Applied Clay Science 49 (2010) 98–107

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c l a y

Stability of bentonites in salt solutions

II. Potassium chloride solution — Initial step of illitization?
S. Kaufhold a,⁎, R. Dohrmann a,b
a
BGR, Bundesanstalt für Geowissenschaften und Rohstoffe, Stilleweg 2, D-30655 Hannover, Germany
b
LBEG, Landesamt für Bergbau, Energie und Geologie, Stilleweg 2, D-30655 Hannover, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Bentonites are supposed to be suitable materials for the production of geotechnical barriers in high level
Received 18 January 2010 radioactive waste (HLRW) repositories if the bentonites' swelling capacity is maintained at the conditions
Received in revised form 6 April 2010 expected; e.g. in contact with different solutions which may occur during the long term storage. Among all
Accepted 13 April 2010
other common cations, K+ is believed to play a special role in contact with smectites because it can be
Available online 4 May 2010
adsorbed irreversibly and may cause collapse of the interlayer space.
In the present study 36 different bentonites were reacted with KCl-solutions at 60 °C with and without
Keywords:
Illitization
wetting — drying cycles and extensive drying. The study was conducted mainly to study the mechanism of
Smectite alteration irreversible K+ fixation and the resulting loss of swelling capacity (LOS).
Bentonite stability The K+ exchange for the originally present cations was to some extend buffered by carbonates (minor
K-smectite components of some bentonites). Such buffer reactions are supposed to be relevant for real HLRW repository
Smectite collapse situations.
The expected decrease of the swelling of the bentonites depended on the adsorption energy of the probe
molecules (water, EG = ethyleneglycol, Cu-triene). The results of different methods (XRDEG, water
adsorption, CECCu-triene, soda-soluble silica) indicated that the smectite fraction of the products (on average)
was composed of approximately 50% swelling K+ smectite, 45% non-swelling collapsed K+ smectite (50% of
which with fixed K+), and 5% illite which probably formed by dissolution and precipitation. This illite was
detected by the increase of soda-soluble silica. In contrast to the solvation with ethyleneglycol, which only
measures the collapsed layers rather than illite particles, the determination of soluble-silica is regarded as
optimum for differentiating between collapsed layer domains and real illitization.
The number of collapsed layers of the K-smectites depended on the layer charge density (LCD) but not on the
tetrahedral charge. A model is proposed which explains the correlation of collapsed interlayers and LCD.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
Bentonites are supposed to be suitable materials for the produc-
tion of geotechnical barriers in high level radioactive waste (HLRW)
repositories if the bentonites' swelling capacity is maintained at the
conditions expected. Accordingly bentonites have to be stable with
respect to high temperature (dry conditions), wetting-drying cycles,
and in contact with different kinds of solutions. Among all other
cations K+ is believed to play a special role in contact with smectites
because it can be adsorbed irreversibly and may cause collapse of the
interlayer space (e.g. Weiss and Koch, 1961; Push, 2002a,b).
If bentonites are reacted with different kinds of solutions, different
reactions as cation exchange, dissolution, precipitation, or recrystal-
lization are reported (e.g. Bauer and Velde, 1999; Hofmann, 2003;
Herbert et al., 2004; Hofmann et al., 2004; Kasbohm et al., 2004;
⁎ Corresponding author.
E-mail address: s.kaufhold@bgr.de (S. Kaufhold).
Suzuki et al., 2008). The common dread is the irreversible transfor-
mation of smectites into non-swelling clay minerals (such as illites)
which is commonly detected by changes of the XRD pattern
(formation of 10 Å units instead of 13–15 Å units). With respect to
the application as HLRW bentonite it is essential to investigate
whether this collapse was reversible (swelling capacity maintained)
or not. Kaufhold and Dohrmann (2009) discussed the problems of
irreversible collapse of smectitic layers and proved that NaCl solutions
at 60 °C for 5 months did not irreversibly affect the properties of
bentonites.
In contrast to Na+, K+ is known to play a special role with respect
to a possible smectite alteration because K+ can reside in the
ditrigonal cavities of the tetrahedral sheet (accompanied by dehy-
dration) which decreases the interlayer space. The final stage of K+
adsorption is the formation of a collapsed layer (≈10 Å). This
behavior is specifically observed in case of K+ as exchangeable cation
and can be explained by the lower hydration energy and by steric
reasons (diameter of K+ fits particularly well to the dimension of the
ditrigonal cavity, Lagaly, 1993).

