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A Proposed Modification to Barium Chloride Method
for CEC Measurement of Calcareous Clayey Soils
Ouhadi, VR
Civil Engineering Department, Faculty of Engineering
Bu-Ali Sina University Hamedan, Iran
vahidouhadi@yahoo.ca
Abstract- Cation exchange capacity (CEC) is one of the major
characteristics of clayey soils which its correct is directly
related to their industrial, engineering determination, and geo
environmental engineering applications. It is reported by several
studies that the CEC measurement of calcareous clayey soils
cannot be precisely determined due to the solubility of calcite
fraction. In addition, the appropriate soil weight for CEC
determination is a common challenge among researches. This
paper is aimed to propose a modification to the barium chloride
method for CEC measurement of calcareous clayey soils. In
this paper the common barium chloride method for CEC
measurement is developed by saturating the exchangeable
solution with carbonate calcium prior to addition of exchangeable
solution to soil samples. A smectite soil was used in this study.
The achieved results indicate that the proposed modification to
the barium chloride method solves the common problems
associated with the traditional barium chloride method in
calcareous soils. Furthermore, the modification is simple in
application and its performance takes an acceptable period of
time.
Keywords- cation exchange capacity; calcareous clays; smectite;A. Soil Samples
barium chloride; calcite
I. INTRODUCTION
Soil Cation Exchange Capacity (CEC) is one of the important
geo-environmental characteristics of clayey soil parameters that
influence swelling [1] and cohesion [2] of clays. The traditional
method used to determine soil CEC may unavoidably introduce
errors if applied to calcareous soils. This is attributed to the fact
that calcium (Ca) salts in calcareous soils are easily dissolved
and interfere with the CEC determination [3].
One of the suggested methods for determining the CEC of
calcareous soils was the use of buffered BaCl2-TEA
(triethanolamine) at pH 8.2 as a saturating solution [4]. Other
researches have modified this method to provide a procedure
that is un-buffered and has an ionic strength close to that found
in highly weathered soil [5]. Later on, other researches modified
the Gillman's method by increasing the concentration of both
the saturating and replacing solutions and by eliminating the
adjustment of electrical conductivity [6]. Their results supported
the previous works who had addressed that the sum of cations
extracted by divalent salt solution (BaCl2 or SrCl2)
978-1-4244-8165-1/11/$26.00 ©2011 IEEE
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Deiranlou, M
Civil Engineering Department, Faculty of Engineering
Bu-Ali Sina University Hamedan, Iran
m.deiranlou@yahoo.com
gives a very good estimation of CEC. Their method is not only
faster, but it measures the CEC that exists in the field [6].
Furthermore, prior research shows that the use of BaCl2 is
favored by its strong replacing power without being preferentially
adsorbed, and the fact that it does not cause the collapse of
expanded phyllosilicates as does K+ or NH4+ [7].
However, it should be emphasized that according to Corpena et
al. [8], BaCl2 can dissolve substantial quantities of CaSO4 and
MgCO3 and small amounts of CaCO3. Another error can be
introduced by CaCO3 dissolution caused by BaCO3 precipitation
[9]. Therefore it can be concluded that by the use of barium
chloride as a source of replacement cation for CEC measurement,
an error in CEC determination can be expected.
Based on the discussion above, this paper is intended to
propose a modification to the traditional barium chloride method
for cation exchange capacity measurement of calcareous clayey
soils.
II. MATERIALS AND METHODS
The Smectite soil used in this research was provided by
“Iran Barit Company”. The specimens were air-dried and the
fraction <2 mm was used in all subsequent analyses. Organic
content is determined according to ASTM methods [10]. The
specific surface area (SSA) was measured using the ethylene
glycol monoethyl ether (EGME) method [11]. The carbonate
content of the soil was determined by titration [12]. Calcium
arbonate (CaCO3) was removed from smectite by washing soil
with 0.1M HCl and further three-step soil washing with distilled
water. All experiments of this paper were performed on triplicate
samples for each test to verify the reproducibility of results. The
geo-environmental characteristics of the smectite sample are
given in Table 1.
B. Soil/ Calcite Mixtures
Smectite samples which had 2%, 8% (original smectite
sample), 12%, 20%, and 30% calcite were used in this study.
The original smectite sample had 8% natural carbonate. It was
de-carbonated by acid washing, as it was addressed in the
previous section, to reduce its calcite concentration to 2%. In
addition, 4%, 12%, and 22% laboratory carbonate was manually
added to original smectite samples to achieve the required
mixtures of smectite rich in carbonate.
Machine Translated by Google
TABLE I. GEO-ENVIRONMENTAL CHARACTERISTICS OF SMECTITES
Characteristics
Quantity Measured
Mineral composition Montmorillonite, Quartz,
In decreasing abundance Calcite
pH in H2O 10.31
pH in CaCl2 (0.01 N) 9.58
pH in KCl (1N) 8.72
Carbonate content 8%
Organic content <1%
Specific surface area (SSA) (m2 /g) 418
C. Preparation of Calcite Saturated Barium Chloride
One of the problems associated with the application of the
traditional BaCl2 method [13] in calcareous soil is the
dissolution of calcite which produces extra calcium ions at
relatively low pH. To prevent the dissolution of calcium ions
from calcite, it was decided to perform the traditional BaCl2
method with calcite saturated BaCl2. For this purpose the
preparation of calcite saturated BaCl2 exchange solution was
prepared as a replacement solution in the traditional BaCl2 method.results of Figure 1 can be interpreted as follows: The presence
Dohrmann [14] has previously suggested the application of
calcite rich solution for CEC measurement in silver-thiourea
method. For preparation of the replacement solution, 24.43 g
