Indian Geotech J (October 2021) 51(5):1069–1077
https://doi.org/10.1007/s40098-020-00464-w
TECHNICAL NOTE
Evaluation of Sequential Extraction Procedure (SEP) to Validate
Binding Mechanisms in Soils and Soil-Nano-Calcium Silicate
(SNCS) Mixtures
K. Kotresha1 • Syed Abu Sayeed Mohammed2
Arif Ali Baig Moghal5
Received: 13 April 2020 / Accepted: 28 October 2020 / Published online: 25 November 2020
 Indian Geotechnical Society 2020
Abstract The soils in hazardous waste sites contain heavy
metals which would leach into groundwater by various
biotic and abiotic processes and eventually pose a threat to
human health by contaminating the drinking water. In order
to understand pattern of heavy metal leachability, the field
conditions can be simulated by adopting various types of
sequential extraction methods. In this study, an attempt was
made to evaluate the effectiveness and selectivity of a
sequential extraction process to determine heavy metal
binding mechanisms in soils and soil treated with nano-
calcium silicate (NCS). A five-step sequential extraction
(SE) procedure was adopted on four soils obtained from a
& Arif Ali Baig Moghal
reach2arif@gmail.com; baig@nitw.ac.in
K. Kotresha
kotresh3@gmail.com
Syed Abu Sayeed Mohammed
abubms@gmail.com; abusayeed.cv@hkbk.edu.in
P. F. Sanaulla
sanahkbk@gmail.com
Afzal Ali Baig Moghal
afzalalibaig@gmail.com
1
Senior Research Fellow (SRF), Department of Civil
Engineering, HKBK College of Engineering, Bengaluru
560045, India
2
Department of Civil Engineering, HKBK College of
Engineering, Bengaluru 560045, India
3
Department of Chemistry, HKBK College of Engineering,
Bengaluru 560045, India
4
Department of Civil Engineering, Aalim Mohammed Salegh
College of Engineering, Avadi, Chennai 506004, India
5
Department of Civil Engineering, National Institute of
Technology, Warangal 506004, India
• P. F. Sanaulla3 • Afzal Ali Baig Moghal4 •
sanitary dumpsite, automobile and battery work units from
different localities of Bangalore and a steel plant com-
missioned at Toranagallu, Bellary, India. The soils were
mixed with NCS at varying range of 0.5 to 2% by dry
weight of the soil. The NCS-amended soils were spiked
with cadmium (Cd2?), nickel (Ni2?) and lead (Pb2?) in
concentrations to the tune of 3000 mg/kg. It has been
observed that there seems to be a gradual increase in
binding ability for the targeted heavy metals when soils
were amended with NCS compared to untreated soils. This
binding phenomenon was attributed to the presence of
exchangeable ions, carbonates, oxides of iron and man-
ganese, organic matter and residual fractions. It was
noticed that the residual fractions in soils amended with
NCS attenuated maximum quantity of metal ions with Pb2?
at 21.46%, followed by 18.8% for Cd2? and 9.25% for
Ni2? compared to untreated case. Further, this work
highlights the role of residual fraction in enhancing the
retention capacity of soils by encapsulation of higher
concentrations of contaminants. The current study corrob-
orated the fact that the addition of NCS aids in the better
encapsulation of selected heavy metal ions.
Keywords Cadmium  Lead  Nano-calcium silicate 
Nickel  Sequential extraction
Introduction
Contaminants in soils due to anthropogenic activities and
their transport to various layers and finally reaching the
groundwater have been a major issue from the past few
decades [1]. However, the use of heavy metals in industrial
activities would inevitably cause contamination of soil,
thereby threatening the hygiene of our food and damaging
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our health. The heavy metals accumulated in soils get
transported to human food chain through plants and ani-
mals [2–4]. India has more than 10 proclaimed brown
fields, and an analysis of the major contaminants at these
sites reveals mostly heavy metals such as chromium, cad-
mium, nickel and lead along with other contaminants. The
soils in different layers are damaged beyond their capacity
to remediate and require herculean efforts to retrieve them
to their natural state. This necessitates a comprehensive
study on such heavy metal-contaminated sites. Many
conventional techniques to remediate such sites based on
physical, chemical and biological treatment methods have
been in use and have also met with some success
depending on the degree of pollution [5].
But many a times it has been found that the treatment
methods would become ineffective or may not be efficient
due to factors such as economic viability and being
effective only in short term and would lose its efficacy in
the long run, and hence, the remediation exercise would
become futile. This makes us to evolve new methods of
remediation and find better materials which are robust and
can stand vagaries of time. Also an in-depth understanding
of the various processes taking place during the interaction
of these heavy metals with soils and materials used as
amendments to enhance the soil properties needs to be
studied.
Mohammed et al. [6] have worked extensively on the
use of various amendments to attenuate heavy metals.