0169-1317/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2010.04.009
 S. Kaufhold, R. Dohrmann / Applied Clay Science 49 (2010) 98–107
K+ fixation often is regarded as an initial step towards illitization
although the actual mechanisms of illitization still are a matter of
considerable debate. According to e.g. Lee et al. (2009) two different
mechanisms are particularly important: i) layer by layer (solid state)
transformation (Hower et al., 1976) and ii) dissolution / precipitation
(Boles and Franks, 1979). Dissolution and precipitation (or crystalli-
zation: ‘DC’) of smectite in the presence of K+ is known to result in the
formation of illite and silica (occurring as separate phases). In
contrast, it is still not clear if a solid state illitization process
(sometimes abbreviated as ‘SST’) exists and how it exactly proceeds
(does K+ fixation induce illitization?). A vast number of studies exist
dealing with illitization which cannot be completely discussed here.
However, a recent comprehensive summary about illitization is
provided e.g. by Honty et al. (2004) and detailed information can be
gained e.g. from Meunier and Velde (2004).
Not much doubt exists about the fact that illite is energetically
more stable than smectite when K+ ions are present. The actual
thermodynamic status of clay minerals, however, is also a matter of
considerable debate. Lippmann (1979, 1982) pointed out that
according to the invalidity of Gibbs' phase rule the transformation
of smectite has to be described by a disequilibrium model. Aja and
Rosenberg (1996) discuss this from a thermodynamic point of view.
Metastability can also be described in a way that ‘all gradients of
temperature, pressure, and composition in a system have not been
eliminated’.
Iillitization of smectite in the presence of K+ takes place in case of
elevated temperature and/or high pH (Eberl et al., 1993; Bauer and
Velde, 1999). The latter promotes smectite dissolution even at low
temperature resulting in illitization by dissolution and precipitation.
However, illitization was also reported at low temperature as product
of wetting-drying (WD) cycles (Eberl et al., 1986). This transforma-
tion is possibly a solid-state reaction. The idea is that K+ ions, during
drying, loose the water shells and move into the ditrigonal holes
where they are strongly bound. The product has a basal spacing
of ≈10 Å which is typical of illite/muscovite and hence pretends the
presence of illite. Considering a combination of chemical and
mineralogical methods, Mosser-Ruck et al. (2001) showed how illite
and non-swelling K-smectite can be distinguished.
The reasons for the K-fixation process are also still under
discussion. In this respect the tetrahedral charge and the symmetry
of the charge distribution (on both sides of the tetrahedral sheet) are
believed to be important. According to Tettenhorst and Johns (1966),
the prerequisite for the K+ ions to move into the ditrigonal holes is the
tetrahedral charge and the collapse to 10 Å occurs when the two
tetrahedral charges are opposed. Other authors claimed that the total
permanent charge (octahedral + tetrahedral charge) is the decisive
factor. A summary of studies claiming that either the charge location
or total charge determines K-fixation is given by Schultz (1969). He
concluded that the total charge (layer charge density) is more
important than the charge location. Horváth and Novák (1976) also
found that the tetrahedral charge determined by the structural
formula method is irrelevant with respect to K-fixation. Interestingly,
they suggested that the charge distribution of the whole particle is
important.
The hydration energy of K+ has to be overcome to reach a more
stable state (as fixed cation). When the K+ ions are fixed in the
ditrigonal holes, rehydration is prevented. The key question is how
illite with a much higher tetrahedral charge forms from the K+ fixed
smectite? No doubt exists about the fact that the combination of
illitization promoting parameters (e.g. wetting and drying + high pH;
Eberl et al., 1986) will increase the illitization rate.
The aim of this study is to assess the long term stability of smectite
in contact with potassium ions both at dry and wet conditions. In
contrast to many studies, the present study considers a significant set
of different well characterized bentonites. Using this approach, it was
attempted to identify particularly stable bentonites which in turn
99
would be favourable materials for the production of a geotechnical
barrier for HLRW repositories. The hypothesis was that the highly
charged smectites tend to fix K+ and hence can be considered as more
reactive with respect to a possible formation of nonswelling layers in
the case that K+ bearing solutions enter the HLRW repository.
2. Materials and methods
Thirty six different bentonites (dominated by smectite of the
montmorillonite-beidellite series) and two I/S mixed layer mineral
containing clays were used in this study. The precursor materials were
characterized by Kaufhold and Dohrmann (2008), Kaufhold et al.
(2008), and Ufer et al. (2008). Ufer et al. (2008) did not consider the I–
S containing samples B30 and B35 and changed the sample assign-
ments accordingly: sample B31 was labelled B30 and sample B36 was
labelled B34 (B30 and B35 were simply omitted). Most of the
materials were kindly provided by bentonite producing companies
and not all companies allowed publication of locality. Therefore,
localities are not provided in this study. For the present study, it is
more important to consider differences of the bentonite properties
than differences of locality. The most important variability of the
sample set refers to the exchangeable Na+ (0–100%), smectite content
(60–93 mass%), layer charge density (0.20–0.38 eq/FU), Fe2O3 con-
tent (1–16 mass%), and BET specific surface area (7–130 m2/g).
The chemical compositions were analyzed using a PANalytical
Axios and a PW2400 XRF spectrometer. Samples were prepared by
mixing with a flux material and melting into glass beads. The beads
were analyzed by wavelength dispersive X-ray fluorescence spec-
trometry (wavelength-dispersive-XRF). To determine loss on ignition
(LOI) 1000 mg of sample material were heated to 1030 °C for 10 min.
After mixing the residue with 5.0 g lithium metaborate and 25 mg
lithium bromide, the mixture was fused at 1200 °C for 20 min. The
calibrations were regularly validated by analysis of reference
materials and 130 certified reference materials (CRM) are used for
the correction procedures.
For XRD analysis the powders were dispersed using 60 mg in 2 mL
of deionized water and 10 min. sonication in an ultrasonic bath.
Oriented mounts were prepared by suction of the dispersions through
3 mm thick ceramic tiles of approximately 4 cm². These films were X-
rayed from 2 to 35° 2 theta using a Seifert 3003 TT (air dried, AD, and
ethylene glycol, EG, solvated) with Cu radiation, automatic slit and
secondary graphite monochromator. Counting time was 10 s per step
and irradiated length was 10 mm.
The water uptake capacity was determined by weighing 5 g
sample in aluminum cups (diameter 4 cm) and the water uptake
capacity was measured gravimetrically at 50, 60, and 70% relative
humidity (r.h.) provided by a climate oven (Binder APT.Line KBF).
Samples were maintained at each relative humidity for one week and
weighed outside the oven after each week. Finally, the samples were
dried at 105 °C in order to determine the initial dry mass.
The CEC was determined by the Cutriene method according to Meier
and Kahr (1999) and was also used for the quantification of the
tetrahedral charge after the Li-treatment according to Greene-Kelly
(1953).
The amount of soluble silica was determined by using 0.200 g
(pre-dried at 105 °C for 24 h) sample and 50.0 mL 2% sodium
carbonate solution. The dispersion was shaken at 60 °C for 24 h and
the supernatant analyzed with respect to Si using ICP-OES. The
reproducibility was approximately ± 0.1 mass%.
Two series of experiments were conducted to investigate the effect
of long-term treatment (5 months) of bentonites with KCl rich
solutions (KLTS) and the effect of wetting and drying on the K+
fixation of homoionic K+ smectites (KWD). The investigation of
kinetics e.g. or the behaviour at hydrothermal conditions have to be
addressed in a different study.
100 S. Kaufhold, R. Dohrmann / Applied Clay Science 49 (2010) 98–107

