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Soils and Foundations xxx (2017) xxx–xxx
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Swelling characteristics of soils subjected to acid contamination

Chavali Rama Vara Prasad a, P. Hari Prasad Reddy a,⇑, V. Ramana Murthy a,
P.V. Sivapullaiah b
a
Department of Civil Engineering, National Institute of Technology, Warangal, India
b
GITAM University, Bangalore, India

Received 7 October 2016; received in revised form 3 September 2017; accepted 6 October 2017

Abstract

The ever-increasing number of failures of industrial structures due to the heaving of acid-contaminated foundation soils has neces-
sitated a better understanding of soil behavior under changing and extreme environmental conditions. Thus, this paper attempts to
micro-mechanistically explain the swelling characteristics of soils contaminated with inorganic acids. Three soils with widely varying
physical and chemical properties, namely, natural black cotton soil and commercially available bentonite and kaolin clay, were selected
for the investigation. Special Teflon-made oedometer cells, which are entirely non-reactive to acid, were used to assess the swelling behav-
ior. The soils were inundated with two concentrations of sulfuric acid and phosphoric acid and allowed to swell. The results indicate that,
in montmorillonitic soils, the type of cation in the exchangeable complex plays a dominant role in governing the swelling behavior of
clays during acid contamination. The mineralogical changes due to cation exchange reactions, along with the partial mineral dissolution,
resulted in the acid-induced swelling in montmorillonitic soils. In the kaolin clay, the face-to-edge association of the particles due to the
adsorption of H+ by broken edges led to an increase in swelling along with mineralogical changes.
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Keywords: Acid; Montmorillonite; Kaolinite; Swelling; Mineralogy; Microstructure

1. Introduction behavior to some extent, anthropogenic processes severely

alter the engineering behavior of soils leading to progres-
Soil contamination has become one of the greatest con- sive structural failures. The growing rate of the acid con-
cerns for geotechnical engineers around the world as it tamination (pH < 1) of soils and the consequent effects
involves complex chemical reactions between soils and con- on the volume change behavior of these soils is reflected
taminants. Soil contamination can occur through natural in the number of reported failures of industrial structures
processes or through anthropogenic processes (Gratchev (Grant et al., 1974; Vronskii et al., 1978; Sridharan et al.,
and Towhata, 2013). Weathering processes, acid rain and 1981; Stephenson et al., 1989; Joshi et al., 1994;
acid rock drainage fall into the category of natural pro- Shekhtman et al., 1995; Assa’ad, 1998; Yamanaka et al.,
cesses (3 < pH < 7), whereas the accidental leakage or spil- 2002; Al-Omari et al., 2007; Parfitt et al., 2010). In some
lage of a variety of chemicals during transportation or instances, the cost to repair the structure exceeded the orig-
storage fall into the category of anthropogenic processes inal cost to build the structure (Izbash et al., 1989; Isaev
(pH < 1). Although natural processes can affect the soil et al., 1995). These structural failures have necessitated a
better understanding of soil behavior under changing and
Peer review under responsibility of The Japanese Geotechnical Society. extreme environmental conditions. Prompted by these case
⇑ Corresponding author at: Department of Civil Engineering, National histories, an attempt is made in the present work to study
Institute of Technology, Warangal 506004, India.

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0038-0806/Ó 2017 Production and hosting by Elsevier B.V. on behalf of The Japanese Geotechnical Society.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

