Environmental Pollution 265 (2020) 114811

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

A feasibility study of Indian fly ash-bentonite as an alternative

adsorbent composite to sand-bentonite mixes in landfill liner*
Chandra Bhanu Gupt a, Sanandam Bordoloi a, b, Sreedeep Sekharan a, Ajit K. Sarmah c, *
a
Department of Civil Engineering, Indian Institute of Technology Guwahati, Guwahati, 781039, Assam, India
b
Department of Civil and Environmental Engineering, Hong Kong University of Science and Technology, Hong Kong Special Administrative Region
c
Department of Civil and Environmental Engineering, The Faculty of Engineering, The University of Auckland, Private Bag 92019, 1142, Auckland, New
Zealand

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

Article history: Multi-layered engineered landfill consists of the bottom liner layer (mainly bentonite clay (B)) upon
Received 23 January 2020 which the hazardous wastes are dumped. In current practice, sand (S) is mixed with bentonite to
Received in revised form mitigate the adverse effects of using bentonite alone in the liner layer. Incorporation of waste and un-
3 May 2020
utilized fly ash (FA) as an amendment material to B has been explored in terms of its hydro-mechanical
Accepted 12 May 2020
Available online 1 June 2020
properties, but not gauged its adsorption potential. Indian subcontinent primarily relies on the thermal
power source, and FA dumps have already reached its full capacity. The objective of this study is to
explore the adsorption characteristics of four B-FA composite mixes sourced within India, considering
Keywords:
Landfill liner
Pb2þ as a model contaminant. The effect of fly ash type, fly ash amendment rate and adsorbate con-
Bentonite centration was explored in the current study and juxtaposed with B-S mixes, based on 960 batch
Fly ash adsorption tests. Both B-FA and B-S mixes reached equilibrium adsorption capacity within 65 min. At
Sand higher adsorbate concentrations (commonly observed in the liner), B-FA mixes exhibited superior
Adsorption adsorption capacity, mainly one mixed with Neyvelli fly ash (NFA). The effect of higher amendment rate
Microstructure had little impact on the adsorption capacity at different concentration, but gradually decreased the
percentage removal of Pb2þ. The B-S mix showed a drastic decrease in percentage removal at higher
adsorbate concentration among all tested mixes. Systematic characterization including geotechnical
properties, microstructure and chemical analysis was also done to interpret the obtained results. Both
Freundlich and Langmuir models fitted the isotherm data well for all B-FA mixes. The maximum
adsorption capacity from the isotherm was correlated to easily measurable Atterberg limits by two
empirical relationships.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction waste and progresses downwards as “leachate” (Oman € and

The exponential increase in hazardous and municipal solid
waste (MSW) due to urbanization and increased population has
necessitated the construction of engineered landfills (Busch et al.,
2010; Naveen et al., 2017; Kumar et al. 2019). Multi-layered engi-
neered landfill consists of the liner layer on which the hazardous
wastes are dumped (Fig. 1) (Slack et al., 2007). The cover layer is
employed over the waste only after the landfill reaches its full ca-
pacity. During this stage, the waste layer is exposed to multiple
cycles of rainfall wherein the rainwater reacts with the hazardous
*
This paper has been recommended for acceptance by Philip Smith.
* Corresponding author.
E-mail address: a.sarmah@auckland.ac.nz (A.K. Sarmah).
Hynning 1993). Low permeable soil layer, having hydraulic con-
ductivity less than 107 cm/s is generally employed in liners to
restrict or delay the leachate migration to the groundwater table
(Shaikh et al., 2019). The bentonite clay (B) was employed due to its
rheological properties (fine-grained with high surface area and
negative charge), resulting in low permeability and high metal ion
adsorption (Xu et al., 2008; Amer et al., 2010). However, bentonite
liner is susceptible to shrinkage cracks upon drying, has low
compressive strength and expensive material to import where it is
not found locally (Sivapullaiah and Baig, 2011). Thus, there is a need
for finding an alternative liner material for amending the negative
consequences of using only bentonite and minimize its use, which
is a costly mined material.
The current demand for electricity from thermal power plants

