and Rodriguez .Badiola, 1980), a great
similarity to rhyolites was found, although there are some significant
differences.
For this reason, the values previously given have been slightly corrected,
THE FORMATION OF BENTONIT E: MASS BALANCE EFFEC TS 267

SPAIN

F':1 QUATERNARY
~

~ MIOCENE LIMESTONE

o VOLCANIC ROCK

• J UR ASSIC
LIMESTONE

0 123045

~---
Fig. 1. Geographical and geological locations of the samples .
268 E. CABALLERO ET AL.

TABLE!
Mineralogical composition of bentonites

Sample Sm Plag Q Z Try Cal FK

MM·I 83 5 [ 2 9
MM·2 65 9 2 2 22
LP·I"' 62 28 I 2
EC·! 44 40 2 4 10
EC·2 41 53 8 6 5 5
EC·3 64 2 3[ 3
ECA 55 29 4 2 10
EC-5 41 32 8 14
VB.["3 50 3 9 17 [3
VB·2 97 3
SF· I"' 74 12 2 2 5
LT· I 98 2
LT-2 98 2
LT-3 98 [
LT·4 97 2
LT·5 98 2
LT·6 83 3 7
LT-7 99 [
LT·8 93 3 [ 3
LT9 [00
LT·9/l [00
LT·9/2 100
LT·9/3 98
LT-9/4 99
LT·IO 99
LT·IO/I 100
LT·IO/2 96 2 2
LT· I0/3 96 2 2
LT·10/4 97 I 2
LT·10/5 98 I I
LT·10/6 99 I
LT· 1I 98 2
LT·II/I 100
LT· I 1/2 100
LT-ll/3 100
LT-II/4 93 2 3
PC·I/l 86 12 1
PC·I/2 89 9 [
PC·I/3"' 51 15 7 8
PC·I/4 87 12
PC-I/5 92 7
PC·2/1 96 4
PC·2/2 96 4
PC·2/3 94 4 2
PC-2/4 94 6
PC·2/5 88 12
PM-! 77 18 5
PM-2 95 3 2
PM-3 95 3 2
PM-4 93 7 4
PM-5 90 8 2
PM·6 88 10 2
Srn e smectite; Plag-plagioclasc; Qs-quartz: Z=zcolite; Try e trydimite; Cal e calcite: FK= K-feldspar.
"IContains 7% amphibole.
•2Contains 5% amphibole.
•3Contains 3% mica and 4% gypsum.
"Contains 19% jarosite.
THE FORMATION OF BENTONITE: MASS BALANCE EFFECTS 269

