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OPEN Change in the site density and

surface acidity of clay minerals by
acid or alkali spills and its effect on
Received: 12 February 2019
Accepted: 24 June 2019 pH buffering capacity
Published: xx xx xxxx
Inhyeong Jeon & Kyoungphile Nam

Changes in the site density and surface acidity constants (i.e. pKa1 and pKa2) of kaolinite and
montmorillonite were determined after acid or alkali spills, and pH buffering capacity was evaluated as
a parameter of soil function change. Surface complexation modeling with potentiometric titrations and
Fourier-transform infrared spectroscopy showed that acid or alkali spills did not significantly change the
surface properties of kaolinite. In montmorillonite, however, acid spills decreased the basal site density
from 832 to 737 mmol kg−1 by dissolving substituted octahedral cations and decreased pKa2 from 7.32
to 5.42 by dissolving SiOH. In response to alkali spills, the basal site density increased to 925 mmol kg−1,
and the edge site density increased from 84.8 to 253 mmol kg−1 due to AlOH and SiOH formation; thus,
pKa2 decreased to 6.78. The pH buffering capacity of acid- or alkali-spilled kaolinite at pH 6 did not
significantly change, while that of acid- or alkali-spilled montmorillonite increased from 30.3 to 35.9 and
56.0 mmol kg−1, respectively. Our results indicate that these spills greatly altered the surface properties
of montmorillonite, but unexpectedly, increased the pH buffering capacity of montmorillonite.

As the chemical industry develops, chemical accidents occur annually, and of them, acid or alkali spills are of
great concern because of their high frequency and hazard1. According to the Chemistry Safety Clearing-house
database2, acid or alkali spills accounted for 46% of the chemical accidents in South Korea3,4. If acid or alkali
spills onto soil, most of the physicochemical properties of soil are altered, such as pH, organic matter content,
base saturation, exchangeable cations, and surface area5–9. Although neutralizers have been poured onto acid- or
alkali-spilled soils for pH recovery10,11, neutralization cannot recover nonreversible dissolution of organic mat-
ter or clay minerals and the change in cation exchange capacity (CEC) caused by the structural deterioration12.
Changes in these properties will alter soil functions, particularly pH buffering capacity. Because pH buffering
capacity is related to soil productivity and the water quality of stream water near soil13, studies of the change in
pH buffering capacity of acid- or alkali-spilled soil after neutralization are needed.
For this purpose, the effects of acid or alkali spills on organic matter and clay minerals, the soil constituents
that determine the pH buffering capacity of soils, should be analyzed. In the case of organic matter, acid or alkali
spills desorb or dissolve it14–16; thus, the pH buffering capacity decreases. However, the effect of these spills on
clay minerals is unclear. Little attention has been paid on changes in clay minerals’ properties due to these spills.
Only a few studies revealed that an acid or alkali treatment at room temperature over two weeks not only altered
a crystal structure of clay minerals but also increased surface area8. Instead, many studies have focused on an acid
or alkali activation treating clay minerals with high concentration of acid or alkali, and its effect on clay minerals’
surface area, porosity and surface acidity17–19. Also, there have been several studies on soil acidification phenome-
non, and they revealed that the long-term acidification led to chemical weathering of clay minerals and decreased
the base saturation20–22.
However, these reaction conditions are unrealistic in natural environment after acid or alkali spills. To predict
the pH buffering capacity of acid- or alkali-spilled clay minerals, clay minerals’ site density and surface reaction
constants should be determined. It has been known that two major pH buffering reactions of clay minerals are
protonation or deprotonation reaction of edge sites, and proton exchange reaction of basal sites23,24. Previous
studies have successfully identified the site density of surface functional groups in clay minerals and their surface

Department of Civil and Environmental Engineering, Seoul National University, Seoul, 08826, Republic of Korea.
Correspondence and requests for materials should be addressed to K.N. (email: [email protected])

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Figure 1. XRD patterns of three different (left) kaolinite and (right) montmorillonite samples. Black,
red, and blue lines represent the XRD patterns of untreated, acid-spilled, and alkali-spilled clay minerals,
respectively. Kaolinite and montmorillonite contained an anatase and a quartz as an impurity, respectively,
which is consistent with the previous baseline study on the XRD patterns of KGa-1b kaolinite and Swy-2
montmorillonite24.