https://doi.org/10.1016/j.envpol.2020.114811
0269-7491/© 2020 Elsevier Ltd. All rights reserved.
2 C.B. Gupt et al. / Environmental Pollution 265 (2020) 114811
Fig. 1. Overview and origin of fly-ash bentonite composites sourced from different parts of India.
(Fig. 1) in developing countries like India (70% in comparison to
other sources) has grown in the past few decades (Singh et al.,
2015; Goswami et al. 2020). Burning of coal in thermal power
plants results in the production of waste fly ash (FA), which is
dumped on land or transported to ash ponds (Asokan et al. 2004;
Sandeep et al., 2016; Sarode et al., 2010). Indian FA majorly contains
varying amounts of SiO2 (20e60%), Al2O3 (5e35%), Fe2O3 (10e40%),
CaO (1e12%) and MgO (0e5%) (Ahmaruzzaman, 2010; Shivpuri
et al., 2011; Sivapullaiah and Baig, 2010). It was reported that
only 60% of FA produced in India was utilized in sectors such as the
cement industry, geotechnical and transportation infrastructures
and agriculture (Yao et al., 2015). Ash deposits adjacent to the
thermal power plants are piling up rapidly and the problem of its
disposal is reaching an alarming state with limited disposal space.
FA is pozzolanic (can increase soil strength), cohesionless (resists
shrinkage), and has relatively high cation exchange capacity (CEC)
as compared to sand (Palmer et al., 2000; Sivapullaiah and
Lakshmikantha, 2004). In current practice, coarse-grained and
inert sand (S) has been mixed with bentonite to mitigate the
negative effects of using bentonite alone in the liner (Sivapullaiah
et al., 2000; Mukherjee and Mishra, 2019). Sand is getting cost-
lier, has negative effects of river dredging and its global resources
are dwindling as reported in current literature (de Leeuw et al.,
2010; Meng et al., 2018). Judging from the inherent properties of
FA and the need for bulk usage of the accumulating waste, it is
viable to explore the utilization of bentonite-fly ash (B-FA) mixes as
an alternate liner material.
Notable research has been done on bentonite-fly ash composite
as liner material in the past decade (Nhan et al., 1996; Hettiaratchi
et al., 1999; Phani Kumar and Sharma, 2004; Younus and Sreedeep,
2012). However, all of these studies focus majorly on the hydro-
mechanical assessment of the composite for liner applications.
Hettiaratchi et al. (1999) investigated the compressive strength,
tensile strength, flexibility, cracking potential of different fly ash-
bentonite composites and found the majority of them suitable for
liner materials. The inclusion of FA in bentonite decreased the
plasticity, swelling potential, optimum moisture content (OMC),
while increased the maximum dry density (MDD), which further
makes it suitable for liner material (Phani Kumar and Sharma,
2004; Singh et al., 2015). The hydraulic conductivity value also
ranges as per landfill liner material in multiple studies (Sivapullaiah
and Lakshmikantha, 2004; Younus and Sreedeep, 2012). However,
majority of these studies focused on the heavy metal retention
capacities of fly ash-bentonite composites as future scope to have a
holistic understanding as a liner material. Deka and Sreedeep
(2017) conducted batch adsorption tests on Indian fly ash-
bentonite samples based on 1:1 ratio of the two material and the
model contaminant was chosen as lead (Pb2þ). Pb2þ is a common
contaminant in MSW and sources out from batteries, and electronic
goods with a reported concentration in landfill at 400 mgL1
(Aucott, 2006). Pb2þ poses various health hazards (anemia, head-
ache, diarrhea and poisoning) leading to the kidney and brain
dysfunction, which is particularly true for Indian subcontinent (Das
et al., 2016; Das et al., 2018; Kushwaha et al., 2018; Goswami et al.
 C.B. Gupt et al. / Environmental Pollution 265 (2020) 114811 3

