Clay Minerals (1997) 32, 319-322
NOTE
Comparison of the methylene blue absorption and the ammonium
acetate saturation methods for determination of CEC values of
zeolite-rich tufts
One of the most important properties of zeolitized
volcaniclastic materials is the cation exchange
capacity (CEC). Numerous techniques are available
for measuring CEC and the methylene blue
absorption (MBA) (Nevins & Weintritt, 1967) and
the ammonium acetate saturation (AMAS)
(Chapman, 1965) methods are two of those
commonly used. The aim of this study was to
compare the results obtained by the two methods
when used with zeolite-rich materials.
Materials
Samples of pyroclastic rocks from the Santorini
and Polyegos (Milos group) islands were used in
this study. Both islands belong to the South Aegean
Sea Volcanic Arc in Greece (Fig. 1).
The materials from Santorini (Akrotiri pyroclas-
tics) can be characterized as tufts and lapilli tufts
with some minor flows or breccias of hornblende
dacite. Heulandite type 3 (clinoptilolite) as the
dominant authigenic mineral has replaced the vitric
component of the tufts (Tsolis-Katagas & Katagas,
1989; Kitsopoulos 1995a, 1996a; Kitsopoulos &
Dunham, 1996).
In Polyegos, zeolite minerals were found within
pyroclastic flows and surge deposits. The principal
authigenic mineral is mordenite which was formed
by hydrothermal alteration (Kitsopoulos, 1995a,
1996b; Kitsopoulos & Dunham, 1996).
Analytical methods
The fine powders (<125 ~tm) used in both
methods were first washed with de-ionized water
to remove any soluble phases present and then
thoroughly dried. The MBA method is based on the
measurement of the maximum absorption of the
sample for a nominally 0.01 N solution of
methylene blue. The AMAS method involves the
saturation of the sample by ammonium acetate
9 1997 The Mineralogical Society
solution at pH 7. The AMAS method was slightly
modified regarding saturation time and the use of
the saturated samples according to Kitsopoulos
(1995b). The ammonia electrode technique was
used to measure ammonia, but instead of using the
solutions which were obtained after the NaC1
washing, use of the saturated samples was preferred
(Busenberg & Clemency, 1973).
Results and discussion
From the results obtained (Table 1) it was
obvious that there was a distinct difference
between the two sets of data. The CEC values
obtained from the MBA method were much lower
than those which might be expected for zeolitic
materials and were also much lower than those
obtained from the AMAS method. It was already
known that the MBA method, for almost pure
bentonite samples, does not usually give the real
CEC of the material examined; at best it yields 80%
of the real CEC values (Morgan, 1990). Although
the homogeneity of the samples and the quality of
the measurements were secured, the two methods
yielded significantly different results for zeolitic
materials. The values given by the MBA method
were 4.15-28.46% of the AMAS values for the
Santorini material, and 1.19-11.25% of the AMAS
values for the Polyegos material. The only
exceptions were the three samples P23, P27 and
P30 from Polyegos in which kaolinite rather than
zeolite is the dominant phase. These samples were
collected from the southern part of the island and
used in this study as 'controlling samples'. Their
MBA values were 91.2, 82.9 and 79.4% of the
relevant AMAS values. Therefore, the MBA
method can give 80-90% of the CEC when used
with kaolinite-rich samples.
The fact that the MBA values, in the case of
mixed zeolite and clays samples, are related to CEC
contributed mainly by the clays can be seen by
320 Note

/" /
N
/J - ./

GREECE

e e o
o

0 I O0 k m
South Aegean Sea Volcanic Arc [,, I

FIG. 1. The South Aegean Sea Volcanic Arc. 1: Santorini; 2: Polyegos; 3: Milos; 4: Kimolos (2, 3 and 4 form the
Milos group of islands).

comparing the results from the two areas. In
general, the absolute MBA and the MBA/AMAS%
values were lower in Polyegos where illite is the
principal clay mineral resulting in lower CEC
values than in Santorini where smectites (with
much higher CEC values) and only a few illite-
smectites are present. It is also indicative that the
two Polyegos samples containing some illite-
smectite (P6 & P19) exhibited the higher CEC
values given by the MBA method.
The reason why the M B A method seems
inappropriate for zeolite-rich samples relates to
the zeolite structure, the size of the channels
present, and the position of the exchangeable ions
in zeolites. The structure of these minerals is
characterized by the presence of a channel system
with two main channels parallel to the c axis named
A and B, and a channel C parallel to the a axis or
to [102] (Koyama & Takeuchi, 1977). It is obvious
that the size of the zeolitic channels and the mole
size of the indexing ion should be similar in order
that the indexing ion can penetrate the channels and
replace the cations which are situated in cavities
within these channels. In heulandite, the sizes of the
 Note 321