2.1. Long term stability (KLTS)

The long-term batch reactions (bentonites + KCl) were carried out

as follows: 4.0 g of each sample were added to 40.0 mL 1 M KCl
solution (approximately 10 times the CEC of the bentonite). The
dispersions were in sealed 50 mL PE tubes. The tubes were shaken in a
water bath at 60 °C for 5 months. The dispersions were centrifuged for
10 min at 4000 rpm and the clear supernatants decanted. To collect all
dissolved ions, again 3 x 40 mL deionized water were added and, after
homogenization, the dispersions were centrifuged. After decantation
all supernatants were collected and analyzed by ICP. The solid was
dialyzed to remove the final traces of soluble ions. The solid then was
dried at 60 °C and ground by a mortar mill.

2.2. Wetting drying cycles (KWD)

The K+ saturated smectites were prepared by reacting with KCl for

Fig. 1. Amount of silica dissolved during the long term experiments with KCl solution
24 h (concentrations corresponds to 100fold CEC). After repeating this and in the NaCl-test.
process two times, the samples were washed with deionized water,
dialysed, dried at 60 °C for 72 h, and ground. After determination of the
CEC and the amount of soda-soluble silica, the samples were mixed with Interestingly, the amounts of silica dissolved throughout both
50 mL water and heated to 105 °C for 3 days followed by drying for 4 days. experiments were highly correlated which indicates that related
This wetting drying cycle was repeated four times before again the CEC parameters determine the amount of dissolved silica (Fig. 1). The
and soda-soluble silica were determined. After the wetting drying cycles amount of dissolved silica in the NaCl and KCl solutions neither
the rest of the sample was heated to 120 °C for 1 month and analyzed depended on pH, exchangeable Na+ (which could be possible because
again with respect to CEC and soda-soluble silica. Finally all samples were of detachment of colloidal particles, e.g. Kaufhold and Dohrmann,
analyzed by XRD, and the water uptake capacity was determined. 2008) nor on the amount of soda-soluble silica (which is highly
The acronyms used in the present study are summarized in Table 1. correlated with amorphous silica compounds). The exact mechanism
of silica dissolution, therefore, is not clear. As the amount of dissolved
silica was small, it is not expected that other mineralogical methods
3. Results and discussion can help to identifiy the reason for the different silica solubilities.
The amount of Al in solution was negligible (b0.1 mg/L) indicating
3.1. Long term stability (KLTS) that b0.01 mass% of structural Al was dissolved. The solutions mainly
contained Ca2+, Mg2+, and Na+ which were exchanged for K+. After the
For comparison, the experimental setup was similar to the NaCl KLTS experiment all smectites contained N50% K+ related to the CEC, the
test (Kaufhold and Dohrmann, 2009). In NaCl solutions, only cation average degree of occupation was 82% (NaCl test: 87%; Kaufhold and
exchange and no structural changes was observed. In contrast to the Dohrmann, 2009). The NaCl test (Kaufhold and Dohrmann, 2009)
NaCl test slightly more SiO2 was dissolved from the bentonties in the proved that carbonates buffered the cation exchange as carbonates
K+ solutions (Fig. 1). The absolute amount of dissolved silica, (mostly calcite) were dissolved throughout the experiment and
however, was negligible and the effect of this dissolution will be throughout the dialysis and their cations occupied some permanent
hardly identified by other methods such as CEC, XRD, or similar. charge sites in competition to Na+ ions. The same result was found in
the present study with KCl: the degree of interlayer K+ occupation
Table 1 depended on the amount of carbonates and/or gypsum which –
Summary of acronyms used in the present study. probably particularly during the dialysis – buffered the cation exchange
by partial dissolution. Thus, a 100% K-bentonite can hardly be produced
Special acronyms used in the General acronyms used in the
present study present study from a carbonate containing bentonite. In conclusion, the results of the
LOS Loss of swelling HLRW high level radioactive
capacity Repository waste repository
LOSCEC LOS determined by LCD Layer charge density
Cu-triene method
LOSWUC LOS determined by water uptake Cu-triene Cu-
measurements triethylenetetramine-
complex
LOSXRD LOS determined by XRD CEC Cation excahnge
capacity
WD Wetting drying Opal A, C CT Low crystalline silica
polymorphs
KWD K+ interaction wetting XRD X-ray diffraction
drying test
KLTS K+ interaction long EG Ehtyleneglycol
term test
NCl-tes Results from Kaufhold and AD Air dried
Dohrmann (2009)
FAA Attractive force in case 10 Å units TOT layer without
of opposing charges interlayer