TABLE II

Chemical composition of bentonites

Sample Si0 2 AI20 3 Fe20, Ti0 2 CaO MgO Na20 K20 CO2 H 2O+

MM-I 59.88 17.74 4.91 0.42 5.47 2.34 1.11 0.33 2.13 6.39
MM-2 69.29 15.84 4.27 0.54 1.05 1.56 2.20 0.50 0.15 4.65
LP-I 61.54 17.86 7.21 0.57 2.77 2.24 2.22 0.38 1.35 4.34
EC-I no 14.32 1.07 0.11 1.04 0.64 0.64 3.03 0.60 2.56
EC-2 76.77 13.67 0.84 0.10 1.22 0.66 0.31 2.78 0.73 2.61
EC-3 72.72 15.60 2.08 0.09 0.38 1.61 0.55 1.98 0.07 4.24
EC-4 69.77 17.94 1.45 0.10 0.75 0.58 1.40 4.04 0.38 3.07
EC-5 71.65 16.37 2.00 0.10 0.88 0.84 1.33 3.93 0.45 2.14
YB-l 69.31 13.32 2.01 0.12 4.52 0.69 2.58 1.32 3.49 2.32
YB-2 64.61 2l.47 2.77 0.12 0.28 2.29 1.0 I 1.57 0.05 6.06
BF-I 62.79 18.46 5.58 0.53 3.07 1.73 1.34 0.60 1.61 5.19
LT-I 54.81 26.15 2.37 0.00 1.19 4.56 0.94 0.42 0.00 9.11
LT-2 56.02 26.38 1.52 0.00 1.19 4.43 0.75 0.50 0.00 9.96
LT-3 59.24 24.11 0.06 0.00 1.18 5.08 0.93 0.33 0.04 9.62
LT-4 57.95 23.51 1.67 0.00 1.76 4.35 0.74 0.33 0.09 9.75
LT-5 59.18 22.71 1.17 0.00 1.75 4.90 0.83 0.25 0.00 9.96
LT-6 53.91 21.66 1.69 0.00 8.83 3.86 1.00 0.40 5.37 3.98
LT-7 60.l7 22.08 0.90 0.00 3.55 3.26 0.66 0.33 0.44 9.53
LT-8 57.53 23.34 1.39 0.00 3.12 4.48 0.92 0.33 0.00 9.61
LT-9 59.65 23.42 1.11 0.00 0.78 4.92 0.66 0.25 0.00 9.72
LT-9/1 60.04 22.27 0.86 0.00 1.41 5.05 0.58 0.34 0.00 9.63
LT-9/2 58.19 23.66 1.41 0.00 1.38 4.96 0.61 0.25 0.00 9.44
LT-9/3 58.60 23.40 2.24 0.00 1.15 5.25 0.63 0.24 0.66 8.72
LT-9/4 58.87 23.31 1.41 0.00 1.39 5.58 0.62 0.17 0.04 8.81
LT-IO 57.86 23.35 3.11 0.00 1.95 4.49 0.65 0.33 0.00 9.39
LT-IO/l 54.80 26.10 2.60 0.00 1.56 5.18 0.74 0.33 0.00 9.47
LT-IO/2 58.64 23.67 0.00 0.00 2.02 4.63 0.66 0.25 0.00 9.31
LT-IO/3 57.98 22.94 1.96 0.00 1.58 5.67 0.70 0.33 0.09 9.57
LT-IO/4 59.62 22.64 0.33 0.00 1.44 6.43 0.69 0.25 0.09 9.51
LT-IO/5 58.41 23.92 1.09 0.00 1.94 4.87 0.69 0.25 0.00 9.27
LT-IO/6 58.99 24.47 0.63 0.00 1.40 4.04 0.76 0.34 0.00 9.77
LT-II 57.00 25.03 1.22 0.00 1.98 4.78 0.66 0.33 0.00 9.64
LT-ll/l 55.13 25.93 2.96 0.00 1.19 4.84 0.38 0.25 0.00 9.25
LT-ll/2 56.41 25.38 2.81 0.00 1.14 4.64 0.49 0.30 0.00 9047
LT-II/3 61.79 21.17 0.00 0.00 0.80 6.14 0.38 0.25 0.00 9.44
LT-ll/4 58.59 21.46 1.92 0.00 1.94 5.15 1.29 0.54 0.13 8.97
PC-I/l 61.47 22.53 3.35 0.51 2.60 2.05 2.45 0.61 0.07 6.23
PC-Ij2 61.93 20.04 3.59 0.52 1.94 3.00 2.74 0.67 0.18 6.94
PC-I/3 52.63 15.94 13.79 0.39 1.23 1.24 3.64 0,81 0.04 8.49
PC-I/4 59,83 22.42 4.15 0.46 2,85 1.58 2,88 0.81 0.00 5,04
PC-lj5 60,78 20.59 4.88 0,29 1.11 3.79 1.95 0.58 0.00 6.09
PC-2/ I 62.03 20.67 3,01 0,22 1.05 5.28 2,51 0.50 0.42 6.57
PC-2/2 63.92 20,62 2,74 0.25 0.72 5,21 2,14 0.47 0.05 5.81
PC-2/3 60.11 19,10 3.41 0.30 1.28 5.11 2,16 0,80 0,08 5,92
PC-2/4 61.22 20041 3.96 0.26 1.05 5,36 1.85 0,53 0.00 6,39
PC-2/5 61.31 20,06 3.78 0.38 1.00 5.31 1.89 0.57 0.00 6,25
PM-I 65.98 16.47 1.92 0,24 2,06 1.34 3.12 1.80 0,00 6,68
PM-2 67.07 17.26 2.21 0,22 0,39 5.02 1.94 0.41 0.10 6.22
PM-3 63.56 20.11 2.98 0.45 0,85 5.13 2.42 0.87 0.60 6.08
PM-4 61.18 20.08 3.64 0,24 1.37 5.12 2.40 0,67 0.00 6.08
PM-5 62.36 20.04 4.42 0.39 1.62 4.76 2.54 0.78 0.00 6.93
PM-6 61.96 20.30 3.01 0.25 0,58 3.60 3.33 1.25 0.00 6.23
270 E. CABALLEROET AL.