Concentration of Dissolved Constituent Elements

Clay minerals Condition Al Si Fe Mg
mg (g clay minerals)−1
Acid 2.67 ± 0.15 0.74 ± 0.04 0.25 ± 0.01 0.03 ± 0.00
Kaolinite
Alkali 21.8 ± 1.00 25.0 ± 2.3 0.48 ± 0.14 0.02 ± 0.00
Acid 9.09 ± 1.56 18.8 ± 6.2 11.3 ± 1.19 1.99 ± 0.34
Montmorillonite
Alkali 1.24 ± 0.28 104 ± 11.5 2.61 ± 0.16 0.11 ± 0.06

Table 1. Dissolution of the clay minerals’ constituent elements by acid or alkali spills measured by ICP-OES.
The concentration of dissolved elements are the average values of triplicate experiments.

reaction constants using surface complexation modeling25,26. Nevertheless, a few studies exist investigating alter-
ations of surface properties of clay minerals at ambient temperature following intensive acid or alkali treatment,
which is similar to acid or alkali spills, by using surface complexation modeling. In addition, clay minerals play a
significant role in the pH buffering capacity of soils with low organic matter content resulting from acid or alkali
spills; thus, knowledge of the changes in clay minerals’ properties after these spills is essential to interpret the pH
buffering capacity of the soils.
The goals of this study were to investigate changes in the site density and surface reaction constants of the
neutralized clay minerals after acid or alkali spills and evaluate their effect on the pH buffering capacity as an indi-
cator of soil function. Kaolinite (KGa-1b, Georgia) and montmorillonite (SWy-3, Wyoming), which are typical
1:1 and 2:1 clay minerals, respectively, were selected in this study. Three different samples (untreated, acid-spilled,
and alkali-spilled) were prepared by treating with deionized water, 5 M HCl, and 5 M NaOH, respectively, and
they were neutralized, and their surface properties before and after acid or alkali spills were compared. The site
density and surface acidity constants were determined by a potentiometric titration using surface complexation
modeling, and the change in the pH buffering capacity resulting from acid or alkali spills was investigated.

Results and Discussion

XRD characterization of three different clay minerals. The XRD patterns of three different kaolinite
and montmorillonite samples are shown in Fig. 1, and the results of quantitative analysis are summarized in
Supplementary Table S1. The untreated kaolinite and montmorillonite were mainly composed of pure kaolin-
ite (98%) and montmorillonite (79%), respectively. The untreated kaolinite contained an anatase (2%), and the
untreated montmorillonite contained a quartz (13%) and cristobalite (8%). The results are consistent with the
previous baseline study on the XRD patterns of KGa-1b kaolinite and Swy-2 montmorillonite27.
The XRD patterns and quantitative analysis showed that while acid or alkali spills had little effect on the
crystalline structure and the mineral identity of kaolinite, they had some effects on those of montmorillonite.
Newly formed constituents were not observed in both acid- or alkali-spilled kaolinite and montmorillonite. The
proportions of kaolinite and anatase in both acid- and alkali-spilled kaolinite did not change as a result of each
spill. In montmorillonite samples, however, acid spills did not significantly change the proportion of montmoril-
lonite, while decreased that of quartz to 4% and increased that of cristobalite to 14%. Alkali spills increased the
proportion of montmorillonite to 88%, while decreased those of quartz and cristobalite to 9 and 3%, respectively.

Dissolution of major elements of clay minerals by acid or alkali spills. The concentrations of dis-
solved elements of kaolinite and montmorillonite as a result of acid or alkali spills are summarized in the Table 1.

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0.0003 0.0003

KAOLINITE MONTMORILLONITE

0.0002 0.0002

0.0001 0.0001

TOTH [M]
TOTH [M]
0.0000 0.0000 Untreated_0.1 M NaNO3
Untreated_0.01 M NaNO3
Untreated_0.001 M NaNO3
-0.0001 -0.0001
Acid spilled_0.1 M NaNO3
Acid spilled_0.01 M NaNO3
Acid spilled_0.001 M NaNO3
-0.0002 -0.0002
Alkali spilled_0.1 M NaNO3
Alkali spilled_0.01 M NaNO3
3 4 5 6 7 8 9 3 4 5 6 7 8 9
Alkali spilled_0.001 M NaNO3
pH pH

Figure 2. Titration curves of three different (left) kaolinite and (right) montmorillonite samples obtained from
potentiometric titrations. The Y-axis is the molar concentration of the total added proton in the solution. The
black, red, and blue symbols represent untreated, acid-spilled, and alkali-spilled kaolinite or montmorillonite,
respectively, and the circle-, rectangle-, and triangle-shaped symbols represent a 0.1, 0.01, and 0.001 M NaNO3
condition, respectively. All experimental data were well fitted with predicted titration curves using SCM (see
Supplementary Fig. S1).