Lime, cement, fly ash and nano-based compounds were
used as admixtures to enhance properties of soils to retain
heavy metals. Sorption, leaching and desorption studies
were carried on tropical and semi-arid soils. Irrespective
of the materials used, it has been found from extensive
literature that initially the contaminant is retarded and
over a period of time the active ingredients of soils react
and release the contaminants back into the environment
[7]. This is a matter of concern as permanent sorption in
the interstices of soil does not take place. Hence, any
remediation becomes a short-term solution. In this work,
three heavy metals commonly found at brownfields such
as Cd, Ni and Pb have been used to understand their
behavior under different environmental settings. The
simulations include natural environment, localized small
urban setup for percolation of heavy metals, a sanitary
dumpsite having a contaminant load of more than
10 years and a massive industrial setup having very high
potential for pollution [8].
It is intended that the results from this study will provide
new insights into the behavior of Cd and Pb. It has been
reported in the literature that Pb and Cd are subjected to
periodic and prolonged saturation in soils. Soils from mines
are highly enriched in Cd and Pb. Numerous studies on
mining-affected river systems have shown that sorption and
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Indian Geotech J (October 2021) 51(5):1069–1077
co-precipitation of metals with Fe and Mn oxides are
among the most important chemical processes of contam-
inant (Pb, Zn, Cd and Cu) binding in stream sediments and
alluvial soils. It has been reported that smelter activities
play a predominant role in severely contaminating local
soils and downward migration of Pb occurs at a rate of 0.3
to 0.36 cm/year. Similarly, we were able to conduct caged
TCLP (toxicity characteristics leaching procedure) on Cd,
Ni and Pb and found that it was 3.1812 and 0.3445 cm/
year, 1.145 and 0.072 cm/year, 1.14063 and 0.100 cm/year
for raw and amended soils, respectively, for an initial
concentration of 3000 mg/kg, which is in confirmation of
the work conducted by Wang et al. [9]. Hence it can be
deduced that for extreme concentrations of heavy metals it
is imperative to monitor their behavior.
Generally, sorption studies are carried out to determine
the maximum retention capacity of soils and soil amend-
ments, but it has its own disadvantages, many a times the
classical sorption deals only with isotherms and basically
classified as homogeneous or heterogeneous sorption. But
in reality, particularly for soil systems it is more complex
than simple sorption and hence many complexation theo-
ries are available. Researchers now work basically on these
and also simulate the field condition using many related
simulation software. All these do have certain limitations,
and many new equations are being developed to address
these issues. These techniques seem to be too tedious and
hence to quickly assess the sorption taking place and at
different phases of soils. In this study, a part of a major
project was undertaken to ascertain the use of NCS-based
soil amendment and understand the behavior of heavy
metals in terms of sorption, leaching, desorption and
mechanistic analysis using sorption isotherms, Lagrangian
first- and second-order equations, simulations using visual
MINTEQ application software, concluding it with
sequential extraction procedure.
Sequential extraction procedure (SEP) has been applied
to evaluate the contribution of assorted phases in the
sorption of soils, which are classified into 5 phases. A
comparison is made for use of nano-calcium silicate (NCS)
[10], as a soil amendment and the difference it makes in
providing stable sorption more so to encapsulate in the
interstices of soil permanently. In this study, soils prone to
high degree of heavy metal pollution were selected and
SEP tests were conducted so as to ascertain their behavior
in different phases, the speciation of heavy metals and their
fate in each phase has been studied. The main aim of this
work was to quantify the amount of heavy metal available
in each phase and its significant contribution in retention;
emphasis is given to 4th and 5th phase as they are relatively
stable phases and contribute for permanent retention. These
phases represent encapsulation of heavy metals in the
interstices of soil. The use of a nano-admixture brings in a
Indian Geotech J (October 2021) 51(5):1069–1077
controlled condition; hence, in this study the advantage of
using a controlled and uncontrolled condition on soils and
its effects on heavy metals retention at different phases
needs to be evaluated [11, 12].
Sequential extraction procedure is a very tedious
experimental work to be carried out very carefully, and
each phase has to be continued from the previous phase.
Hence, many researchers in their respective works tend to
do this as a small work to justify their major experimental
data obtained. But in this paper the authors have tried to
specifically analyze the different aspects involved in the
SEP process and tried to document the observations. An
attempt has been made to understand the contribution of
various phases as it has not been documented before. The
current work is a step toward understanding the relative
contributions from each phase so that relevant standards
can be framed.
Furthermore, the fundamental mechanisms of immobi-
lization of heavy metals that control long-term properties
assume importance. Typically, extraction tests are applied
to investigate the binding mechanisms of heavy metals in
treated soils. However, a single extraction method alone is
insufficient to explain the intrinsic reactions over a wide
range of external environments. Therefore, sequential
extraction has been proposed to study the evolution of
speciation of selected metal ions. Sequential extraction is a
sequentially selective extraction method which uses dif-
ferent chemicals to react with metal ions. During sequential
extraction, various soluble chemical products are formed at
different stages and released into the aqueous environment.