TABLE 1. CEC values (mEq/100 g) obtained using the channels parallel to b (Breck, 1974), and ~ 7 x
methylene blue absorption (MBA) and ammonium 6.7 A (minimum dimensions of widest channel as
acetate saturation (AMAS) methods (S: Santorini given by Deer et al., 1992).
samples; P: Polyegos samples).
The methylene blue molecule is known as a 'raft-
like' mole and it has been given schematically by
Sample MBA AMAS (MBA/AMAS)% Kipling & Wilson (1960). Its sizes were estimated,
by the same authors, as follows: length (L) 16.0 A,
S103 7.72 186.09 4.15 breadth (B) 8.4 ~, and a minimum thickness of
S104 37.49 131.74 28.46
4.7 ~,. This leads to a projected plan area of
S105 22.19 126.58 17.53
S106 12.49 193.02 6.47 134.4 ~ 2 Although other workers (as quoted by
S108 10.56 132.27 7.98 Taylor, 1985) have increased the projected plan
Sll0 10.02 185.71 5.40 area up to 195 ~2, the value by Kipling & Wilson
Sl13 14.41 131.11 10.99 (1960) still shows the molecule to be quite
Sl15 16.52 138.00 11.97 significant in size. In addition, methylene blue
Sl16 17.62 197.72 8.91 moles diluted in concentrations similar to the one
Sl17 8.26 151.76 5.44
used in the MBA method, might exist in a
Sl19 17.85 217.68 8.20
S120 21.12 189.88 11.12 monomer (1 molecule) - dimer (2 molecules)
S121 19.55 178.94 10.93 equilibrium (Taylor, 1985).
S124 14.47 214.68 6.74 If the relevant sizes and the conditions under
S126 18.19 197.56 9.21 which methylene blue exists are considered, it is
S130 11.96 221.60 5.40 obvious that the size and the projected plan area of
S 132 8.44 130.42 6.47
the specific organic ion is larger than the size of the
S137 13.88 180.48 7.69
S139 19.33 182.46 10.59 specific zeolitic channels in the heulandite type of
S140 11.89 153.22 7.76 minerals and the mordenite. The methylene blue
S141 12.33 186.82 6.60 ion, in this case, cannot penetrate the channels and
S142 12.64 183.12 6.90 subsequently reach and replace the cations present
S145 7.90 161.44 4.89 in the zeolitic structure. This 'inability' of the
S146 8.90 134.41 6.62 methylene blue ion can be exploited and be used as
P2 3.70 113.08 3.27 a 'molecular probe' technique to acquire quantita-
P4 3.15 170.18 1.85 tive data from zeolite-clay mixtures. The technique
P5 5.32 139.64 3.81 can involve the measurement of the CEC of a series
P6 12.93 114.89 11.25 of known relevant compositions of zeolite-clay
P8 2.50 148.66 1.68 mineral mixtures in a scale of 0 - 1 0 0 % and the
P10 3.62 116.09 3.12 construction of nomograms from which the CEC of
P11 5.00 188 2.66
an unknown sample will be then related back to the
P13 3.70 161.74 2.29
P14 2.93 151.04 1.94 relative presence of zeolites and clays. In this case
P17 5.24 179.59 2.92 it must first be assumed that the percentage of
P19 9.53 169.07 5.64 phenocrysts present in the zeolite-rich materials can
P21 2.68 33.34 8.04 be estimated by another well established technique,
P23 1.56 1.71 91.23 e.g. point counting, and secondly it must also be
P27 2.04 2.46 82.93
assumed that the entire microcrystalline mass of the
P30 1.89 2.38 79.41
P34 1.91 160.02 1.19 materials consists of an assemblage of clays and
zeolite minerals.

channel parallel to a have been found to be 4.0 x
5.5 A while those of the channels parallel to c are
4.0 x 7.2 ,~ (Breck, 1974). For the same mineral,
Deer et al. (1992) quoted as minimum dimensions
of the widest channel the values ~ 7 . 9 x 3.5 A. In
mordenite the relevant sizes are 6.7 x 7.0 A for the
channel parallel to c and 2.9 x 5.7 .~ for the
Conclusions
The MBA method can be applied to clay-rich
samples producing up to 90% of the CEC values,
but it should not be applied to samples rich in
zeolites. If it is, the CEC values then obtained
should refer only to the presence of the clays in the
samples. The MBA method yielded at best 30% of
322 Note

the value obtained with the AMAS method,
reflecting the relative amount and nature of clay
minerals present. Therefore, the MBA method can
identify the presence of clays within the zeolitized
matrix of pyroclastic materials. In this way it could
be used for the determination of the content of
zeolites in a sample. The use of an organic indexing
ion with zeolite-rich samples for the purpose of
estimating their CEC should always take account of
the channel size of the specific zeolite minerals
present.
ACKNOWLEDGMENTS
The author would like to thank Ansel Dunham of the
Geology Department of Leicester University for
reading the manuscript and making useful comments, Kitsopoulos K.P. (1995b) The appliance of the ammo-
Helen Louka for checking the manuscript, and the
Geology Department of Leicester University for
providing the necessary analytical facilities. The
suggestions made by two anonymous referees helped Kitsopoulos K.P. (1996a) Zeolitization of the Akrotiri
to improve the manuscript. The State Scholarship
Foundation (SSF) of Greece is acknowledged for
providing the financial support. The author is also
grateful to Sue Button and Emma Mansley, of the
Geology Department of Leicester University for their Kitsopoulos K.P. (1996b) The genesis of a mordenite
help on technical aspects.
Geology Department, K. P. KITSOPOULOS
Leicester University,
Leicester, LE1 7RH, UK
Present address:
16 Aiolou St.,
Paleo Faliro,
175 61 Athens,
Greece.
Received I December 1995; revised 12 September 1996. Nevins M.J. & Weintritt D.J. (1967) Determination of
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