Kaolinite Montmorillonite
Alkali- Acid- Alkali-
Untreated Acid-spilled spilled Untreated spilled spilled
Surface reaction constants (pK)
≡ SOH2+ ↔ ≡ SOH + H + (pKa 1) −4.55 −4.38 −4.72 −5.79 −5.93 −5.00
≡ SOH2+ ↔ ≡ SOH − + H + (pKa 2) 5.49 5.94 6.34 7.32 5.42 6.78
≡ X − ⋅ Na+ + H + ↔ ≡ X − ⋅ H + + Na+ (pK H) −2.90a −2.90a −2.90a 1.51 0.72 1.85
Functional group density
Edge site density (mmol kg−1) 35.8 40.6 38.6 84.8 85.3 253.2
Basal site density (mmol kg−1) 8.3 5.9 8.2 832.0 737.0 925.0

Table 2. Optimized surface properties of three different kaolinite and montmorillonite samples using FITEQL.
The Ka1, Ka2, edge site density and basal site density were fitting parameters and optimized. In montmorillonite
samples, KH was also included in fitting parameters. The detailed procedure of parameter optimization is
summarized in the Supplementary Information. aNot determined by optimization, but the average value of
other research55,68–70.

The dissolved Al and Si concentrations of kaolinite after acid spill were 2.67 mg-Al g −1 and 0.737 mg-Si g−1,
respectively, and those after alkali spill were 21.8 mg-Al g−1 and 25.0 mg-Si g−1, respectively. Kaolinite was more
susceptible to alkali spill than to acid spill. In the case of montmorillonite, while the dissolved Al and Si con-
centrations after acid spill were 9.09 mg-Al g−1 and 18.8 mg-Si g−1, respectively, those after alkali spill were 1.24
mg-Al g−1 and 103 mg-Si g−1, respectively. While more than five times of the octahedral cations such as Al, Fe
and Mg were dissolved by acid spill than by alkali spill, the tetrahedral cation, Si, was dissolved five times more
by alkali spill than by acid spill. The high dissolution of octahedral cations as a result of acid spill was proba-
bly because protons preferentially attack the isomorphic substituted elements in octahedral sheet during acid
treatment28.

Irreversible alteration on site density and surface acidity constants resulting from acid or alkali
spills. The titration curves of three different kaolinite and montmorillonite samples under different NaNO3
concentration are shown in Fig. 2. As shown, acid or alkali spills have a greater effect on the titration curves of
montmorillonite than those of kaolinite, and the background electrolytic concentration had a limited effect on the
titration curves of both kaolinite and montmorillonite at pH values of 4–9. The reversibility test of three different
kaolinite and montmorillonite samples under 0.01 M NaNO3 are shown in Supplementary Fig. S3. Although some
hysteresis was observed, it was not pronounced. It could be because the factors such as CO2 input and dissolu-
tions of clay minerals were controlled during the experiments29. The optimized values of the surface properties
obtained from FITEQL 4.0 are summarized in Table 2.
Table 2 shows that an acid or alkali spill did not significantly change the edge and basal site density, which
refers to variable charged sites on the mineral edges and permanent negatively charged sites on basal planes,
respectively, of kaolinite (i.e. less than 5 mmol kg−1). An acid or alkali spill increased the edge site density of kao-
linite from 35.8 to 40.6 and 38.6 mmol kg−1, respectively, and changed the basal site density of kaolinite from 8.3
to 5.9 and 8.2 mmol kg−1, respectively. In the case of montmorillonite, an acid or alkali spill significantly changed
the edge and basal site density (i.e. greater than 100 mmol kg−1) except for the edge site density of the acid-spilled
montmorillonite. An alkali spill greatly increased the edge site density from 84.8 to 253.2 mmol kg−1. In addition,
an acid or alkali spill changed the basal site density from 832 to 737 and 925 mmol kg−1, respectively.

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Figure 3. FT-IR spectra of (left) kaolinite and (right) montmorillonite. Black, red, and blue lines represent
untreated, acid-spilled, and alkali-spilled kaolinite or montmorillonite.