FA Attractive force in case
of nonopposing charges
Fsolv Repulsive force due to solvation
Fig. 2. Influence of the amount of carbonates (mainly calcite) and gypsum on the degree
energy
of K+ occupation in the interlayer space.
 S. Kaufhold, R. Dohrmann / Applied Clay Science 49 (2010) 98–107 101

NaCl reaction (Kaufhold and Dohrmann, 2009) were confirmed by the

reaction with KCl solutions (Fig. 2).
After the reaction with NaCl solutions no significant difference of
the CEC before and after the experiment could be detected. In
contrast, a 10% decrease of the CEC (on average) was found after the
KLTS experiment (Fig. 3). An increase of the amount of soda-soluble
silica of the same order of magnitude was also observed (Fig. 4) which
indicates that structural changes of the smectites occurred.
The decrease of the CEC can be easily explained by the exchange of
the originally present cations (Ca2+/Mg2+/Na+) by K+ ions and
fixation of the K+ ions. This process could have proceeded either
during the 5 months reaction or during the 3 days of drying the
products at 60 °C. The irreversible collapse does not explain the
increased amount of soda-soluble silica because the assumption that
K+ in the ditrigonal holes weakens the tetrahedral structure (Si–O–Si
and Al–O–Si bonds) is not likely. Free silica is typically produced
during illitization. In the presence of K+, illite is more stable than Fig. 4. Comparison of the amount of soda-soluble silica before and after the KLTS test.
smectite but contains less Si. Hence, smectite dissolution and illite
precipitation would explain the increased amount of soluble silica.
soda-soluble silica, caused by the presence of opal (A, C, CT), showed a
3.2. Wetting drying cycles (KWD) decrease of soda-soluble silica just after the K+ exchange. Kaufhold
and Dohrmann (2009) proved that the amount of soda-soluble silica
One aim of the present study is to investigate the mechanism of K+ of those samples strongly depended on the amount of XRD-detectable
fixation and/or illitization of smectites. Particularly valuable informa- cristobalite. Theoretically, it should depend mainly on the amount of
tion can be obtained by comparing the K+ fixation and/or illitization (XRD-) amorphous silica but a rather good correlation was obtained
with the properties of the various bentonites considered in the with the amount of cristobalite as determined by XRD using the
present study. The idea was to attain K+ fixation and/or illitization of Rietveld method (Ufer et al., 2008). Obviously, cristobalite is
all samples under the same conditions and to compare the degree of commonly accompanied by silica of lower crystallinity which would
alteration with the properties of the bentonites and smectites. The explain the correlation. The fact that the KWD step1 samples with high
samples derived from the KLTS test, however, were not perfect for a amount of soda-soluble silica showed lower values indicated that
detailed mineralogical and structural study because of the incomplete probably some of the soda-soluble silica was already dissolved
cation occupation (Fig. 2). Therefore, all bentonites were carefully throughout the preparation of the K+ bentonites — because in
saturated with K+ by repeated reaction with KCl which resulted in an contrast to the KLTS experiment many washing steps and changes of
average degree of K+ occupation of 95% (exchangeable K+ related to solutions were performed. All samples with a low initial amount of
CEC). These samples (step 1 = S1) were then subjected to wetting soda-soluble silica (≤2 mass%) on the other hand, showed an increase
drying cycles (step 2 = S2) and finally heated to 120 °C (step 3 = S3). of the amount of soda-soluble silica which in turn indicated that
Surprisingly the CEC decreased by 10% (Fig. 5) just after K saturation illitization or a similar process took place (which was not observed in
(drying 60 °C, 3 days) which is similar to the result of the long term the case of the NaCl test; Kaufhold and Dohrmann, 2009).
experiment KLTS (60 °C, 5 months). Apparently, the first decrease of the
CEC (loss of swelling capacity determined by CEC =LOSCEC) is a fast
reaction and takes place readily. Upon wetting and drying (step 2) an 3.3. The loss of swelling
additional 20% LOSCEC was observed. Step 3, the additional heat
treatment, did not lead to further LOSCEC. All data are presented in Table 2. The CEC and the amount of soda-soluble silica were determined of
The soda-soluble silica data (Table 2) have to be critically all products. The common method to determine the LOS is XRD of
considered because particularly samples with a high amount of ethyleneglycol solvated samples. One additional option is to deter-
mine the water uptake (Figs. 6 and 7).