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the ill effects and to elucidate the mechanism of the swelling the formation of such structures in an acidic environment
behavior of clays subjected to inorganic acid was verified by Wang and Siu (2006). The third mechanism
contamination. is the adsorption of anions by the soils in an acidic environ-
The existing literature suggests that notable changes in ment. Krebs et al. (1960) reported that the adsorption of
the mineral structure with the dissolution of octahedral sulphates and chlorides leads to a reduction in the liquid
cations can take place at high concentrations of acids limits of montmorillonite, whereas the adsorption of phos-
(Grim, 1953; Sokolovich, 1973; Mitchell, 1993; Mal’tsev, phates leads to an increase in the liquid limits. On a similar
1998; Gates et al., 2002; Komadel, 2003; Jozefaciuk and note, Sivapullaiah (2009) reported that the adsorption of
Bowanko, 2002; Tyagi et al., 2006; Onal, 2007; Panda phosphates leads to decreased compression indices of
et al., 2010; Komadel, 2016). Volume changes observed homoionic kaolinite and montmorillonite clays. The fourth
in soils subjected to acid contamination (pH < 1) in most mechanism is the changes in the diffuse double layer due to
field cases have largely been credited to mineralogical the replacement of exchangeable cations by hydrogen ions
changes. However, the studies carried out by most in an acidic environment. Gajo and Maines (2007) reported
researchers on soils have been limited to slightly acidic con- a significant reduction in the compressibility of bentonite
ditions (3 < pH < 6) in order to mimic the conditions in due to the collapse of the double layer. Subsequent to this,
natural systems (Kamon et al., 1997; Sunil et al., 2006; Gratchev and Towhata (2013) reported a remarkable
Gajo and Maines, 2007; Gratchev and Sassa, 2009; reduction in strength due to changes in the double layer.
Gratchev and Towhata, 2011; Gratchev and Towhata, The fifth mechanism is the neogenic formations.
2013; Gratchev and Towhata, 2015). Few studies have Shekhtman et al. (1995) reported that the formation of
reported on the volume change behavior of sulfuric acid- sulphate-based minerals, such as gypsum, halotrichite,
contaminated soils (Sivapullaiah et al., 2008; Sivapullaiah potash alums, soda alums, tamaruchite and melanterite,
et al., 2009; Sivapullaiah, 2015; Ponnapureddy et al., during sulfuric acid contamination leads to heave in soils.
2017; Hassanlourad et al., 2017), and the effect of phospho- Mal’tsev (1998) concluded that high swelling in soils con-
ric acid on the swelling behavior of soils has so far been taminated with acid solutions can be attributed to miner-
scanty. Until recently, phosphoric acid has been utilized alogical changes. On a similar note, Sivapullaiah et al.
as a stabilizing material to improve soils (Lyons and (2009) reported that the high induced swelling in black cot-
Mcewan, 1962; Ingles, 1970; Sokolovich, 1973; Ghazali ton soil subjected to sulfuric acid contamination is attribu-
et al., 1991; Medina and Guida, 1995; Eisazadeh et al., ted to mineralogical changes.
2012). However, considering the damage potential of phos- From the above review, it can be inferred that the vol-
phoric acid and its wide usage, the aim of the present work ume change behavior of soils is significantly affected by sev-
is to establish the mechanisms controlling the swelling eral mechanisms under acidic conditions. Predicting the
behavior of soils contaminated with phosphoric acid and volume change behavior of soils contaminated with highly
sulfuric acid. concentrated acids becomes a difficult task. In this study,
A brief review of literature suggests that the following therefore, the swelling behavior of sulfuric acid- and phos-
mechanisms may affect the engineering behavior of soils phoric acid-contaminated soils were evaluated with the
in an acidic environment. The first mechanism is the disso- help of mineralogical and micro-structural changes for a
lution of the mineral structure and the leaching of cations better understanding of the governing mechanisms of soils
from the soil. Sivapullaiah et al. (2008) reported that cation with distinct mineralogy in highly acidic environments.
exchange reactions lead to an increased swelling in calcitic
soil due to sulfuric acid contamination. Spagnoli et al. 2. Materials and methods
(2012) reported a notable increase in shear strength in the
acidic environment due to the dissolution of Al3+, which 2.1. Soils and solutions used
acts as a coagulant by increasing the internal resistance.
Liu et al. (2013) highlighted that the displacement of Three soils with widely varying physical and chemical
cations by hydrogen ions leads to a decrease in the liquid properties, namely, natural black cotton soil and commer-
limits and the swelling index of the three montmorillonitic cially available kaolin clay and bentonite, were selected for
soils. Gratchev and Towhata (2015) reported that the dis- this laboratory investigation. The expansive black cotton
solution of calcium carbonate from kaolinitic soils results soil (BCS), predominant with the montmorillonite mineral,
in higher liquid limits, plasticity indices and compression was collected by an open excavation from a depth of one
indices. Bakhshipour et al. (2016) reported that the leach- meter below the natural ground level at NIT Warangal
ing of iron and aluminum from the residual soil increases Campus, India. The commercially available green ben-
the Atterberg limits, the optimum moisture content and tonite (BT) was purchased from Vidhya Enterprises, Chen-
permeability, and decreases strength and the maximum nai, India and the commercially available white kaolin clay
dry density. The second mechanism is the changing of the (KT) was purchased from Godavari Mines and Minerals,
charge on the edges of the clay particles which results in Visakhapatnam, India. All the clays were oven dried and
the formation of more open and flocculated structures sieved through a No. 40 (425l) sieve prior to usage. The
(Olphen, 1991). The high compressibility of soils due to physical properties and chemical composition of the clays