of BaCl2 was dissolved in de-ionized water and the solution
was filled up to 1000 ml with de-ionized water in a volumetric
flask. Then, 4 g of fine-grained calcite (Merck) was added to
the solution. After this step, the solution was stirred vigorously value because of the reduction of barium ions concentration
for 2 h on an end to end shaker. Then, the sample was kept
for 24 hours settling. Finally the supernatant was filtered to
remove any suspended calcite grains. This solution was used
as electrolyte substitution in the traditional BaCl2 method.
D. CEC Measurement by Common Barium Chloride Method
The common BaCl2 method [13] was used to determine
the CEC of soil samples. For this purpose, between 0.3 to 0.7
g of dry soil sample was weighed into a 50 ml centrifuge tube.
Then, 30 ml of 0.1 M BaCl2 solution was added as electrolyte
to the centrifuge tube. Then, the tube was shaken slowly in
an end to end shaker for 2 hours. After this step, the pH of
soil solution was measured. Finally, the sample was
centrifuged at 2500 rpm for 5 min and the supernatant solution
was filtered through Watman 42 filter paper. The solution was
collected in polyethylene bottles for analysis of exchangeable
cations and barium ion concentration. The amounts of cations
remaining in the supernatant were analyzed using an atomic
absorption spectro-photometer (GBC 932 AB Plus).
E. Selection of Suitable Solution/ Solid Ratios
The selection of suitable solution/solids ratios is important 50 percentage of calcite. As the results plotted in Figure 1, the
to optimize the precision of the CEC results. Appropriate
solutions/solid ratios should be used to achieve reasonable
results with small errors. In one aspect if an inappropriately
large solution/solid ratio is chosen, the soil structure will
become so flocculated therefore, very small amounts of
exchangeable cations will be extracted during the CEC
experiment. On the other hand, if an unsuitably small solution/
solid ratio is chosen, the selectivity of the index
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cations would be too small to replace all the cations during
the exchange experiment. Furthermore, if the same volume of
solution is used in all instances, then the sample mass will be
the determining factor for optimum precision of the CEC and
exchangeable cations. In this paper, 0.3, 0.5 and 0.7 g of soil
samples were used for CEC measurement experiments.
III. RESULTS AND DISCUSSION
To investigate the influence of the carbonate on the results
of the traditional barium chloride method for CEC measurement,
a series of smectite samples were mixed with different
quantities of carbonate. Furthermore, for each specific mixture
of smectite and carbonate, the barium chloride method was
performed on three samples with 0.3, 0.5, and 0.7 g initial
weight. This was done to take into account the influence of
soil sample weight on the CEC measurement results. Figure
1 shows the results of these experiments. As can be seen in
Figure 1, with increasing the quantity of calcite in smectite
sample, an increase in CEC of sample is observed. In addition,
the results of Figure 1 show that for each experiment at a
specific concentration of calcite, as the initial weight of soil
sample increases the soil shows a larger CEC. The achieved
of barium chloride will dissolve a part of the calcite of soil
sample. In such a case the barium carbonate (BaCO3) will
precipitate. Since in CEC measurement the cation exchange
capacity will be calculated based on the reduction of barium
ions in electrolyte due to its adsorption by soil, the formation
of BaCO3 will cause to estimate the CEC more than its real
in electrolyte due to the formation of barium carbonate. This
is the main reason for achieving a wrong CEC with the
application of the traditional barium chloride method in
calcareous soils. For this reason in the results of Figure 1 as
the concentration of calcite is increased we are facing with an
increase in CEC. Furthermore, according to the results of
Figure 1, for the similar volume of electrolyte in the experiment,
the influence of calcite solubility on the results of CEC is more
distinguishable at lower quantities of soil. In other words, lower
soil-electrolyte ratio gives larger CEC. This is because at
smaller soil quantities, the exchangeable solution has a larger
solubility ability for calcium carbonate fraction of soil [14].
There is another very interesting point in the results of Figure
1. According to the results of Figure 1, for 0.5 and 0.7 gram
samples, there is a specific concentration of calcite in which
increasing the calcite concentration from that quantity does
not affect the CEC results. It means that at a very large
quantity of calcite, the exchangeable solution will not solubilize
any more calcite. Therefore the formation of barium carbonate
will be stopped. To make sure about this conclusion, CEC
was measured for two 0.5 gram smectite samples with 40 and
cation exchange capacity has not changed in these two
mixtures of calcite and smectite samples. Furthermore, if in
Figure 1, one changes the horizontal axis to the weight of
calcite in smectite sample instead of calcite percentages,
another interesting conclusion can be observed. In such a
case the quantity of calcite is more than 0.14 grams, regardless
of the weight of calcite in the sample, the CEC will not change.
In fact, at this specific quantity of calcite in smectite sample, the reactio
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in solution will be equilibrated. In other words, at this specific
quantity of carbonate (0.14 g calcite in 35 ml of 0.1 M BaCl2, or
4 g in 1000 ml), the solution is saturated with soluble calcite.
This quantity of carbonate was chosen for an exchangeable
solution in the proposed modified method.
To overcome the above mentioned problems in CEC
measurement of calcareous soil, based on the above discussion
and comments presented by previous researchers [14], BaCl2
solution was saturated by carbonate calcium prior to the
application of barium chloride method, as it was addressed in
material and method section. Figure 3 shows the achieved
results for CEC measurement of similar samples as Figure 1 by
the use of modified BaCl2 method.