TABLE III

Regression equations [Barth's ( 1948 ) cations versus smectite content %I

y X ao b r n Sign.
Si %Sm 72.08 -0.25 0.835 52 1 %0
Al %Sm 8.79 0.13 0798 52 1 %0
Fe %Sm 3.97 - 0.03 0.333 52 5%
Ti %Sm 0.30 0.002 0.339 52 5%
Ca %Sm - 0.05 0.0 1 0.352 52 5%
Mg %Sm - 3.85 0. 10 0.848 52 1 %0
Na %Sm 4.44 - 0.02 0.299 52 5%
K %Sm 4.57 - 0.04 0.782 52 1 %0
H %Sm -9.06 0.55 0.791 52 1 %0
ao= Y axis intercept; b =slope; r= correlation coefficient; n::::number of data; Sign.=st atistic
significance.

taking into account the relation between the oxides of calc-alkaline rocks and
the Si0 2 content in the rocks from this region (Lopez and Rodriguez Badiola,
1980). The final result for parent rock composition is as follows:
Si0 2=79.01 %; A1 20 3= 10.80 %; Fe203=OAO %; Ti0 2=O .36 %;
CaO=O.60 %; Na20=2.37 %; K20=3.95 %; and H 20+=2 .51 %.
The MgO value is still zero. This rock is a rh yolite, according to the classi-
fication of Lopez and Rodriguez Badiola (1980) which in its form is a mod-
ification of that of Pecerillo and Taylor (1976).

Mass balance

Once the parent rock composition is known , losses and gains of matter can
be established . For th is purpose, Barth's values are recalculated so that all
samples contain as much aluminium as the original rock. This assumption is
based on the absence of proper physicochemical conditions for the solution
of aluminium, as evidenced by the study of the composition of hydrothermal
solutions in the region carried out by Caballero et al. (1985). It is assumed,
therefore, that all the Al in the rock passed over to smectite. Afterward, these
values for cations are recalculated to the weight of the corresponding oxides,
and finally, the oxide contents of the inferred parent rock are subtracted from
the composition of each bentonite. These values are shown in Table IV, ex-
pressed as percentages of loss or gain in relation to the parent rock.
From the data obtained, Si exhibited the most important losses, whereas ,
considering average values for depos its, there were minor losses for K and
Na, and gains in Mg, Fe, Ca and H 20 .
The silica loss, with a mean value of close to 50 % (weight basis) , is an
evidence that the process must be considered highly destructive, since one ton
of parent rock only yields half a ton of bentonite, on the average. Now, in
THE FORMATION OF BENTONITE: MASS BALANCE EFFECTS 271