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are presented in Tables 1 and 2, respectively. All the phys- contamination on the swelling characteristics of the soils.
ical properties of the soils were classified in accordance Special Teflon oedometer rings were made, which were
with the Unified Soil Classification System (USCS). The entirely non-reactive to acid. The soils were mixed thor-
procedure described by Cokca and Birand (1993) was used oughly with distilled water at the optimum moisture con-
to evaluate the cation exchange capacity of the basic soils. tent, corresponding to the maximum dry density, and
The chemical composition of the clays was evaluated with were placed in sealed plastic bags. The plastic bags were
the help of the X-ray fluorescence (XRF) spectroscopy placed in a desiccator for 24 h to attain a uniform moisture
technique. A Phillips PW 2404 X-ray fluorescence spec- content. Silicon grease was applied to the inner surface of
trometer was used for the XRF analysis. The grain size dis- the oedometer rings to reduce the friction during com-
tribution curves of the three clays are shown in Fig. 1. paction. The soil specimens were then compacted (static
Concentrations of sulfuric acid and phosphoric acid, in compaction) in oedometer cells (6 cm in diameter and 2
the range of 12–40 N, are used for different industrial pur- cm in height) to their maximum dry density and a height
poses, and when these acid solutions leak into the subsoil of 1.4 cm. The volume of the pore fluid used for all the soil
and get diluted, their concentrations may drop to a range specimens was about 500 ml and testing was carried out at
of 1–4 N (Sivapullaiah et al., 2009). Thus, solutions of dis- a room temperature of 27 °C. The prepared clay specimens
tilled water and 1 N and 4 N concentrations of commer- were inundated with distilled water and 1 N and 4 N con-
cially available sulfuric acid (Assay 98%) and phosphoric centrations of sulfuric acid and phosphoric acid solutions
acid (Assay 88%), respectively, were used as the pore fluids as the pore fluids. The swelling displacement readings were
in this study to mimic those conditions. measured using dial gauges until no significant changes in
displacements were observed. The final swelling displace-
2.2. Atterberg limits ments, along with the original heights of the specimen,
were used to calculate the percentage of swelling in the ver-
Soils in batches of 400 g were mixed with various con- tical direction. In a significant number of cases, the exper-
centrations of acid solutions (solid:solution, 1:2.5) and iments were repeated twice to check the reproducibility of
placed in sealed plastic bags which were stored in a the results. The representative soil samples collected at
desiccator for a period of 500 h. The liquid limits were the end of the oedometer tests were oven dried for 24 h.
determined by the cone penetration method (ASTM The dried samples were manually pulverized into fine pow-
D4318-10) and the plastic limits were obtained by the 3 der using a mortar and pestle and allowed to pass through
mm thread method. a No. 200 sieve (75 lm). The fine powder was then ana-
lyzed using an X-ray diffraction analysis and scanning elec-
2.3. One-dimensional free swell tests tron microscopy tests to identify the mineralogical and

One-dimensional tests were conducted according to

ASTM D4546-A (2014) to investigate the effects of the acid

Table 1
Physical properties of soils used.
Property Bentonite Kaolin Black
clay cotton soil
Specific gravity 2.31 2.65 2.63
Liquid limit (%) 252 52 60
Plastic limit (%) 67 27 18
Plasticity index (%) 185 25 42
Clay, <2 mm (%) 67 21 26
Silt, 75–2 mm (%) 33 79 41
Fine sand, 425–75 mm (%) – – 33
USCS soil classification CH CL CH
Cation exchange capacity (meq/100 g) 56.95 5.62 37.5
Maximum dry density (kN/m3) 13.3 14.8 16.5
Optimum moisture content (%) 29.8 27.3 16.6 Fig. 1. Grain size distribution curves of soils used.