Figure 1. Variations of CEC versus calcite quantity for smectite in

traditional BaCl2 method.

Figure 2 shows the pH variations for the same samples of Figure 3. The variations of CEC of smectite versus its calcite concentration
in modified BaCl2 method
previous Figure as a function of calcium carbonate in smectite.
While the pH is a function of calcium concentration in soil
As can be seen for the proposed method, not only the results
samples, it does not show significant changes at different soil
are relatively insensitive to the calcite concentration in soil
quantities. Furthermore, the results of Figure 2 indicate that as
sample, but also the scattering of achieved CEC is much less
the quantity of calcite increases in soil sample, the soil shows
in comparison to that of the traditional BaCl2 method .
more buffer behavior in which the buffering tends to a relatively
To make sure about the accuracy of the achieved results for the
constant value. This is another reason for the saturation of
proposed modified method, the pH of these series of samples
electrolyte by carbonate at large quantities of calcite in the soil
mixture. was measured and presented in Figure 4.

Figure 4. Variations of pH for smectite versus its calcite concentration in

Figure 2. Variations of pH for smectite versus its calcite concentration in modified BaCl2 method
traditional BaCl2 method

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TABLE II. COMPARISON OF THE TWO CEC METHODS BY STATISTICS PARAMETERS
Method of one-step BaCl2-calcite extraction
Weight
of soil (g) Summation of cations CEC
(cmol/ kg-soil) (cmol/ kg-soil) (cmol/ kg-soil)
0.3 62.22 65.22 3.73
0.5 60.69 52.68 3.62
0.7 60.08 43.42 4.21
As can be seen in Figure 4, the measured pH is also
insensitive to calcite variations in the soil sample. Since soluble
carbonate is one of the major sources for increasing the pH,
therefore achieving constant pH in this case means that with
saturation of the soil solution by carbonate, the solubility of
calcite in solution is stopped. Consequently, the presence of
calcite in such a case has not affected the CEC measurement
procedure.
Still there is one more question that should be answered.
Since different CEC was achieved for different soil
exchangeable solutions, therefore one may ask for appropriate
soil quantity to achieve the most correct value for CEC. To
answer this question a statistical evaluation was performed.
The summary of this statistical evaluation is presented in Table
2. In this Table, the mean value for CEC measurement, standard
deviation and coefficient of variation for CEC measurement is
presented, for each specific soil weight with different percentages
of carbonate in soil mixture. As an example, as the results of
Table 2 show the CEC of smectite with an initial weight of 0.3 g
is 103.95 cmol/kg-soil for the traditional BaCl2 method. This
measured CEC was 65.22 cmol/kg-soil for the modified CEC
method. In these two cases the standard deviation which is
representative of scattering data was 58.93 cmol/kg-soil for the
traditional BaCl2 method. This was decreased to 3.73 cmol/kg
–soil for the modified BaCl2 method. The same significant
reduction in COV was observed in these two series of
experiments in which the COV decreased from 59.69 to 5.71.
These results approve the accuracy and reliability of the results
of the proposed modified barium chloride method.
IV. CONCLUDING REMARKS
The BaCl2 method which is known as a quick and reliable
method for CEC measurement of acidic soil is not applicable to
calcareous clayey soils. In this paper a modification for this
method is proposed. Based on this modification by saturating
the exchangeable BaCl2 solution with calcite before it has been
applied to the soil sample, the dissolution of calcite is prevented.
Therefore, the common errors due to the measurement of extra
calcium ions in the supernatant will not occur. The achieved
results of this paper showed that the proposed modification
gives reasonable and acceptable results for smectite laboratory
samples rich in calcite.
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Method of one-step BaCl2 extraction
SD COVs CEC SD COVs
(%) (cmol/ kg-soil) (cmol/ kg-soil) (%)
5.71 103.95 58.93 56.69
6.86 77.11 44.32 57.48
9.69 64.32 31.06 48.33
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