TABLEIV

Barth's ( 1948) balance. Percentage oflosses ( - ) and gains (+ ) at constant Al

Sample Si Fe Ti Ca Mg Na K H Total
loss
MM-I -42.56 2.59 -0,10 2,73 1.42 1.69 -3.75 1.38 -39.98
MM-2 - 31.77 2.51 0.01 0.12 1.06 -0.87 -3.61 0.66 -31.89
LP-I -41.80 3,96 -0.02 1.08 1.35 -1.03 -3.72 0.11 -40.06
EC-I -20.94 0.41 -0.28 0.18 0.48 -1.89 -1.66 -0.58 -24,27
EC-2 -19.23 0.25 -0.28 0.35 0,51 -2.13 -1.79 -0.48 -22.79
EC-3 -28.62 1.04 -0.30 -0.34 1.11 -1.99 -2.58 0.43 -31.24
EC-4 -37.01 0.47 -0.30 -0.15 0,35 -1.53 -1.52 -0.66 -40.34
EC-5 -31.74 0,92 -0.29 -0,02 0,55 -1.49 -1,36 -1.10 -34.53
VB-I -22.81 1.23 -0.26 3.06 0.56 -0.28 -2.88 -0.63 -22.01
VB-2 -46.51 0.99 -0.30 -0.46 1.15 -1.86 -3.16 0.54 -49.61
BF-I -41.27 2.86 -0.05 1.20 1.01 -1.59 -3.60 0.53 -41.91
LT-I -56.37 0.58 -0.36 -0.11 1.88 -1.98 -3.78 1.25 -58.89
LT-2 -56.08 0,22 -0.36 -0.11 1.81 -2.06 -3.75 1.57 -58.75
LT-3 -52.47 0.37 -0,36 0.07 2.28 -1.95 -3.80 1.80 -54.96
LT-4 -52.39 0.37 -0,36 0,21 2,00 -2.03 -3.80 1.97 -54.03
LT-5 -50.87 0.16 -0.36 0.23 2.33 -1.98 -3.83 2.23 -52,09
LT-6 -52.13 0.44 -0.36 3.80 1.92 -1.87 -3.75 -0.53 -52.47
LT-7 -49.58 0,04 -0.36 1.14 1.59 -2.05 -3.79 2.15 -50.85
LT-8 -52.39 0,24 -0.36 0,84 2,07 -1.94 -3.80 1.94 -53.39
LT-9 -51.50 0,11 -0.36 -0.24 2.27 -2.07 -3.83 1.97 -53.65
LT-9/1 -49,89 0.02 -0.36 0.08 2.45 -2.09 -3.79 2.16 - 51.42
LT-9/2 -52.45 0.24 -0.36 0,03 2.26 -2.09 -3.84 1.80 -54.40
LT-9/3 - 51.96 0.63 -0,36 -0,07 2.42 -2,08 -3,84 1.51 -53.74
LT-9/4 - 51.73 0.25 -0.36 0,04 2,59 -2.08 -3.87 1.57 -53.59
LT-IO -52.25 1.04 -0.36 0,30 2.08 -2.07 -3.80 1.83 -53.22
LT-I0/l -56.33 0.68 -0.36 0.05 2,14 -2.06 -3.81 1.41 -58.30
LT-I0/2 -52.25 -0.40 -0.36 0.32 2.11 -2,07 -3.84 1.74 -54.75
LT-1O/3 -51.7! 0.52 -0,36 0,14 2.67 -2.04 -3.79 2.00 -52,58
LT-1O/4 -50.57 -0.24 -0.36 0,09 3.07 -2.04 -3.83 2,03 -51.86
LT-I0/5 -52.64 0,09 -0.36 0,28 2,20 -2.06 -3.84 1.68 -54,65
LT-1O/6 -52.97 -0.12 -0.36 0.02 1.78 -2,03 -3,80 1.80 -55,69
LT-II -54.42 0,13 -0.36 0,25 2.06 -2.09 -3,81 1.65 -56.58
LT-!!/! -56.05 0.83 -0.36 -0.10 2.02 -2.21 -3,85 1.34 -58.38
LT-II/2 - 55.Ql 0,80 -0.36 -0,11 1.97 -2.16 -3,82 1.52 -57.17
LT-ll/3 -47.49 -0.40 -0,36 -0.19 3.13 -2.18 -3,82 2.31 -49.00
LT-ll/4 -49.52 0,57 -0,36 0.38 2,59 -1.72 -3.68 2,00 -49,74
PC-I/! -49.54 1.21 -0,12 0.65 0.98 -1.20 -3.66 0.48 -51.20
PC-I/2 -45.63 1.53 0.08 0.45 1.62 -0,89 -3.59 1.23 -45.37
PC-1/3 -43,35 8,94 -0.10 0,23 0,84 0,10 -3.40 3,24 -33.49
PC-1/4 -50.19 1.60 -0.14 0,77 0,76 -0.98 -3.56 -0.08 -51.82
PC-l/5 -47.13 2,16 -0,21 -0.02 1.99 -1.35 -3.65 0.68 -47.52
PC-2/1 -46.60 1.17 -0.25 -0.05 2.76 -1.06 -3.69 0.92 -46.79
PC-2/2 -45,53 1.04 -0.23 -0,22 2.73 -1.25 -3.70 0.53 -46.64
PC-2/3 -45.02 1.53 -0.19 0,12 2.89 -1.15 -3,50 0.84 -44.48
PC-2/4 -46.62 1.70 -0,22 -0.04 2,84 -1.39 -3,67 0.87 -46,54
PC-2/5 -46.00 1.64 -0,16 -0.06 2,86 -1.35 -3,64 0,85 -45.87
PM-l -35.74 0.86 -0.20 0.75 0.88 -0.32 -2.77 1,87 -34,68
MP-2 -37,04 0,98 -0.22 -0.36 3.14 -1.16 -3.69 1.38 -36.96
PM-3 -44,88 1.20 -0.12 -0,14 2,76 -1.07 3.48 -0.76 -44.98
PM-4 -46.10 1.56 -0.23 0,14 2,75 -1.08 -3,59 1.20 -45.36
PM-5 -45.40 1.98 -0.15 0,27 2,57 -1.00 -3.53 1.22 -44.04
PM-6 -46.05 1.20 -0,23 -0.29 1.92 -0,60 -3.28 0.80 -46.53
272 E . CABALLERO ET AL.