Fig. 5. Decrease of the CEC (loss of swelling determined by CEC = LOSCEC) after cation
occupation (S1), followed by wetting-drying cycles (S2), and additional extensive
Fig. 3. Comparison of the CEC before and after the KLTS experiment. drying (S3).
102 S. Kaufhold, R. Dohrmann / Applied Clay Science 49 (2010) 98–107

Table 2
CEC and soda-soluble silica (sol. SiO2) of the KWD experiment. The values represent the state of the material after each reaction step.

CEC Sol. SiO2 CEC Sol. SiO2 CEC Sol. SiO2 CEC Sol. SiO2

Initial Initial S1 (step 1) S2 (step 2) S3 (step 3)

[meq/100 g] [wt.%] [meq/100 g] [wt.%] [meq/100 g] [wt.%] [meq/100 g] [wt.%]

IB 1 102 0.6 86 1.1 74 1.1 77 1.2

IB 2 102 0.6 86 1.2 75 1.1 77 1.3
IB 3 104 2.5 89 2.7 75 2.7 78 3.0
IB 4 107 0.4 93 1.0 77 1.1 81 1.2
IB 5 100 0.4 91 0.8 80 0.8 80 1.1
IB 6 110 0.6 92 1.1 79 1.3 77 1.6
IB 7 99 0.8 84 1.1 73 1.1 74 1.4
IB 8 72 3.5 60 2.2 52 2.0 50 2.2
IB 9 70 9.8 61 8.9 54 4.2 53 4.9
IB 10 96 0.5 79 1.0 68 1.0 70 1.2
IB 11 99 0.7 82 1.2 67 1.2 70 1.5
IB 12 110 0.6 92 1.0 77 1.0 80 1.2
IB 13 87 0.5 68 1.2 62 1.1 55 1.3
IB 14 86 0.8 74 1.3 62 1.3 57 1.5
IB 15 68 0.6 67 1.1 55 1.1 54 1.1
IB 16 69 0.7 59 1.1 47 1.1 50 1.2
IB 17 103 0.7 89 1.0 76 1.1 78 1.3
IB 18 107 1.9 89 2.5 77 2.3 76 2.7
IB 19 85 1.1 78 1.5 69 1.3 67 1.6
IB 20 85 4.2 75 2.9 62 3.0 60 3.2
IB 21 93 0.6 86 1.2 74 1.2 76 1.3
IB 22 98 4.2 80 4.2 69 4.9 71 5.1
IB 23 104 0.6 87 1.1 78 1.2 78 1.3
IB 24 101 0.5 89 1.1 77 1.2 77 1.3
IB 26 88 7.8 78 8.0 67 9.4 68 10.0
IB 27 89 3.0 77 2.1 62 2.1 66 2.4
IB 28 82 4.7 64 4.2 53 5.3 51 5.8
IB 29 77 0.5 65 1.3 53 1.2 53 1.3
IB 30 36 0.6 26 0.8 21 0.7 20 0.8
IB 31 81 3.8 72 3.0 60 3.1 62 3.2
IB 32 85 0.0 78 2.0 60 2.0 64 2.4
IB 33 81 2.4 77 1.8 63 1.9 68 2.2
IB 34 85 0.5 76 0.9 64 1.0 62 1.1
IB 35 38 0.5 35 0.8 31 0.8 28 0.9
IB 36 53 1.0 51 1.4 43 1.3 45 1.5
IB 37 80 0.9 79 1.4 66 1.5 71 1.7
IB 38 65 0.8 64 1.1 60 1.0 60 1.2