Regarding the surface acidity constants (i.e. pKa1 and pKa2), an acid or alkali spill did not cause meaningful
changes in the kaolinite (i.e. less than a 0.5 pKa value) except the pKa2 of the alkali-spilled kaolinite increased
from 5.49 to 6.34. In the case of montmorillonite, the pKa values greatly changed compared to those of the kaolin-
ite (i.e. greater than a 0.5 pKa value) except for the pKa1 value of the acid-spilled montmorillonite. The pKa1 value
of the alkali-spilled montmorillonite increased from −5.79 to −5.00, while the pKa2 value of the acid-spilled
montmorillonite greatly decreased from 7.32 to 5.42 and that of the alkali-spilled montmorillonite decreased to
6.78. In addition, the proton exchange reaction constant of montmorillonite (pKH) changed from 1.51 to 0.72 and
1.85 as a result of an acid or alkali spill, respectively.
According to the Fig. 2, titration curves of the kaolinite and montmorillonite only slightly changed under the
different concentrations of background electrolyte. In the case of kaolinite, this was probably because the edge
site density was approximately five times higher than the basal site density, which was consistent with previous
studies24,30. Thus, the effect of the proton exchange reaction of the kaolinite’s basal sites on the titration curve was
relatively small in a range of pH 4–9 (see Supplementary Fig. S2). In contrast to the kaolinite, the basal site density
of montmorillonite was approximately 5–10 times higher than its edge site density, which was consistent with
previous research summarized in Bourg et al.25. However, the concentration of the electrolyte also had a slight
effect on the titration curves of montmorillonite, and this might be because montmorillonite used in this study
has a high affinity to Na+. Basal sites were saturated with Na+ at pH values of 4–9; thus, the proton exchange reac-
tion could be negligible within this pH range (see Supplementary Fig. S2). This indicated that the pH buffering
of both kaolinite and montmorillonite was largely determined by the edge site reactions rather than those of the
basal sites at pH 4–9. Thus, it is reasonable that the larger change in the titration curves of the montmorillonite
compared to that of the kaolinite resulting from acid or alkali spills was probably because of the greater alterations
on the edge sites’ properties in the montmorillonite.

Structural modification due to acid or alkali spills. FT-IR spectra of the three different kaolinite and
montmorillonite samples are shown in Fig. 3; the band assignments of the Clay Minerals Society’s source clay
(KGa-1b kaolinite, Swy-2 montmorillonite) were used in this study31,32. All absorption bands, particularly the
Si-O of the tetrahedral sheet at 400–1100 cm−1, Si-O-Si at 472 cm−1, Al-O-Si of the octahedral sheet at 541 cm−1,
and the OH hydroxyl groups at 915, 938, and 3600–3700 cm−1, of the untreated kaolinite were observed and the
positions of the bands were nearly the same as the reference. However, the untreated montmorillonite (Swy-3)
used in this study had a similar but slightly different shape and position of bands compared to the Swy-2 mont-
morillonite in the reference. The absorption band assigned for Al-O-Si, found in Swy-2 at 524 cm−1, was observed
near 512 cm−1, and the band assigned for the Si-O of the tetrahedral sheet, found in Swy-2 montmorillonite
at 1041 cm−1, was not observed in the untreated montmorillonite. Instead, the strong band at 1080 cm−1 was
observed, and it might be because the untreated montmorillonite contained some quartz and cristobalite whose
bands assigned to the Si-O were observed near 1080 cm−1 31. It is supported by the FT-IR spectra observed at 778
and 798 cm−1, which are assigned to the Si-O of quartz and cristobalite, respectively. These results are consistent
with the result of XRD analysis (Fig. 1 and Table S1) and the FT-IR baseline study. The other bands were similar
to those of the Swy-2 montmorillonite. Absorption bands at 842, 885, and 917 cm−1 were assigned to octahedral
sites where isomorphic substitution occurred, and the band at 3627 cm−1 was assigned to the hydroxyl groups of
octahedral cations, particularly Al3+ 33.
Acid or alkali spills did not significantly change the FT-IR spectra of the kaolinite. All the absorption bands
were in the same position and the intensity of the bands was minimally altered. This indicated that limited struc-
tural alteration occurred. This is consistent with little changes in XRD patterns and quantitative analysis of kao-
linite after an acid or alkali spill (Fig. 1 and Table S1). It is also supported by the results of the titration experiment
in which surface reaction constants and site density did not appreciably change as a result of an acid or alkali spill
(Table 2). In addition, previous studies revealed the similar result that kaolinite, which is one of the non-swelling
minerals, is the most resistant clay mineral to acid or alkali attacks8,34.
The acid- or alkali-spilled montmorillonite showed different FT-IR spectra compared to those of the untreated
montmorillonite (Fig. 3). As a result of acid spill, the intensity of the bands assigned to the isomorphically