order to remove all this SiO2 in solution, large amounts of water are needed.
Actually, taking into account the solubility of Si0 2 at 60°C - which is the
mean temperature of bentonite formation in this region (Leone et al., 1983)
- it is possibleto calculate, using data reported by Fournier and Rowe ( 1977),
that more than 2300 m' water is necessary to leach 0.5 ton of Si0 2 • That is to
say, for each ton of unaltered pyroclastic material more than 2300 m' water
is necessary to form 0.5 ton of bentonite. This is the minimum amount of
water needed to maintain the silica in solution .
These high amounts of water can contribute small quantities of elements
which can enter into the smectite network. For instance, for the estimated
water/rock ratio (2300/1) all the MgO (2.33 % as mean value) contained in
the Trancos Deposit could be contributed by a solution containing 28 ppm
MgO (about 1 meqjl). This is a common value for aquifers which have per-
colated through metamorphic and sedimentary formations (Hem, 1970). It
can also be deduced that Fe gains (PC/l deposit) could be obtained from a
solution with more than 6 ppm of Fe content; this value corresponds to solu-
tions of meteoric origin (Hem, 1970). Similar calculations can be made for
the rest of the elements.
Taking into account the geographic location of the samples (Fig. 1) it can
be observed that total Si0 2 losses are more important in the northern zone.
The same is valid for the gains in Mg2+ (Table V) and H 20+. This fact must
be related, on the one hand, to the hydrodynamic history of these solutions.
Caballero et al. (1985) conclude that the hydrothermal solutions acting in
the region came from the northern ranges (Sierra Alhamilla and Cabrera)
and that, while travelling southward through deep fractures, they were heated,
and in this way the percolated materials were altered. These authors also sug-
gested that the chemical composition of solutions should have changed dur-
ing their migration. Thus, exchangeable Mg in smectites decreases toward the
south, which is in accordance with the greater Mg contribution in the north.
The variations in matter loss encountered in the N-S direction must be
related also to the reactivity of solutions. The solutions probably lost part of
their altering capacity as they travelled southward due to a gradual transfer of
ions between the solutions and the pyroclastic materials. Thus, the solution
TABLE V

Geographic variation of MgO% and MgV

'
MgO Mg V
'
(% )

Los Trancos (LT) 4.86 0.760

Serrata de Nijar (PC, PM) 3.93 1.032
Zona Centro (BF ,MM, LP) 1.97 1.178
Zona Sur (VB, EC) 1.04 0.904
 THE FORMATION OF BENTONITE: MASS BALANCE EFFECTS 273

should undergo essentially a proton loss (hydrogen metasomatism after

Remley and Jones, 1964) and a gain in solutes, derived from the hydrolysis
of volcanic materials, until reaching total inactivity when a compositional
equilibrium with the volcanic rocks is attained (Helgeson et al., 1969).