EG solvation yielded different basal spacings of the smectites. Only
a few bentonites showed full expandability (class 1). Values below
16.9 Å indicated the presence of non-swelling domains (class 2: 16.5–
16.9 Å, class 3: 15.5–16.5 Å, class 4: b15 Å). These classes correlated
with the decrease of the water uptake (Fig. 7a, b). Carbonates still
played a role, obviously because the carbonate-rich samples provided
Ca2+ ions probably during the wetting steps. Hence, carbonate poor
samples were plotted for comparison. Unfortunately, the number of
carbonate-poor samples was too low (Fig. 7b) to unambiguously
prove that LOSXRD and water uptake (LOSWUC) were related. This
correlation was expected because EG and water are solvating
molecules with comparable adsorption energy. The CEC index cation
Cutriene, on the other hand, exchanges all cations and is adsorbed more
selectively than EG which explains why the XRD classes do not
correlate with the LOSCEC (Fig. 7c, d).
The main conclusion (Fig. 7) is that the determination of the LOS
depends on the method applied. On average a decrease of the water
uptake (LOSWUC) of 50% was measured (e.g. 7 mass% water uptake
compared to 14 mass% of the initial material). Cutriene, on the other hand,
indicated lower LOS values (approximately 25%). This can be explained
by the fact that both adsorption mechanisms and energies are different.
Cutriene does not solvate the cations but replaces the K+ ions. The results
indicate that Cutriene can exchange some K+ ions which already reside in
the ditrigonal holes causing partial interlayer collapse.
Now the question arises how these values (LOSCEC, LOSXRD,
LOSWUC) are related to possible illitization (Fig. 8): The decrease of
the water uptake (LOSWUC, Fig. 8a, b) as well as the basal spacing in EG
(LOSXRD, Fig. 8c, d) depend on the layer charge density (LCD) which
was expected because this effect is e.g. used for LCD estimation
(Christidis and Eberl, 2003). The reason for this relation is discussed
controversially (as explained in the introduction). The model that
tetrahedral charge determines the LOS together with the finding that
the LCD correlates well with the LOSWUC and LOSXRD implies that there
is a correlation of the LCD and the amount of tetrahedral charges of
the smectites. For 36 bentonites of the present study no such trend
was observed (Fig. 9). On the other hand the well known correlation
between LCD and the position of the 001 reflection of K+-smectites
was confirmed in the present study (Fig. 8). In contrast, LCD and
LOSCEC were not correlated (Fig. 8e, f).
The LOSWUC and LOSXRD obviously depended on the layer charge
density (Fig. 8). A model is proposed (Fig. 10) which can explain these
correlations (Fig. 8) and the fact that the LCD is not related to the
amount of tetrahedral charge (Fig. 9).
Generally, swelling of smectites occurs in the case that the
solvation forces prevail over attraction forces (Fig. 10 a: Fsolv N FA).
The competition between both forces depends on the solvation
(hydration) energy. In a very simple model, the electrostatic
attraction between an interlayer cation and the negative charges
will be increased in the case of two opposing charges. Hence, FAA is
significantly larger than FA. The experimental results prove that the
charge location (tetrahedral or octahedral) is not relevant here. Of
course K+ is more strongly attached to tetrahedral sites but this
difference obviously does not explain the different LOS values and
hence is considered to be less important. According to this model FAA
 S. Kaufhold, R. Dohrmann / Applied Clay Science 49 (2010) 98–107 103

Fig. 6. Classification of the samples in the wetting-drying cycles (after S3) according to XRD (oriented films after EG salvation). Class 1 = 16.9 Å, class 2 16.5–16.9 Å, class 3: 15.5–
16.5 Å, class 4: b15 Å. The two I–S containing samples were not considered here.

Fig. 7. Correlation of the LOSXRD (XRD classes) with the LOSWUC (decrease of water uptake) and the LOSCEC (CEC decrease). a and c show all samples, b and d only those with a calcite
content b 1 mass%.
104 S. Kaufhold, R. Dohrmann / Applied Clay Science 49 (2010) 98–107

Fig. 8. Correlation of the layer charge density (LCD) and the loss of swelling capacity (LOS) determined by water uptake (a, b), XRD (c, d), and CEC (e, f).