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substituted octahedral cation sites (i.e., Al-(Mg, Fe, Al)-OH) decreased. This result was probably because of the
great amount of dissolution of Fe and Mg in montmorillonite after acid spill (Table 1). It is also supported by the
XRD quantitative analysis that the proportion of montmorillonite did not change by acid spills. It implied that the
decrease in the basal site density of the acid-spilled montmorillonite was due to the dissolution of isomorphically
substituted octahedral cation sites. In addition, acid spill decreased the intensity of the band for the Si-O-Si sites
of montmorillonite, while the Si-O band at 1080 cm−1 was shifted to 1090 cm−1 at which the Si-O band of cris-
tobalite was assigned31. Together with the results of the XRD quantitative analysis (Table S1), the FT-IR spectra
indicated that acid spills dissolved Si from montmorillonite and cristobalite was formed. Madejová also observed
the similar trend in smectite that the amorphous silica was newly formed after acid treatment32.
In contrast to acid spill, alkali spill increased the intensity of the band assigned to the isomorphically sub-
stituted octahedral cation sites of montmorillonite, which corresponds with the optimized basal site density
in Table 2. Alkali spill increased basal site density by about 10% (Table 2), which matched with the increasing
ratio of montmorillonite by alkali spills (Table S1); Thus, the possible reason for the increase can be ascribed
to the enrichment of montmorillonite by alkali spill. Regarding the Si environment in montmorillonite, alkali
spill decreased the intensity of Si-O bands of quartz and cristobalite at 778, and 798 cm−1, respectively, which is
consistent with the XRD results of alkali-spilled montmorillonite. The absorption band assigned to the Si-O of
the tetrahedral sheet, which was not observed in the untreated or acid-spilled montmorillonite, appeared in the
alkali-spilled montmorillonite at 1041 cm−1. In addition, the intensity of the band assigned to hydroxyl group at
3627 cm−1 increased by alkali spills, which corresponds to the increase in the edge site density of alkali-spilled
montmorillonite from titration experiment (Table 2). According to Table 2, the alkali-spilled montmorillonite had
different Ka values with those of the untreated montmorillonite. The results of FT-IR analysis and optimized Ka
values indicate that alkali spills increased the proportion of montmorillonite by dissolving quartz and cristobalite,
and also changed the surface functional groups’ properties by forming new AlOH and SiOH in montmorillonite.
FT-IR spectra demonstrated that montmorillonite was more vulnerable to acid or alkali spills compared to
kaolinite, and had good agreement with the optimized site density (Table 2). This was probably because H+ and
OH− could attack not only the edges but also the swollen interlayer of the montmorillonite8,34. The results indi-
cated that the extent of change in the surface properties resulting from an acid or alkali spill varied with the type
of clay mineral, and especially, an expandability should be carefully considered.

Interpretation of the change in Ka2 using first principle molecular dynamics results. Experimentally
derived Ka represented the average Ka of the reactive edge sites in the clay minerals. It is difficult to directly com-
pare the Ka derived from the titration experiment to those calculated from first principle molecular dynamics
(FPMD)35,36. In addition, the interpretation of pKa1, generally less than 0, optimized from the titration experiment
was inherently limited because the titration data at the pH near pKa1 were meaningless because of the dissolution
of the clay minerals. However, a previous study showed that the experimental Ka2, optimized by assuming one edge
site with a constant capacitance model, well matched the Ka calculated from FPMD37; thus, it is possible to interpret
pKa2 in terms of the theoretically calculated pKa. Liu et al. compared the optimized Ka values of kaolinite and mont-
morillonite from various titration experiments with the theoretical values calculated based on FPMD; these values
are summarized in Supplementary Table S237,38. The pKa values of three different kaolinite and montmorillonite
samples optimized from this study coincided well with the calculated and experimentally fitted values from other
references. This indicated that the edge sites detected from the titration experiments represented surface functional
groups as summarized in Supplementary Table S2.
The pKa2 of the untreated and acid-spilled kaolinite (5.49 and 5.94) was similar to calculated pKa of AlOH sites
of kaolinite (5.7), while that of the alkali-spilled kaolinite (6.34) was near the average value of calculated pKa of
AlOH and SiOH sites of kaolinite (6.3). However, considering little changes in kaolinite samples’ titration curves,
XRD, and FT-IR, the differences in pKa values were just theoretically generated during the optimization process.
In case of montmorillonite, the pKa2 of the untreated montmorillonite (7.32) was similar with the average value of
calculated pKa of SiOH and AlOH sites of montmorillonite (7.87), while that of the acid-spilled montmorillonite
(5.42) was near the calculated pKa of AlOH sites of montmorillonite (approximately 5.5). It indicated that acid
spills decreased SiOH sites of montmorillonite and this is consistent with FT-IR spectra results that acid spills
dissolved Si from the untreated montmorillonite and formed the cristobalite. Because theoretical pKa of edge sites
was calculated from pure clay minerals, the formation of cristobalite would make pKa of the acid-spilled mont-
morillonite further different from the untreated montmorillonite. Also, decrease in substituted octahedral sites
of the acid-spilled montmorillonite might affect pKa2, because isomorphic substitutions increased the adjacent
edge sites’ pKa37,38. In the case of the alkali-spilled montmorillonite, pKa2 (6.78) was between that of the untreated
and acid-spilled montmorillonite. Both SiOH and AlOH increased after alkali spills (Fig. 3); thus pKa2 changed
less than the acid-spilled montmorillonite. These results indicated that changes in pKa2 by acid or alkali spills was
primarily because of dissolution or formation of surface functional groups, which have different theoretical pKa
values.