Table 2
Chemical composition of soils used (in percentages).
Soil SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O TiO2 P2O5 MnO SO3
Bentonite 38.2 25.7 21.5 5.7 3.7 1.18 0.25 2.16 0.36 0.50 0.12
Kaolin clay 34.5 49.0 6.5 2.3 5.3 0.034 0.17 1.22 0.15 0.17 0.11
Black cotton soil 43.6 22.8 14.7 7.3 7.5 0.255 0.63 1.71 0.28 0.47 0.14

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morphological changes that may have occurred due to the

acid contamination.

2.4. X-ray diffraction tests

The powder X-ray diffraction technique was used to

assess the mineralogical changes induced by the acids in
the soils during contamination. The X-ray diffraction anal-
ysis of the contaminated soil samples was carried out with a
PANanalytical X-ray diffractometer. The dried powder
samples were scanned between two theta values of 6–70°
with a step size of 0.02°. The X-ray Tube, operated at 60
kV and 55 MA, uses an accelerator ultra fast detector.
The qualitative identification of minerals was conducted
using X’pert high score plus software based on a database
provided by the Joint Committee of Powder Diffraction
Data Service (PCPDFWIN, 1999).
Fig. 2. Swelling behavior of bentonite inundated with different pore fluids.
2.5. Scanning electron microscopy

Scanning electron microscopy tests were performed to concentration of acids. Equilibrium swelling of about
examine the significant role of the morphological changes 67% and 50% was attained by the bentonite with 1 N and
in the swelling behavior of the acid-contaminated soils. A 4 N H2SO4, respectively. Similarly, the time-swelling curve
TESCAN VEGA 3LMU microscope with a conventional of the bentonite exhibited swelling of about 76% and 61%
tungsten-heated cathode, having live stereoscopic imaging with 1 N and 4 N H3PO4, respectively. The acids replace
using 3D beam technology, was employed to obtain high the commonly found exchangeable cations with hydrogen
resolution images of the soil microstructure. The dried soil ions (Mitchell 1993; Gratchev and Towhata 2011). The
samples were mounted onto double-sided carbon tape dominant sodium cation (Na+) in bentonite gets replaced
glued to the flat surface of the SEM stub and then coated by hydrogen (H+) ions. Although both are monovalent
with a thin layer of gold for 120 s using the SC7610 mag- cations, the ionic radius of the sodium (1.02 Å) ions is lar-
netron sputter coater prior to scanning. The SEM images ger than that of the hydrogen ions (0.012 Å), and the swel-
used in the study were selected from numerous images of ling due to Na+ as exchangeable cations is much greater
the selected soil samples taken at different magnifications. than that due to H+ because of the larger ionic radius of
The micrographs shown are those with the magnifications the hydrated Na+ ions. This process leads to a decrease
that best demonstrate the distinctive microstructure of in swelling in both of the acid solutions. Moreover, the
the soils. observed swelling in bentonite with sulfuric acid is less than
that of phosphoric acid. This is attributed to the lower ten-
3. Results and discussions dency of the phosphoric acid to release H+ ions compared
to the sulfuric acid. A significant reduction in the liquid
3.1. Effect of acid contamination on swelling behavior of limit of the bentonite upon interaction with the acids pro-
bentonite vides more support to the reduction in swelling (Fig. 3).
The XRD patterns of the bentonite inundated with
The results of oedometer free swell tests on bentonite water and acid solutions are shown in Fig. 4. Bentonite is
inundated with water and different concentrations of acid dominant with sodium montmorillonite along with kaolinite
solutions are presented in Fig. 2. The time-swelling curve and quartz. The formation of a new mineral, gypsum, was
of the bentonite inundated with water exhibits an equilib- observed in the bentonite with 1 N H2SO4 and 4 N
rium swelling of about 116%. Bentonite, predominant with H2SO4. Gypsum is a calcium sulphate hydrate mineral.
exchangeable sodium ions, has highly developed diffuse ion As stated earlier, the hydrogen ions replace the exchange-
layers that promote inter-particle repulsion and a dispersed able cations of the clay mineral. The replaced cations com-
particle arrangement. The high percentage of swelling upon bine with the sulphate anions present in the solution and
inundating with water is recognized to be a manifestation result in the synthesis of a new sulphate mineral. The for-
of the diffuse double layer repulsive forces acting between mation of calcium sulphate minerals also contributed to
the clay particles which are directly related to the concen- the swelling observed in the bentonite. Shekhtman et al.
tration of sodium ions in the exchange complex (1995) reported that the formation of sulphate-based min-
(Sridharan et al., 1990). In this study, the bentonite exhib- erals, such as gypsum, halotrichite, potash alums, soda
ited a reduction in swelling due to the acid contamination, alums, tamaruchite and melanterite, during sulfuric acid
and the swelling decreased with an increase in the contamination leads to heave in soils. However, the volume