is supposed to be larger than Fsolv in the case of K+ occupation which
leads to the collapse. The FAA/FA ratio of a real smectite particle, in
turn, is affected by the layer charge density because statistically the
probability for the existence of two opposing charges increases with
increasing LCD. The existence of two opposing charges is assumed to
be the prerequisite for the occurrence of a collapsed domain. An actual
collapse, the formation of 10 Å units, occurs if the cation resides in the
ditrigonal holes of both sides. Based on the experimental data
obtained in the present study, the key of the model is that octahedral
charge is a sufficient cause for the K+ to move into these holes. No
doubt exists about the fact that tetrahedral charge binds the cation
more strongly but octahedral charge on both sides is obviously
sufficient for the occurrence of a collapse.
In summary: we assume collapsed domains exist in case of two
opposing charges (regardless which type) which for statistical
reasons occur more frequently between layers of high charge density.
 S. Kaufhold, R. Dohrmann / Applied Clay Science 49 (2010) 98–107
Fig. 9. Layer charge density determined according to Lagaly (1994) and amount of
tetrahedral charge (in %) determined by CEC measurements after Li-treatment
(Greene-Kelly, 1953).
These results support the view that the total charge determines
the collapse of K+ smectite particles (as Weir, 1965; Schultz, 1969;
Sawhney, 1969; Horváth and Novák, 1976).
3.4. Different behavior of different bentonites
The different values of LOSWUC and LOSXRD of the different
bentonites could be explained by different LCD. On the other hand,
the LOSCEC was not correlated with the LCD or with another bentonite
property. Interestingly, the most resistant samples (lowest LOS
values) were also less reactive in the NaCl test (Kaufhold and
Dohrmann, 2008) and less sensitive towards extensive drying which
also affects the swelling capacity (Kaufhold and Dohrmann, in press).
The challenge now is to try to identify the reason for this different
behavior. Unfortunately no parameter was found which explained the
different behavior of the bentonites. Among 36 bentonites, two
particularly resistant (low LOS values) and three comparably reactive
samples (high LOS values) were identified (Table 3) but no reason for
these differences could be evaluated. Based on the model presented in
the preceding chapter the layer charge distribution possibly explains
the differences. A homogenous layer charge density distribution
would result in a large number of opposing charges. Theoretically, in
the case that all charges have the same distance, all charges would be
opposing which would result in total collapse (equal distances of the
charges would enable the TOT layers to arrange in a way that all
charges are opposing).
Fig. 10. Model trying to explain the reason for the dependence of the XRD results on the LCD despite the missing correlation of LCD and tetrahedral charge. a) situation at an
individual charge site: swelling occurs in case the solvation energy exceeds the attraction forces (FA = attraction force in case of one charge; FAA = attraction force in case of two
opposing charges, regardless if tetrahedral or octahedral charge); b) model: in the case of K+ occupation (FAA N Fsolv N FA).
105
Additional information regarding illitization can be gained from
considering the chemical balance, particularly the ratio of silica
formed related to the initial smectite mass. Considering ideal formulas
(e.g. no tetrahedral charge of a montmorillonite), the illitization
process of a low charged illite (0.6 eq/FU) can be written as follows:
þ VI þ
ðNa Þ0:3 ðAl1:7 Mg0:3 ÞðSi4 O10 Þ þ 0:6K þ 0:15Al2 O3 ⇒
VI IV þ
K0:6 ðAl1:7 Mg0:3 ÞðSi3:7 Al0:3 O10Þ þ 0:3SiO2 þ 0:3Na
A Na+ montmorillonite without any tetrahedral charge and a
perfect octahedral sheet (sum = 2.0; commonly the sum slightly
exceeds 2.0) is reacted with sufficient K+ to produce a low charged
illite which still has octahedral charge. The formation of an illite
without octahedral charge, which can possibly form upon dissolution
and precipitation, would imply the formation of a separate Mg
mineral (e.g. chlorite).
To estimate the ratio of silica formed related to the initial mass of
the smectite, the reaction given above is applicable. Thus, approxi-
mately 20 mass% silica would be produced by complete illitization of a
smectite. This value, of course, strongly depends on the assumed
composition of the product (illite) and would be different if the LCD of
the illite is close to one.
The silica produced at the low temperature of the KLTS and KWD
experiments is supposed to possess a low degree of crystalline order.
Similar SiO2 products are probably obtained by acid activation and/or
natural postformational processes (Kaufhold and Decher, 2003).
These silica forms can be quantitatively dissolved by hot soda
solutions. The soda-soluble silica after step 3 (S3) increased by
0.8 mass% on average which corresponds to the illitization of b5% of
the smectite. Unfortunately, the soda-soluble silica values have to be
critically considered because they are strongly affected by naturally
present silica phases. Therefore, particularly small values (e.g.
0.3 mass% difference before and after) are questionable.
4. Summary and conclusions
The present study confirmed that the reaction between KCl solutions
and smectites differs from the reaction of NaCl solutions and smectites.
Cation exchange – which can be buffered by carbonates – occurs in both
cases. Indication for a different reaction is provided by the larger
concentration of silica in solution and the amount of soda-soluble silica
which suggests that at least some smectite dissolution and illite
precipitation occurred (b5%). On the other hand, a significantly higher
loss of swelling capacity (LOS) was observed in the presence of KCl
which depended on the method applied (Cuadros and Linares, 1996;
Mosser-Ruck et al., 2001). LOSXRD corresponded to the decrease of the
water uptake (≈50%). These LOS values could be explained by the layer
106 S. Kaufhold, R. Dohrmann / Applied Clay Science 49 (2010) 98–107

Table 3
Comparison of parameters of five bentonites representing the least and the most reactive (regarding LOS) materials of the sample set. Negative values indicate an increase of the CEC,
most probably as a result of pH changes caused by cation exchange (Kaufhold et al., 2008).