Effect of acid or alkali spills on pH buffering capacity. The pH buffering capacity was the reciprocal of
the slope of the titration curve, and it was calculated from the following Equation (1):

(
pH buffering capacity at pHx = − TOTHpHx+0.1 − TOTHpHx /0.1 ) (1)
where, TOTHpH x (mol L ) is the total amount of proton added to the suspension of clay minerals during the
−1

titration until the suspension pH reaches a value of x. Because the initial pH of the suspension of all the clay
minerals ranged from 5.5 to 6.5, the pH buffering capacity at pH 5.5, 6.0 and 6.5 was calculated from the titration
curves predicted by using surface complexation modeling under 0.001 M NaNO3 condition (Fig. 4).

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70

pH buffer capacity [mmol kg-1 (pH unit)-1]

60

50

40

30

20 Untreated kaolinite
Acid spilled kaolinite
Alkali spilled kaolinite
10 Untreated montmorillonite
Acid spilled montmorillonite
Alkali spilled montmorillonite
0
5.5 6.0 6.5
pH

Figure 4. pH buffering capacity of three different kaolinite and montmorillonite samples at pH 5.5, 6.0, and
6.5. Open and cross-hatched bars represent kaolinite and montmorillonite, respectively, and black, red, and blue
bars represent untreated, acid-spilled, and alkali-spilled kaolinite or montmorillonite, respectively.

Acid or alkali spills slightly decreased the pH buffering capacity of the kaolinite at pH 5.5, 6.0, and 6.5 from
19.2, 17.6, and 14.6 mmol kg−1 to 17.6 or 18.2, 15.8 or 16.6, and 14.2 or 14.6 mmol kg−1, respectively. In the case
of montmorillonite, these spills increased the pH buffering capacity at pH 5.5, 6.0 and 6.5 from 37.7, 30.3 and
27.9 mmol kg−1 to 44.5 or 63.2, 35.9 or 56.0, and 32.7 or 55.8 mmol kg−1, respectively. Because the surface reaction
constants and site density determined the pH buffering capacity, the pH buffering capacity of montmorillonite,
of which the surface properties were greatly altered by the acid or alkali spills compared to those of kaolinite, was
more affected by these spills than kaolinite.
Acid or alkali spills do not result in meaningful changes in the pH buffering capacity of kaolinite, but, unex-
pectedly, increased the pH buffering capacity of montmorillonite. It indicated that acid or alkali spills do not
have an adverse effect on the pH buffering capacity of clay minerals, which is the indicator of soil functions,
after neutralization. However, in reality, soils contain not only clay minerals, but also organic matter; thus, the
pH buffering capacity of acid- or alkali-spilled soils could change in a different manner from that of a single clay
mineral alone. Organic matter is known as the most important component determining pH buffering23, and it
may have a pH buffering capacity 300 times higher than that of kaolinite39. Because acid or alkali spills would
decrease organic matter contents via desorption and dissolution14–16, these spills might cause a decrease in the
pH buffering capacity of acid- or alkali-spilled soils despite an increase in the pH buffering capacity of single clay
minerals. Nevertheless, the results of the pH buffering capacity of clay minerals in this study clearly show that
the pH buffering capacity was not deteriorated, but rather increased in montmorillonite after acid or alkali spills.

Conclusions
In this study, we investigated the change in surface properties of clay minerals due to acid or alkali spills and its
effect on the pH buffering capacity as an indicator of soil functions. Surface complexation modeling indicated
that acid or alkali spills did not significantly change the site density of surface functional groups and their surface
acidity constants in kaolinite. In contrast, acid or alkali spills greatly changed the site density and surface acidity
constants of montmorillonite. Acid spills dissolved isomorphically substituted octahedral cations and SiOH sites
in montmorillonite. In addition, alkali spills dissolved the quartz and cristobalite and edge sites such as AlOH and
SiOH sites were newly formed in montmorillonite. Regarding the pH buffering capacity of clay minerals, acid or
alkali spills did not have an adverse effect on it, but rather increased in montmorillonite. Soil generally contains
organic matter, which plays a significant role in pH buffering, and thus further research with field soil is needed
to delineate the effect of acid or alkali spills.