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(1960), the propensity of phosphate to react with aluminum

would enhance such a replacement in the case of phospho-
ric acid. These reactions may lead to the formation of
wavellite. Previous studies have indicated that the forma-
tion of aluminum phosphate minerals due to exchange
reactions can partially reduce the swelling in soils
(Sokolovich, 1973). The morphological changes in the ben-
tonite inundated with different pore fluids are presented in
Fig. 5. The dispersed undulating film-like microstructure
can be evidenced from the micrograph of the bentonite
with water (Latifi et al., 2016). The undulating film-like
microstructure of bentonite is modified into flake-like
structures upon interaction with sulfuric acid which clearly
highlights the new mineral formations. Conversely, the
micrograph of the bentonite with phosphoric acid only
Fig. 3. Variation in Atterberg limits of bentonite treated with different exhibited more aggregation of the clay particles. In ben-
pore fluids.
tonite, therefore, cation exchange reactions and mineralog-
ical changes can be considered as the dominant processes
governing the swelling behavior of bentonite in highly
acidic environments.

3.2. Effect of acid contamination on swelling behavior of

kaolin clay

The results of oedometer free swell tests on kaolin clay

with different pore fluids are shown in Fig. 6. Kaolin clay
exhibits an equilibrium swelling of about 3% with water.
The small number of exchangeable cations present at the
edges of sheets of the kaolin clay structure do not allow
the clay to swell (Foster, 1954). In the absence of interlayer
cations in kaolinite, interlayer swelling, as can be observed
in montmorillonite, is not possible (Wang and Siu, 2006).
In contrast to bentonite, kaolin clay shows an increase in
swelling with both acid solutions, and the swelling increases
with an increase in the concentration of acids. Kaolin clay
exhibits swelling of about 23% and 41% with 1 N and 4 N
H2SO4, respectively. Similarly, it exhibits swelling of about
22% and 36% with 1 N and 4 N H3PO4, respectively. The
charges on the edges of the kaolin clay particles are seen
to become increasingly positive in an acidic environment
due to the adsorption of hydrogen ions (Olphen, 1991;
Gratchev and Towhata, 2015). The face-to-edge (F-E)
Coloumb attraction prevails as the edge sites become pos-
itive (Wang and Siu, 2006). This process increases the vol-
ume of the kaolin clay which results in high swelling.
Fig. 4. X-ray diffraction patterns of bentonite inundated with different
pore fluids.
Furthermore, the observed swelling in the kaolin clay with
sulfuric acid is higher than that with phosphoric acid. As
stated earlier, this is due to the lower tendency of the phos-
increase due to the sulphate-based minerals was nullified in phoric acid to release H+ ions compared to the sulfuric
the bentonite as a reaction to the cation exchange, thus acid. An increase in the liquid limit with increasing concen-
playing the prevailing role in controlling the swelling trations of both acids supports the observed swelling
behavior. Similarly, the bentonite with 4 N H3PO4 exhib- results for the kaolin clay (Fig. 7).
ited peaks pertaining to wavellite, whereas no mineral The XRD patterns of kaolin clay inundated with differ-
changes were observed in the bentonite with 1 N H3PO4. ent pore fluids are presented in Fig. 8. The kaolin clay pri-
Wavellite is an aluminum phosphate hydroxide hydrate. marily consists of kaolinite along with calcite and ankerite.
The H+ ions can replace the exchangeable aluminum The dissolution of calcite and ankerite, along with the
cations by mass action. And, according to Krebs et al. formation of gypsum (calcium sulphate hydrate) and

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Undulating filmy
microstructure Flake like microsttructure

(a) (b))

ke microstrructure
Flake lik
(c) (c )

Flocculated or aggrregated
microsttructure

Flo
occulated
microstructurre

(d) (ee)