2018). In this context, Pb2þ adsorption of different fly ash-bentonite
mixes, its reaction kinetics, and the comparison with sand-
bentonite mixes warrant further evaluation.
The objective of this study is to explore the adsorption charac-
teristics of four B-FA composite mixes sourced from various loca-
tions in India, considering Pb2þ as a model contaminant. The effect
of fly ash type, fly ash amendment rate and adsorbate concentra-
tion was explored (ASTM C 618 2008a) in the current study and
juxtaposed with B-S mixes. Batch tests were conducted at varying
Pb2þ concentrations from 50 to 1050 mgL1. This was systemati-
cally performed by initially assessing the basic geotechnical prop-
erties followed by interpretation with respect to the chemical
characteristics and microstructural imaging. The obtained experi-
mental data on adsorption kinetics and adsorbate concentration
were quantified using different adsorption isotherm. Based on the
maximum adsorption capacity (qm) obtained from isotherm
models, an attempt was also made to explore a correlation between
qm of the tested materials with the easily measurable Atterberg
limits. This provides geo-environmental practitioners, a simple and
practical approach of estimating the range of adsorption expected
for fly ash-bentonite composites.
2. Materials and methods
mixes were measured in accordance with the ASTM D 4318 (ASTM,
2010). The plasticity index (PI), which is the difference between the
LL and the PL is used later in the study for correlation with
adsorption capacity. The cation exchange capacity (CEC) and spe-
cific surface area (SSA) were evaluated by the ammonium
replacement method (Chapman, 1965) and ethylene glycol mono-
ethyl ether (EGME) procedure (Cerato and Lutenegger, 2002),
respectively. The basic geotechnical, physical and chemical prop-
erties have been tabulated in Table 1. X-Ray Diffraction (XRD)
analysis was performed to determine the mineralogy of parent
materials (Rigaku, Model, Micromax-007HF). The step size, 2q
range and scanning speed was assigned at 0.03 , (3e70 ) and (20
2q/min), respectively. The minerals present were analyzed from the
obtained XRD response using Match software. The surface
morphology of the parent material, mixes and Pb2þ adsorbed mixes
were captured using field emission scanning electron microscopy
(FESEM)-EDX (Zeiss Sigma, Oberkochen, Germany). The surface
functional groups were identified from FTIR spectra by using the
Potassium bromide pellet method (PerkinElmer, Spectrum Two,
Waltham, MA). The chemical oxide composition of the parent
material and bentonite-fly ash composites were analyzed using X-
ray fluorescence (AXIOS, PANalytical, Malvern, UK) and shown in
supplementary section (Table A).

2.1. Physical, geotechnical and chemical characterization 2.2. Test plan and experimental investigations

The pulverized bentonite clay was obtained from Barmer mine
in Rajasthan (Fig. 1), India, while the fly ash was sourced from
various thermal power plants all over India, as tabulated in Table 1.
The particle-size gradation of bentonite and fly ash was conducted
as per ASTM D422-63 (ASTM, 2007) and shown in the supple-
mentary section (Fig A (a)). The specific gravity of the parent ma-
terial and mixtures were determined by using the density bottle
method (ASTM D854-1994). The consistency limits (in terms of
liquid limit (LL), plastic limit (PL) and shrinkage limit (SL) of soil
Batch adsorption study was performed according to ASTM D
4646 (2008b) guidelines for soil and sediments. For performing
the batch sorption study of FAs, B-FA, and B-S mixes, liquid to solid
(L/S) ratio of 20 was considered (ASTM D 4646 2008b). For
bentonite (B), L/S was 50 due to the formation of a thick gel-like
consistency at L/S equal to 20, which prevents proper interaction
of Pb2þ with the bentonite particles (Gupt et al., 2018). Batch
sorption study was performed under controlled pH of 5 (Gupt et al.,
2020) for comparing the adsorption potential of different materials.

Table 1
Physical properties of geo-materials used in this study.