LOSCEC stability tests Bentonite properties

NaCla Dry120b KLTS KWD S1 KWD S2 KWD S3 Cinorg Sol.SiO2 Smtc LCD Tet. charge CEC Naexch. pH BET WUC70 Fe2O3
2
[%] [%] [%] [%] [%] [%] [wt.%] [wt.%] [wt.%] [eq/FU] [% /CEC] [meq/100 g] [%] [m /g] [wt.%] [wt.%] [wt.%]

B-15 −3 1 9 0 16 21 0.4 0.6 70 0.38 64 76 2 8 100 15 9

B-38 −4 7 −6 1 8 8 1.0 0.8 63 0.24 25 65 21 9 22 11 3
B-36 − 20 10 0 3 18 14 0.0 1.0 75 0.20 51 53 1 7 57 11 8
B-16 25 23 22 15 32 27 0.0 0.7 58 0.27 22 67 0 7 59 14 6
B-28 20 24 9 25 41 37 0.0 4.8 69 0.32 20 72 0 7 72 15 2
a
Kaufhold and Dohrmann (2009).
b
Unpublished data, all bentonites were dried for 4.5 years at 120 °C and the CEC determined afterwards.
c
Smectite content according to Ufer et al. (2008).

charge density (the higher the LCD the higher the LOS). The LOS
determined by the decrease of the CEC (LOSCEC), on the other hand,
could not be related to the LCD. The LOSCEC (≈25%) was significantly
lower than the LOSXRD and LOSWUC which means that some of the non-
hydrated K+ ions still can be exchanged by the Cutriene cations. In case of
actual illite, this exchange is kinetically limited as it takes weeks and/or
special conditions to exchange more than 10% of K+. In conclusion, the
LOSXRD and/or LOSWUC is not related to an illitization process.
Considering the increase of the amount of soluble silica suggests that
the Cutriene method does not represent the actual degree of illitization:
the amount of soda-soluble silica increased by approximately 0.8 mass%
(negative values were not considered) indicating approximately 5%
illitization which is significantly below the CEC value (25%).
XRDEG and WUC are neither suitable to detect illitization nor
irreversibly fixed K+. Both methods just provide a value describing a
certain number of layers/domains which do not swell with water or
ethyleneglycol. Cu2+triene is able to exchange some of the non-
solvated K+ ions but only reflects a certain degree of collapse which
does not describe illitization because the amount of soda-soluble silica
would have to be significantly higher. The determination of the
amount of soda-soluble silica is considered to represent actual
illitization but has to be applied critically, particularly in the presence
of different SiO2 phases (opal — cristobalite).
The different LOS values of the K+ wetting and drying cycles
indicated that the smectite fraction of the products (on average) is
composed of 50% swelling K+ smectite, 45% non-swelling collapsed
K+ smectite (50% of which with fixed K+, fixed with respect to Cutriene
exchange at standard conditions) and 5% illite which probably formed
by dissolution and precipitation. A solid state transformation would
not explain the increased amount of soda-soluble silica.
One of the aims of this study was to identify the reason for the
different behavior of the different bentonites. Some bentonites were
found to tend more to collapsed domains than others. The reason for
this different behavior could not be identified, yet. A significant set of
parameters was considered but even no indication for a reason was
found. In this content it is interesting to note that the different trends
towards loss of swelling (LOS) were proven in different experiments.
The samples with the largest LOS values had higher LOS values in the
NaCl test (Kaufhold and Dohrmann, 2009) and in the extensive drying
test (Kaufhold and Dohrmann, in press). In the present study a model
is presented which i) explains different tendencies towards collapse
(in different tests), ii) how this phenomenon is related to the layer
charge density, and iii) why the bentonites lost appreciable swelling
already within days. The model is based on the assumption that two
opposing charges are the prerequisite for complete collapse (to 10 Å).
Accordingly, a homogenous layer charge density (with equal
distances) would cause a higher number of opposing charges which
is considered to be the key for the collapse.
Concerning the real illitization, the different behavior of the different
bentonites possibly can be explained by the solubility of the smectites
which is known to depend on the chemical composition (particularly
Mg and Fe in octahedral sheet, e.g. Cicel and Novak, 1976; Novak and
Cicel, 1978) and on particle diameter and morphology.
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