Mass balance and smectitecharacteristics

From the data obtained it is apparent that there is a relation between the
loss of matter and the smectite content in bentonites. Both variables are re-
lated through the regression equation:
% totalloss=6.1763+0.4695 % smectite, (r=0.866, n=52)
Some interesting conclusions can be drawn from this equation: (1) The Y
axis intercept indicates that there was some loss of matter prior to smectite
formation. The volcanic materials must have been hydrolyzed before smec-
tite formed from the hydrolysis products. (2) The material lossesceased when
the entire original material has been transformed into smectite. Nevertheless,
this is not necessarily always the case, since in other deposits of this region
(data not published) there are bentonites which have suffered variable losses
in matter, although their composition is always 100 % smectite. In such cases
it is necessary to assume that the smectite itself is hydrolyzed and partially
destroyed.
With the purpose of exploring the relation existing between the chemical
composition of smectite and the percentage of matter loss, a series of linear
regressions were calculated (Table VII) using the calculated structural for-
mulae. These crystallochemical formulae have been obtained usingthe method
of Marshall (1949). Samples containing small mineral impurities were dis-
carded. For this reason, we calculated 39 formulae (Table VI).
A new regression between the total matter loss and the percentage of smec-
tite has been done for these data:
% total loss = 14.396+0.388 % smectite (r=0.525, n= 39)
the correlation level is again higher than 1%0.
The most important fact observed in Table VII is that smectite suffered a
change in composition as the material loss increases. Smectite composition
seems to depend on the degree of alteration of volcanic rocks. Thus, the com-
position of an initial smectite (from 14.40 % total loss and a smectite content
close to zero) and a final one (53.20 %total loss and 100% smectite), can be
inferred.
The compositions calculated on the basis of the regression equations in Ta-
ble VII are as follows: initial smectite, (Sis) (Al 1.84 Feo.n M g 2.09 ) X6.26 0 20
(OH)4; and final smectite, (Sh55 Alo.45) (A1 3.39 FeO.33 Mgo.92 ) Xt03 0 20
(OH)4'
274 E. CABALLERO ET AL.