Properties Material, source state, designation and property value

Barmer bentonite Farakka FA Neyvelli FA Badarpur FA Pond ash Sand

Rajasthan West Bengal Tamil Nadu New Delhi Uttar Pradesh Assam

B FFA NFA BFA PA S

Specific gravity 2.9 2.2 2.6 2.2 2.2 2.6

Particle size distribution (%)
Coarse sand (4.75e2 mm) 0 0 0 0 0 0
Medium sand (2e0.425 mm) 0 0 3 0 0 52
Fine sand (0.425e0.075 mm) 5 24 55 8 36 48
Silt (0.075e0.002 mm) 30 74 42 88 61 0
Clay (<0.002 mm) 65 2 0 4 3 0
Atterberg’s limits (%)
Liquid limit 300 e e e e e
Plastic limit 43 e e e e e
Shrinkage limit 10 e e e e e
Plasticity index 257 e e e e e
USCS classification CH e e e e e
Free swell index (%) 686 e e e e e
Total specific surface area (m2/g) 450 12.6 13.2 11.5 10.5 e
(EGME method)
CEC (meq/100 g) 53.7 1.9 10 1.4 1 e
pH (L/S ¼ 20) 9.2 10.5 11.5 8.0 8.5 e
Minerals present Montmorillonite Mullite Mullite Mullite Mullite
Kaolinite Quartz Quartz Quartz Quartz Quartz
Hematite
Illite Hematite Hematite Hematite Agragonite
Quartz Agragonite Agragonite Agragonite Anhydrite
Anhydrite Anhydrite Anhydrite
Calcium oxide
4 C.B. Gupt et al. / Environmental Pollution 265 (2020) 114811

This was done to avoid the precipitation of Pb2þ in the solution
which could take place in the range 8e11.5. Half volume of
deionized water was taken in a volumetric flask, and the required
amount of air-dried adsorbent was added and left overnight. The
pH of the solution was adjusted to 5 by adding 0.1M HNO3 and
0.1 M NaOH and shaking it for 2 h on a rotatory shaker. Any increase
in the pH of the solution was again adjusted to pH ¼ 5 followed by
shaking, and this process was repeated till pH gets stabilized to 5.
After that, the remaining half volume was filled with Pb2þ solution
of double the concertation to get the desired concentration of the
solution. The precipitation of Pb2þ associated with higher pH was
prevented by adopting the above procedure. Any further change in
the pH of the solution and associated precipitation was minimized
by adding 0.1 ml of acetate buffer of pH ¼ 5. The conical flask
containing the solution of sorbent and Pb2þ was kept on the
rotatory shaker at 200 rpm. After 24 h of shaking, the solution was
transferred into the centrifuge tube and centrifuged at 4000 rpm
for 10 min to separate the solid and liquid phase of the solution. The
separated liquid phase sample was collected using the pipette and
filtered through the Whatman grade 42 filter paper with the help of
a vacuum filtration unit. The concentration in the filtrate was
measured using the atomic absorption spectrophotometer (AAS) to
check the equilibrium concentration of the solution.
2.3. Adsorption capacity (qe Þ, percentage removal and adsorption
isotherms
The quantity of Pb2þ sorbed on the adsorbent surface was
calculated by Eq (1):

Fig. 2. Adsorption capacity vs contact time response of bentonite-fly ash mix and bentonite-sand mix.
 C.B. Gupt et al. / Environmental Pollution 265 (2020) 114811 5

Fig. 3. Adsorption capacities of B-FAs and B-S mixes.

   Two popular adsorption isotherm (Langmuir and Freundlich)