Materials and Methods

Preparation and characterization of clay minerals. KGa-1b kaolinite (Georgia) and SWy-3 montmo-
rillonite (Wyoming) were purchased from the Clay Minerals Society’s Source Clays Repository. All chemicals
used in this study were of extra pure or reagent grade. The clay minerals were prepared following a similar proce-
dure to the best practices for analyzing surface properties of montmorillonite reviewed by Duc et al.40–43. Thirty
grams of kaolinite and montmorillonite was dispersed in 1 L of deionized water with a specific resistance of 18.2
MΩ m (Milipore, Bedford, Ma, USA) for 4 h. Prior to the size separation, the pH value of the kaolinite suspen-
sion was adjusted to 9.5 by adding NaOH (98%, Daejung, Korea) to facilitate a dispersion. The <2-μm fraction
of each clay mineral was collected via centrifugation (119 g, 5 min). This fraction was washed with 1 M NaNO3
(99%, Daejung, Korea) and HNO3 (60%, Daejung, Korea) solution at pH 3 and the supernatant was decanted
after centrifugation. This decarbonating procedure was repeated until the supernatant pH reached 341,42,44–46. The
clay minerals were then collected via centrifugation and washed three times with 1 M NaNO3 solution to change
the clays to a Na+ form. Although three washing cycles with NaNO3 might not be enough to make clay minerals
homoionic47, this pretreatment was chosen to allow for closer comparisons to previous studies, which determined
clay minerals’ Ka and site density through surface complexation modeling30,44,48. Excess Na+ was removed by
washing five times with deionized water, and the final pH was in the range from 6 to 7. The collected clay minerals
were freeze-dried, and the clay minerals are referred to as untreated clay minerals.
The CEC of untreated kaolinite and montmorillonite, measured ammonium ion through the ammonium
acetate method49, was 44 and 832 mmol kg−1, respectively. The specific surface areas of the untreated kaolinite and

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montmorillonite, obtained using N2- Brunauer–Emmett–Teller (BET) analysis (ASAP2020, Micromeritics, USA)
through adsorption (32 points) and desorption (23 points) isotherms (see in Supplementary Fig. S4)50, were 12.10
and 33.75 m2 g−1, respectively. These values were used as parameters for the surface complexation modeling30,51–54.

Acid or alkali spill and neutralization. HCl (35%, Daejung, Korea) and NaOH were selected as the strong
acid and alkali, respectively, based on their frequency of chemical accidents and amount of use1,3. One gram of the
untreated kaolinite or montmorillonite was placed in a 50-mL conical tube and 45 mL of 5 M HCl or NaOH was
added to simulate an extreme acid or alkali spill situation. Whole reactions were conducted in a rotating shaker
at 25 °C and 40 rpm for two days. The suspension was centrifuged and the supernatant solutions were filtered
through a 0.22-μm filter (Whatman, UK). After acid or alkali spill experiments, the treated solutions were ana-
lyzed by using inductively coupled plasma optical emission spectrometry (ICP-OES, iCAP 7400, Thermo Fisher
Scientific, USA) to determine the dissolution of the major structural constituents of kaolinite and montmoril-
lonite such as Al, Si, Fe, and Mg.
Separated kaolinite or montmorillonite were washed with deionized water five times to remove excess salts
and dissolved ions. A neutralization process was needed because excess H+ and OH− remaining after washing
and decanting could affect the titration experiment. Thus, the washed kaolinite or montmorillonite were neutral-
ized by adding HNO3 or NaOH until the supernatant pH reached a neutral pH range. The suspensions were cen-
trifuged and decanted and then residual clay minerals were washed three times with 1 M NaNO3 to make them
homoionic. These clay minerals were washed five times with deionized water, and then freeze-dried. The concen-
trations of Al and Si in the suspensions were measured by ICP-OES to check the remaining ions’ concentration,
and they were below one mg kg−1. The whole experiments of acid or alkali spills and neutralization were carried
out in triplicates. The XRD analysis was conducted to analyze the mineral identity of the acid- or alkali-spilled
clay minerals. The CEC of acid- or alkali-spilled kaolinite was 4.7 cmol kg−1, while that of acid- or alkali-spilled
montmorillonite was 737 and 925 mmol kg−1, respectively. The specific surface area of the acid- or alkali-spilled
kaolinite was 13.60 and 14.14 m2 g−1, respectively, while that of the acid- or alkali-spilled montmorillonite was
34.88 and 19.32 m2 g−1, respectively (see in Supplementary Fig. S4).