Fig. 5. SEM images of bentonite inundated with (a) water, (b) 1 N H2SO4, (c) 4 N H2SO4, (d) 1 N H3PO4, and (e) 4 N H3PO4.

aluminum sulphate hydroxide hydrate minerals, is observed hydrogen phosphate hydrate mineral. Heave in soils due
in kaolin clay with 1 N and 4 N H2SO4, respectively. Sim- to the formation of calcium sulphate/aluminum sulphate
ilarly, the dissolution of calcite and ankerite, along with the and calcium hydrogen phosphate minerals have been
formation of monetite and brushite minerals, is observed reported in the existing literature (Stephenson et al.,
with 1 N H3PO4 and 4 N H3PO4, respectively. Monetite is 1989; Joshi et al., 1994; Sivapullaiah, 2015). The dissolu-
a calcium hydrogen phosphate and brushite is a calcium tion of calcite during acid contamination results in the

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Fig. 6. Swelling behavior of kaolin clay inundated with different pore

fluids.

Fig. 8. XRD patterns of kaolin clay interacting with different pore fluids.

changes in kaolin clay due to acid contamination. Sul-

phate-based minerals are characterized by needle-like crys-
tal structures (Azam, 2003), whereas flower-like
microstructures support the formation of the brushite min-
eral (Brundavanam et al., 2014).

Fig. 7. Variation in Atterberg limits of kaolin clay treated with different 3.3. Effect of acid contamination on swelling behavior of
pore fluids. black cotton soil

breaking of the carbonate bonds between clay particles The results of oedometer free swell tests on black cotton
forming ‘‘loose” structures with larger voids which also soil inundated with water and acid solutions are presented
leads to greater swelling and compressibility (Imai et al., in Fig. 10. The figure depicts that the black cotton soil
2006). An increase in swelling of the kaolin clay subjected inundated with water showed a swelling of about 21%.
to acid contamination can also be attributed to the dissolu- The lower swelling of the black cotton soil compared to
tion of calcite, ankerite and aluminum along with the for- the bentonite can be attributed to the presence of calcium
mation of sulphate and phosphate minerals. SEM montmorillonite along with calcite and microcline minerals
micrographs of kaolin clay treated with water and acid in the soil (Fig. 12). The degree of dissociation is not great
solutions are shown in Fig. 9. The kaolin clay exhibited lay- enough in the calcium montmorillonite to cause a significant
ered crystalline structures that appeared much like pages in degree in swelling (Foster, 1954). The black cotton soil
a book with hexagonal crystal (Brady and Well, 1996). The attained an equilibrium swelling of about 24% with 1 N
layered crystalline structures modified into fibrous needle- H2SO4. A marginal increase in swelling was observed in
like microstructures upon interaction with 1 N H2SO4. the black cotton soil with 1 N H2SO4 compared to that
The microstructure of kaolin clay severely transformed of swelling in the black cotton soil with water. However,
into needle-like structures with 4 N H2SO4, whereas as a significant increase in swelling of about 44% was
more flocculated face-to-edge structure/flower-like observed in the black cotton soil inundated with 4 N
microstructures were formed upon interaction with 1 N H2SO4. Similarly, the black cotton soil exhibited swelling
and 4 N H3PO4, which highlights the microstructural of about 4% and 29% with 1 N and 4 N H3PO4,

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Layered crystalline Fibrous needle

microstructure cture
microstruc
(a) ( b)

Needle like
Face-to-ed
F ge floccul ated
microstructure
microstruct
m ure

(c) (d))

Face-to-edge
d/flower likee
flocculated
microstruc
m ture (e))
(e)

Fig. 9. SEM images of kaolin clay interacting with (a) water, (b) 1 N H2SO4, (c) 4 N H2SO4, (d) 1 N H3PO4, and (e) 4 N H3PO4.

respectively. As discussed earlier, the acids replace the com- replace the divalent Ca++ ions. As the ionic radius of the
monly found exchangeable cations around the clay parti- calcium (0.99 Å) ions is larger than that of the hydrogen
cles by hydrogen ions. In black cotton soil, the dominant ions (0.012 Å), the swelling due to Ca++ as exchangeable
cations of Ca++ gets replaced by H+ ions. As hydrogen cations will be much more than that due to the H+ ions,
ions are monovalent ions, two H+ ions are required to because of the larger diameter of the hydrated Ca++ ions.