2þ Vl representing equilibrium sorption was used to model the obtained
Pb adsorption capacity; qe ¼ ðCi  Ce Þ x (1)
Ms data for understanding the sorption behavior of Pb2þ. The rela-
tionship between the quantity of metal ions sorbed on the adsor-
where qe ¼ sorbed amount per unit mass of sorbent in (mg.g1); bent surface and the corresponding equilibrium concentration of
Vl ¼ measured volume of solution used for the batch test (mL); metal cations in the aqueous phase is represented by the sorption
Ms ¼ the mass of adsorbent solid (g) used in the test. Ci and Ce are isotherm. The Langmuir isotherm (Eq. (3)) in its non-linear form
the initial and equilibrium concentration of the solution (mg. L1). was employed as follows:
The removal of Pb2þ in percentage form was determined using
Eq (2): qmax bCe
qe ¼ (3)
  1 þ bCe
Ci  Ce
Percentage Pb2þ removal ¼ x 100 (2) where Ce ¼ the equilibrium metal ion concentration remaining in
Ci
the solution (mg.L1); qe ¼ the metal ions sorbed per unit weight of
6 C.B. Gupt et al. / Environmental Pollution 265 (2020) 114811
Fig. 4. Comparison of adsorption capacities in (aec) mixes (B-FAs and B-S) at a particular amendment proportion and (d) parent amendments.
the adsorbent at equilibrium (mg.g1); b ¼ constant representing
adsorption energy (L$g 1) and qmax (mg$g 1) ¼ constant repre-
senting maximum adsorption capacity.
The Freundlich isotherm, which accommodates multi-layers of
adsorption sites on the solid and most suitable for assessing the
adsorption data at low and intermediate concentrations on het-
erogeneous surfaces, was adopted. The model is presented in its
non-linear form, as given by Eq. (4).
qe ¼ kf Cen
where, qe ¼ equilibrium sorbed concentration (mg g1); Ce ¼ the
equilibrium metal ion concentration remaining in the solution
(mg.L1); kf ¼ Freundlich’s coefficient (mg1n Ln kg1) and
n ¼ Freundlich’s exponent which determines the degree of
isotherm linearity.
3. Results and discussion
3.1. Elemental composition and microstructural characterization
Based on the Fourier-transform infrared (FTIR) spectrum of the
bentonite (supplementary section Fig. A (b)), the transmittance
band observed at 3600 cm1 for both B and FA was due to the
presence of structural OH groups, which makes it extremely hy-
drophilic (Hayati-Ashtiani, 2012). The peaks and stretching at
3600 cm1 decrease with the inclusion of FA and are lowest for
pond ash-bentonite mixture. There is an overtone of the bending
vibration observed at 1637 cm 1 indicating the presence of OH
deformation mode of water. Sharp peak seen at 1030 cm1 with
inflection near 775 cm1 and at 685 cm1 confirm the presence of
quartz minerals due to Si-O bonds (Xu et al., 2008). The presence of
Si-O-Si and Al-O-Si bonds were also reflected by vibrations at bands
along 469 cm1 and 534 cm1, respectively. These peaks gradually
diminish from parent bentonite to fly ashes (particularly for pond
ash). The Al-Al-OH bonds were confirmed for bentonite clay from
distinct peaks at 920 cm1 (Madejova  et al., 2002).
(4) FESEM images of the parent materials (i.e., 4 FAs, B and S) are
presented in Fig. B. All four FAs showed the presence of spherical
particles, which are usually hollow and may contain other
embedded spherical particles of a smaller size in their interiors
(Fernandez-Jime nez et al., 2005). These hollow spherical particles
are called the “cenospheres”, which has the potential to store heavy
metals (Fomenko et al., 2011). Bentonite (B) has flaky clay particles
in a dispersed state with an average diameter of less than 2 mm
confirming the presence of montmorillonite clay mineral of the
Smectite family (Mitchell and Soga, 2005). According to the FESEM
micrograph of sand, the particles were angular, rough-edged, and
incompressible solid. The composite morphology of FA-B mixes is
shown in Fig. C in the supplementary section. The individual flaky