Potentiometric titration. Potentiometric titration has been used to quantify the density of active reaction
sites of clay minerals and determine the surface acidity constants (Ka) of those sites25,26,43,44,46,54–61. The protona-
tion behaviors of three different kaolinite or montmorillonite (untreated, acid-spilled, and alkali-spilled) were
investigated using an automatic potentiometric titrator (G10S, Mettler-Toledo, Switzerland). Duc et al. recom-
mended the best experimental conditions for the titrations to analyze the acid-base properties of montmoril-
lonite42,43,62, and we adapted the procedure with some modifications as follows.
All titration experiments were performed within a pH range of 4–9 at 25 ± 1 °C under an N2-purging condi-
tion. Deionized water was boiled to remove CO2 before making clay suspensions and the base titrant. Kaolinite
(0.1 g) or montmorillonite (0.05 g) was dispersed in 50 mL of background electrolyte (NaNO3) solution, and the
suspensions were purged with N2 for 1 h to exclude CO2. The suspensions were continuously stirred and purged
with N2 during each titration. Titrations of each clay suspension were conducted at three different concentrations
of NaNO3 (0.1, 0.01, and 0.001 M) to investigate the effect of the background electrolytic concentration. Titrant
solutions (0.1 M HNO3 or NaOH), also purged with N2, were added to the suspensions as 5–10-μL increments
every 5 min, and the pH was automatically recorded. Previous research has demonstrated that a short time inter-
val between successive increments of titrant, generally less than 10 min, is reasonable to minimize mineral dis-
solution43,46,56,59,63. Drifts in the measured potential were less than 1 mV min−1 in all titration experiments. Two
independent titrations of each clay suspension, from initial pH to pH 4 and from initial pH to pH 9, were con-
ducted and combined to obtain one titration curve ranging from pH 4 to 9. This pH range was selected because
it is known that the dissolution of kaolinite and montmorillonite is negligible in this pH range44,57,58. In addition,
to check the reversibility of titration experiments, titrations from pH 4 to pH 9 were conducted at 0.01 M NaNO3
condition.

X-ray diffraction measurement. X-ray diffraction (XRD) pattern of the samples of kaolinite and mont-
morillonite was measured with a X-ray diffractometer (D8 ADVANCE with DAVINCI, Bruker, German) using
Cu Kα radiation with a λ of 1.5418 Å and a Lynxeye-XE detector operating at 40 kV and 40 mA at a scan rate
of 2.4° min−1 from 5° to 80°. The TOPAS Rietveld analysis of XRD patterns was used to quantify the content
of mineral components of kaolinite samples. Since it is not precise and difficult to quantify montmorillonite by
Rietveld analysis due to the stacking disorder64,65, the fraction of constituents was analyzed semi-quantitatively by
comparing the integrated intensities of the diffraction peaks of each constituents66.

Fourier-transform infrared spectroscopy. Fourier-transform infrared (FT-IR) spectroscopy was used

to investigate the mineralogical and chemical structure and active surface sites of clay minerals for surface acid-
ity31,32. Clay samples were dried at 110 °C overnight to minimize water adsorption. KBr pellets were prepared
by mixing kaolinite (1.5 mg) or montmorillonite (1 mg) with 240 mg of KBr powder at a pressure of 10 tons.
The FT-IR spectra of the pellets with kaolinite or montmorillonite were recorded using an FT-IR spectrometer
(Nicolet 6700, Thermo Scientific, USA) with 32 scans at a resolution of 4 cm−1 within the range of 400–4,000 cm−1.

Surface complexation modeling. A constant capacitance model with permanent negatively charged sites
on basal plane and variable charged sites on the mineral edges was chosen to model the surface properties of the
kaolinite and montmorillonite30,37,44. The former was referred to as basal sites, while the latter as edge sites. A
proton exchange reaction occurred on the basal sites of the clay minerals, while a protonation or deprotonation
reaction occurred on the edge sites of them. The least square fitting program FITEQL 4.0 was used to optimize
the site densities of the kaolinite and montmorillonite and their surface reaction constants from the titration

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experiment67. The CEC of the kaolinite and montmorillonite was used as the total site density of the kaolinite and
the basal site density of the montmorillonite, respectively25,30,44. Surface properties were optimized from titration
data at three different concentrations of background electrolyte (0.1, 0.01, and 0.001 M NaNO3). FITEQL failed
to converge without fixing the equilibrium constant of the kaolinite’s proton exchange reaction probably because
the titration curves of the kaolinite could be well described without considering the basal sites’ proton exchange
reaction. Thus, pKH of the kaolinite’s proton exchange reaction constant was assumed to be −2.9 (Table 2), which
is an averaged value from references55,68–70. Detailed descriptions of the surface complexation modeling used in
this study and the optimization process are explained in the Supplementary Information.

Data Availability
The datasets generated during and/or analyzed during the current study are available from the corresponding
author on reasonable request.

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Acknowledgements
This work was supported by Korea Environment Industry & Technology Institute through Subsurface
Environment Management Project (2018002450002). The authors would like to thank the Institute of Engineering
Research at Seoul National University for technical assistance.

Author Contributions
K. Nam directed this research and was the overall in-charge. I. Jeon and K. Nam planned and designed the
experiments. I. Jeon performed the experiments and analyzed the data. All authors wrote and reviewed the
manuscript.

Additional Information
Supplementary information accompanies this paper at https://doi.org/10.1038/s41598-019-46175-y.
Competing Interests: The authors declare no competing interests.
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Scientific Reports | (2019) 9:9878 | https://doi.org/10.1038/s41598-019-46175-y 10

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