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Fig. 10. Swelling behavior of black cotton soil inundated with different
pore fluids.

Thus, the replacement of Ca++ by H+ ions led to a decrease

in swelling of the black cotton soil with 1 N H3PO4. How-
ever, with other concentrations of acid solutions, an
increase in swelling was noticed. This swelling can presum-
ably be attributed to the mineralogical changes. The liquid
limit test results (Fig. 11) were not in exact coincidence
with the swelling results at lower concentrations of acids, Fig. 12. XRD patterns of black cotton soil interacting with different pore
which makes it difficult to support the swelling behavior fluids.
in the case of natural soil.
The results of XRD tests for the black cotton soil inun-
montmorillonite transformed into alunogen with 4 N
dated with water and acid solutions are shown in Fig. 12.
H2SO4. High swelling in soils due to the formation of the
The black cotton soil treated with water showed peaks per-
alunogen mineral in the soil contaminated with sulfuric
taining to calcium montmorillonite along with quartz, cal-
acid was reported by Sivapullaiah (2015). Mineral transfor-
cite and microcline as their major minerals. The black
mations with a single peak pertaining to brushite were
cotton soil with 1 N H2SO4 revealed peaks pertaining to
observed with 1 N H3PO4, whereas considerable changes,
new minerals, gypsum and bassanite, along with the disso-
such as the formation of brushite, merlinoite and dawsonite,
lution of calcite, whereas the black cotton soil with 4 N
were observed in the black cotton soil with 4 N H3PO4.
H2SO4 showed alunogen and bassanite minerals along with
Changes in the cation exchange complex of the black cot-
the dissolution of calcite. The peak pertaining to
ton soil and the subsequent cation and anion interactions
lead to new mineral formations. The transformation of
microcline may lead to the formation of merlinoite. Merli-
noite is a mineral of the zeolite group. The formation of
brushite and merlinoite contributed to the increase in swel-
ling with 4 N H3PO4. Volume changes in the soils, due to
the formation of brushite and zeolite, are extensively
described in scientific literature (Joshi et al., 1994;
Chavali et al., 2017). These neogenic formations are attrib-
uted to the increase in swelling in the black cotton soil due
to acid contamination. Fig. 13 illustrates the morphological
changes in the black cotton soil inundated with water and
acid solutions. The micrograph of the black cotton soil
with water depicts an undulating film-like structure
(Latifi et al., 2016). The black cotton soil with the undulat-
ing filmy particle microstructure exhibited a lath-like euhe-
Fig. 11. Variation in Atterberg limits of black cotton soil treated with
dral crystal structure and a needle-like structure with 1 N
different pore fluids. H2SO4 and 4 N H2SO4, respectively. Furthermore, the

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10 C. Rama Vara Prasad et al. / Soils and Foundations xxx (2017) xxx–xxx

Lath like
euhedral crys
stals

Undulating filmy
microstructure

Needle like
microstructure

Flow
wer like
mic
crostructure
Flocculated
microstructure

Fig. 13. SEM images of black cotton soil interacting with (a) water, (b) 1 N H2SO4, (c) 4 N H2SO4, (d) 1 N H3PO4, and (e) 4 N H3PO4.

black cotton soil with 1 N H3PO4 exhibited a flocculated aluminum was observed in the kaolin clay and the black
microstructure, whereas flower-like brushite structures cotton soil with higher concentrations of sulfuric acid,
were evidenced in 4 N H3PO4. which exhibited relatively high magnitudes of swelling.
Overall, acid-induced swelling is evident in all the soils. No significant mineral structure dissolution or consequent
The mineralogical evaluation indicated that the dissolution mineralogical changes were observed with the phosphoric
of the mineral structure along with the leaching of acid. Different forms of calcium sulphate, aluminum

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 C. Rama Vara Prasad et al. / Soils and Foundations xxx (2017) xxx–xxx 11

sulphate, calcium phosphate and aluminum phosphate Technology, Government of India, under Fast Track
minerals were found in all three soils, which resulted in Scheme for Young Scientist [Grant No. SB/FTP/ETA-
the swelling of the soils. Severe morphological changes 412/2012].
were observed in the black cotton soil contaminated with
acids followed by kaolin clay and bentonite. The transfor-
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