and fine particles (less than 2 mm) of B uniformly engulf the FA at
lower mix ratios, thus providing enough sites for adsorption to take
place. This engulfment appears to gradually decrease when the FA
percentage is increased to 70.
The XRD pattern of B (supplementary section (Fig. D)) identified
montmorillonite as the predominant mineral, which favors high
 C.B. Gupt et al. / Environmental Pollution 265 (2020) 114811
metal adsorption (Bhattacharyya and Gupta, 2008), followed by
Kaolinite, Illite and Quartz minerals. For FA, the peaks correspond to
Mullite and Quartz, which are relatively inert, followed by Hematite
and Aragonite mineral having adsorption potential of its own
(Millero et al., 2001; Gimsing and Borggaard, 2007). Sand, however,
is primarily composed of inert quartz with practically low or
negligible adsorption potential.
3.2. Adsorption kinetics and adsorption capacity at varying
adsorbate concentrations
Fig. 2 shows the adsorption capacity and percentage removal
kinetics of Pb2þ for the B-FA and B-S mixes at 1000 mgL1 adsor-
bate concentration. The concentration of Pb2þ observed in the
leachate from different sources was reported to be varying in the
range of 50 mg/L to 1000 mg/L (Jang and Townsend, 2003; Dutta
and Mishra, 2016). Parent bentonite having extremely high CEC
(53.7 meq/100 g) and SSA (450 m2/g) reaches equilibrium
adsorption capacity almost instantaneously within 5 min. In gen-
eral, parent FA (except NFA-class C) requires 120e230 min to attain
equilibrium adsorption capacity (Alinnor, 2007; Mohan and
Gandhimathi, 2009). However, NFA exhibited comparatively
faster equilibrium adsorption within 7 min. The quick adsorption of
NFA was attributed to the higher CEC (9 times higher than other
FAs) and inherently high alkaline nature (pH ¼ 11.5) (Wang et al.,
2009). It was also noted that controlling the pH of the solution
for NFA was difficult and showed the tendency to increase. This
would also have contributed to the high adsorption exhibited by
Fig. 5. Comparison of percentage removal of B-FAs and B-S mixes for a particular amendment proportion (a) 30%, (b) 50%, (c) 70% and (d) parent material.
7
NFA.
For B-FA and B-S mixes, the adsorption process was found to be
relatively faster than parent FAs and reaches equilibrium adsorp-
tion capacity within 65 min. The trend indicates that the presence
of bentonite particles regardless of percentage amendment domi-
nates and attenuates the adsorption process. In terms of magni-
tude, NFA mixes showed higher adsorption capacity as NFA itself is
a good adsorbent. As the hydraulic conductivity of typical B-FA
mixes is extremely low within the range of (108-1010) cm.s1
(Sivapullaiah and Lakshmikantha, 2004; Younus; Sreedeep, 2012),
the contact time is sufficient to adsorb Pb2þ ions in field conditions.
A higher amendment of FA in bentonite resulted in greater Pb2þ
percentage removal. Moreover, the B-FA mixes showed higher
percentage removal (i.e., 70e95%) as compared to B-S mixes
(65e78%). The highest percentage removal was also observed for B-
NFA mixes in comparison to the other three B-FA mixes.
Fig. 3 presents the adsorption capacity of all parent soils and
mixtures with different concentrations of adsorbate (50e1025 mg.
L1). The adsorption capacity naturally increases with higher
adsorbate concentration for all parent materials, as reported in the
 and Hromada, 2013; Deka and Sreedeep,
literature (Melichova
2017; Gupt et al., 2018). The magnitude was highest for pure
bentonite and negligible for sand at all adsorbate concentrations.
There was no appreciable effect of amendment rates on the
adsorption capacity for different adsorbate concentration. The ef-
fect of amendment type was noticeable when the comparison was
made at the same amendment rate (Fig. 4 a-c). All amendments
(both B-FA and B-Sand) result in almost similar adsorption capacity
8 C.B. Gupt et al. / Environmental Pollution 265 (2020) 114811