TABLE VI

Structural formulae of smectites

Sample Si 1v Apv AIYI Fe v l MgY1 X+

LP-I 7.672 0.328 2.452 0.668 1.178 0.614

VB-2 7.672 0.313 2.955 0.270 0.904 0.832
LT-l 7.209 0.791 3.348 0.312 0.479 0.852
LT-2 7.296 0.704 3.328 0.237 0.591 0.830
LT-3 7.553 0.447 3.199 0.146 0.758 0.900
LT-4 7.576 0.424 3.241 0.144 0.763 0.796
LT-5 7.537 0.463 3.224 0.100 0.811 0.867
LT-6 7.388 0.612 3.214 0.234 0.763 0.744
LT-7 7.633 0.367 3.213 0.000 0.918 0.892
LT-8 7.645 0.355 3.231 0.155 0.610 0.975
LT-9 7.599 0.401 3.186 0.178 0.693 0.925
LT-9/1 7.596 0.440 3.027 0.120 0.968 1.071
LT-9/2 7.607 0.393 3.095 0.225 0.738 0.954
LT-9/3 7.614 0.386 3.047 0.135 0.909 1.091
LT-9/4 7.958 0.042 3.154 0.077 0.707 0.931
LT-IO 7.382 0.618 3.105 0.253 0.740 1.064
LT-IO/1 7.331 0.669 3.320 0.192 0.679 0.775
LT-IO/2 7.418 0.582 3.236 0.236 0.589 0.988
LT-1O/3 7.631 0.369 3.016 0.240 0.861 0.879
LT-1O/4 7.761 0.239 3.148 0.133 0.842 0.713
LT-IO/5 7.549 0.451 3.078 0.232 0.793 0.935
LT-IO/6 7.653 0.347 3.197 0.073 0.838 0.860
LT-l [ 7.371 0.629 3.215 0.219 0.720 0.885
LT-l1/1 7.174 0.826 3.204 0.239 0.703 1.092
LT-ll/2 7.349 0.651 3.303 0.231 0.650 0.747
LT-ll/3 7.698 0.302 3.186 0,096 0.869 0.718
LT-ll/4 7,775 0.225 3.038 0.055 1.0[5 0.918
PC-Ill 7.590 0.410 2.997 0.439 0.809 0.483
PC-1/2 7.560 0.440 3.054 0.460 0.716 0.466
PC-1/4 7.708 0.292 2.652 0.658 0.925 0.511
PC-liS 7.623 0.377 2.79[ 0.533 0.898 0.609
PC-2/1 7.559 0.441 2.868 0.310 1.062 0.781
PC-2/2 7.638 0.362 2.751 0.293 1.217 0.793
PC-2/3 7.758 0.242 2.730 0.340 1.172 0.687
PC-2/4 7.700 0.300 2.689 0.381 1.182 0.725
PC-2/5 7.789 0.211 2.815 0.307 1.044 0.755
PM-2 7.831 0.169 2.756 0.193 1.323 0.675
PM-3 7.405 0.595 2.984 0.336 0.969 0.698
PM-4 7.710 0.290 2.792 0.357 1.067 0.709
Si1v =tetrahedral silicon; Al'" = tetrahedral aluminium; AIYI , MgV1 and Fe VI = octahedral cations;
X+ = layer charge.

The initial smectite has less tetrahedral substitution, (AIl V ) and layer charge,
and more (Fe Yl ) and (Mg'") than the final smectite. The composition of the
final bentonite appears to be more correct because the initial one would have
THE FORMATION OF BENTONITE: MASS BALANCE EFFECTS 275

TABLEVII

Regression equations (structural formulae versus total losses %)

y X Qo b r n Sign.
Spv % tot. loss 8.61 -0.02 0.595 39 10/00
AIYI % tot. loss 1.26 0.04 0.815 39 1%0
FeY I % tot. loss 0.86 -0.01 00405 39 1%
MgY I % tot. loss 2.52 -0.03 0.851 39 1%0
X+ % tot. loss -0.03 0.02 0.530 39 1%0
Qo= Y and intercept; b=slope; r=correlation coefficient; n=number of data; Sign.=statistic
significance.

a (Si IV ) content of more than 8; moreover, the sum of octahedral cations is

4.65; which is a value much too high for dioctahedral smectites, as pointed
out by Weaver and Pollard (1973).
These variations in the chemical composition of smectites during altera-
tion process have been previously treated by Caballero et aI. (1985) and Lin-
ares ( 1985, 1987) and confirmed later in studies to be published by the same
authors.
A final aspect, apparently paradoxical, appears when analyzing the relation
between Mg2 + gains (higher in bentonites of the northern zone) and the
(Mg VI) content in smectites (which is low in the northern zone). That is to
say: the (Mg V 1 ) content in smectites decreases as MgO % input increases
(Table V).
The greater Mg2+ gain in the northern zone coincides with greater losses
and smectite percentages which are also higher. Even in the presence of great
amounts of Mg2+, if much smectite is present, the (Mg VI ) content will prob-
ably be low, 'as Mg has to be allocated into the smectite. The opposite takes
place when Mg2+ input is low. In this case the matter loss is low as is also the
smectite content. For this reason, although available Mg2+ is scarce, being
present in small smectite quantities, the (MgV I ) concentration in smectite
will be high.
Finally, as regards the type of smectite formed from rhyolitic rocks, it must
be pointed out that smectites ofthe montmorillonite type predominate, while
beidellites can only be formed if bentonites are nearly 100 % smectite.
ACKNOWLEDGEMENTS

The authors wish to express their thanks to Minas de Gador S.A. for assis-
tance during their visit to the deposits.

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