at lower adsorbate concentrations (marked in blue). This may be Table 2

due to the availability of sufficient adsorption sites of the mixes at Freundlich and Langmuir isotherm model fitted parameters for B, FAs, S, B-FAs mixes
and B-S mixes.
lower concentrations. As the concentration of Pb2þ ions increase
(marked in red), the adsorption sites of B-S mixes are saturated, Materials Freundlich isotherm Langmuir isotherm
while B-FA mixes facilitate for more adsorption. Thus, the usage of Kf (mg1n Ln kg1) n R2 qm (mg g1) b (L mg1) R2
B-FA mixes is more efficient for metal adsorption at higher Pb2þ
B 5.57 2.57 0.99 43.29 0.04 0.93
concentrations commonly expected for landfill leachates FFA 0.75 3.04 0.97 7.54 0.01 0.83
(Wadanambi et al., 2008). Fig. 4d shows that pure NFA is more B-FFA30 1.76 2.39 0.97 18.25 0.02 0.90
effective in adsorbing Pb2þ ions as compared to other parent B-FFA50 1.38 2.37 0.97 17.43 0.02 0.98
B-FFA70 0.95 2.40 0.98 12.95 0.01 0.97
amendment materials. This higher adsorption capacity of NFA was
NFA 0.33 1.14 0.99 104.61 0.002 0.99
further validated by conducting Energy Dispersive X-Ray Analysis B-NFA30 0.88 1.83 0.97 22.54 0.01 0.95
(EDX) tests on two parent FAs (NFA and BFA) at 1025 mg. L1 B-NFA50 0.74 1.53 0.96 33.87 0.01 0.98
adsorbate concentration. The NFA adsorbs almost six-times more B-NFA70 0.70 1.44 0.96 37.84 0.01 0.98
Pb2þ as compared to BFA based on EDX mapping data BFA 1.04 3.71 0.98 6.04 0.02 0.80
B-BFA30 2.38 2.27 0.99 20.83 0.05 0.96
(supplementary section, Fig. E), which further indicates the efficacy
B-BFA50 2.74 2.82 0.98 17.74 0.05 0.96
of NFA as an adsorbent material. This is further evident from the B-BFA70 1.65 2.48 0.96 17.10 0.02 0.99
percentage of Pb2þ shown in the EDX results. PA 1.47 6.95 0.94 3.36 0.87 0.78
The percentage removal of Pb2þ decreases with an increase in B-PA30 2.30 2.34 0.99 20.53 0.04 0.94
B-PA50 2.77 2.92 0.99 15.98 0.07 0.91
the adsorbate concentration for all mixes, as shown in Fig. 5 (a-c).
B-PA70 2.32 3.31 0.99 13.11 0.04 0.90
This can be attributed to available adsorption sites of the mixes for S 4.3E-4 1.13 0.87 0.72 3.7E-4 0.88
Pb2þ to be adsorbed at lower adsorbate concentration. As the B-S30 0.35 1.65 0.99 22.55 0.003 0.97
concentration increases, the sites for adsorption diminishes and B-S50 0.31 1.63 1.00 20.15 0.003 0.99
this is particularly evident for mixes with high amendments. In the B-S70 0.71 2.61 0.98 8.90 0.011 0.97

case of 30% and 50% FFA amendment rates and adsorbate concen-
tration of 1025 mg. L1, the percentage removal was 80% and 72%,
respectively. This percentage removal was further reduced to 57% 3.3. Adsorption isotherms and relating adsorption capacity with
for 70% FFA amendment rate. The percentage removal of NFA was Atterberg limits
comparable to pure bentonite for all the adsorbate concentration
range, as shown in Fig. 5d. Fig. 6(a-d) shows the fitted Langmuir and Freundlich isotherm

Fig. 6. Freundlich and Langmuir isotherm model fitted to FAs, sand, B-FAs mixes and B-S mixes.
 C.B. Gupt et al. / Environmental Pollution 265 (2020) 114811
Fig. 7. Interrelationship of equilibrium adsorption rate with (a) Liquid limit and (b)
Plasticity index.
for the measured data for all mixes and parent materials. The ob-
tained modelling parameters for both isotherms are tabulated in
Table 2. It was observed from the regression coefficient that both
Freundlich and Langmuir isotherm model fitted well with the
measured data with reasonable accuracy (R2 > 0.95). However, for
parent FAs, Freundlich isotherm fitted better (R2 > 0.94) as
compared to the Langmuir isotherm model (R2 > 0.78). The ob-
tained maximum adsorption capacity (qm) from the isotherm was
used to correlate the Atterberg limits for B, B-FA and B-S mixes.
Fig. 7 presents the interrelationship of equilibrium adsorption rate
with liquid limit and plasticity index. The LL and PI of all mixes and
bentonite are reported in the supplementary section (Table B).
Apart from the current study, data points of B and B-FA mixes are
also plotted to explore whether any relationship exists between
adsorption potential of fine-grained soils and its Atterberg limits
(LL, Plasticity index (PI)). Based on the measured and literature data
points considering only divalent metal contaminants (Pb2þ, Zn2þ,
9
Cu2þ), an increase in Atterberg limits directly implies a high equi-
librium adsorption rate. This can be explained because an increase
in SSA (due to inherent mineralogy) directly increases the water
holding capacity, i.e., the liquid limit increases (Muhunthan, 1991;
Dolinar et al., 2007). A recent study by Spagnoli and Shimobe (2019)
co-related the inter-relationship between these two parameters
based on 60 datasets from literature and formulated an empirical
relationship with relative accuracy (R2 ¼ 0.7). Similarly, it is fath-
omable that an increase in available SSA can facilitate more sites for
adsorption. In geotechnics, the LL indicates the water content at
which there is a gradual transition of soil from plastic to liquid
consistency (Yong et al., 2012) and can be measured easily in both
field and laboratory. Two relationships (Eqs. (5) and (6)) are put
forward to predict the equilibrium adsorption rate ðqm Þ with
Atterberg limits (LL and PI) with R2 value ranging from 0.84 to 0.88.
 
LL
112:4
qm ¼ 5:3 þ 3:1e (5)
 
LL
48
qm ¼ 16:2 þ 0:1e (6)
The proposed equations are empirical, and hence caution should
be exercised while applying this with other cations. Furthermore,
the LL obtained in this study is based on only Casagrande method
(Mitchell and Soga, 2005).
4. Conclusions
The feasibility of Indian bentonite-fly ash (B-FA) mixes in com-
parison with conventionally used bentonite-sand (B-S) mix was
demonstrated for landfill liner applications by studying the
adsorption kinetics and capacity. Results showed that both B-FA
and B-S mixes reached equilibrium adsorption capacity within
65 min. In terms of magnitude, B-NFA mixes showed the highest
Pb2þ adsorption capacity among the tested mixes, which can be
attributed to the high CEC and pH of parent fly ash. This was further
verified using EDX measurements. Lower amendment rate of FA
(i.e., B-FA30) resulted in greater Pb2þ percentage removal. At lower
adsorbate concentrations up to 425 mg. L1, both B-FA and B-S
mixes, exhibited comparable Pb2þ adsorption capacity due to
available adsorption sites. However, due to almost saturated
adsorption sites for B-S mixes at higher adsorbate concentrations
(observed in the liner), B-FA mixes exhibited comparatively higher
Pb2þ adsorption capacity. Both the Freundlich and Langmuir
isotherm model fitted well with the measured data for B-FA mixes.
The obtained maximum adsorption capacity (qm) from the
isotherm was correlated to Atterberg limits (Liquid limit and Plas-
ticity index) by two empirical relationships.
The study further advocates the usage of waste fly ash with
bentonite as an effective adsorption medium for large scale appli-
cation in landfill liners. This limits the usage of expensive and
ecologically sensitive sand in liner materials while maintaining the
integrity of landfill liner adsorption requirements. Further study on
the adsorption potential of B-FA mixes is needed considering
different model contaminants. The proposed empirical correlation
between maximum adsorption capacity and Atterberg limits pro-
vides a quick and inexpensive method of estimating adsorption
efficiency in fine-grained materials.
Declaration of competing interest
The authors declare no competing financial interests.
10 C.B. Gupt et al. / Environmental Pollution 265 (2020) 114811
CRediT authorship contribution statement
Chandra Bhanu Gupt: Conceptualization, Data curation, Inves-
tigation. Sanandam Bordoloi: Investigation, Data curation, Writing
- original draft. Sreedeep Sekharan: Funding acquisition, Super-
vision, Writing - review & editing. Ajit K. Sarmah: Writing - review
& editing, Visualization.
Acknowledgment
The authors acknowledge the Department of Science and
Technology, India, for facilitating the funding of the current
research work vide Project No. SR/S3/MERC/0040/2011. The authors
further thank the Central Instrument Facility (CIF), Centre for the
Environment, Environmental Engineering Department at the In-
dian Institute of Technology Guwahati, for providing the necessary
support for completion of this work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.envpol.2020.114811.
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