Even though the SEP is used frequently as a descriptive
tool in the study of contaminated soils, little consideration
has been given to the dynamics of heavy metal binding
with time, across the spectrum of different soil fractions.
To cite an example in leaching or extraction experiments
that is synonymous to a particular leaching scenario, over a
prolonged period of exposure to contaminated soil to a
given solvent, a question can be formulated as to which of
the operationally defined fractions contribute to the ‘‘sol-
uble’’ portion of metal during dissolution, and what are the
dynamics between the metal fractions that are being lea-
ched. To date, there exists a gap in the literature concerning
the changes in the distribution of heavy metals in con-
taminated soils [13–15].
Materials and Methods
Soil Samples
Soil sampling was done from selected sources based on the
anthropogenic sources they were subjected to.
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• The campus of HKBK (13020 26.0200 N and 77 370
40.2200 E), which was relatively clean and did not have
any known history or source of contamination, hence-
forth referred to as S1.
• A locality of South Bengaluru called Mavalli
(12570 1900 N, 77350 2200 E) soil in the vicinity of
automobile and battery service center was collected, in
herein notated as S2.
• Dumpsite of Bengaluru City is called Mavallipura
dumpsite (13040 59.000 N/77430 35.400 E); in order to get
a general representative sample having commingled
waste, soils from a sanitary dumpsite were selected
which had a dumping history of more than 10 years,
herein notated as S3.
• Jindal South West steel plant, Toranagallu, Bellary
District, Karnataka, India (15150 27.6700 N and
76360 43.7000 E), soil samples in the vicinity of a major
industrial complex; particularly, a steel plant was
selected and samples were collected, herein notated as
S4.
Background concentrations of selected heavy metals in
the obtained soil samples were determined using ASTM
D3987 leaching test [16]. These soils were divided into two
batches representing uncontrolled and controlled condi-
tions, in which soils without any amendment were taken as
uncontrolled case having only soil. For controlled condi-
tion (S-NCS) 1.5 g of NCS was mixed with 1 kg of soil. It
was found that for all the soils obtained the concentration
of heavy metals Cd, Ni and Pb was within permissible
limits. A number of heavy metals are available in the actual
field condition, but due to brevity and limitations, an
exhaustive review of the literature was done and it was
found that Cd, Ni and Pb are found in most of the field
conditions and the sites selected in the present study had
these elements in dominant form. Automobile repairs and
battery works unit, a sanitary dump site and JSW steel
plant near Bengaluru region were the sites of study.
Earlier a number of studies were carried out by the
authors, and it was found that for all the cases the range of
heavy metal taken was within 1000 mg/l. In the present
case when samples were drawn from or potentially con-
taminated sites, leaching tests for onsite samples showed
that the heavy metals were within the permissible limits.
But due to the projection that over a period of time the
concentration of contaminants would increase due to more
industrial activities, a contaminant concentration of
3000 mg/l was selected so as to understand the behavior of
soil samples at such high concentrations and termed as the
worst-case scenario. According to toxicity standard charts
of heavy metal ions, for Cd, a contamination level of
0–5 mg/kg is considered low, 5–20 mg/kg is considered
medium, 20–100 mg/kg is considered high, and beyond it
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is considered extreme. Similarly, for lead 0–100 mg/kg is
considered low, 100–500 mg/kg is considered medium;
500–1000 mg/kg is considered high; and beyond it is
considered extreme. The threshold limits of nickel are
similar to that of lead [9, 17].
In this study, the authors have considered worst scenario
and fixed concentrations around 3000 mg/kg. These
extreme values have been earlier reported by Wang et al.
[9] and Aponte et al. [17]. There are many brownfields in
India wherein such concentrations have been reached.
Heavy metals Cd, Ni and Pb with 3000 mg/kg concentra-
tion were spiked individually to all the eight soils and left
for curing. Samples were drawn for conducting tests only
after it had undergone a curing of 90 days. All samples
were taken in triplets to have repeatability and repro-
ducibility. Samples post curing were taken for conducting
the predetermined tests so as to simulate field conditions
and to address a major concern that reliability and efficacy
of amended soils starts decreasing over a period of time
due to desorption of sorbed heavy metals [12]. The phy-
sico-chemical properties of soils were evaluated relying on
ASTM standards and are provided in Table 1. All the soils
were classified as high plasticity clays (CH) as per USCS
classification [16, 18–22].
Chemicals Used
Heavy metals cadmium, nickel and lead used in this study
were procured as analytical grade nitrate salts supplied by
Merck India ltd, Mumbai, India. Standard solutions of
cadmium nitrate, nickel nitrate and lead nitrate were pre-
pared using double-distilled water. The concentration of all
the heavy metals in triplet was determined by using an
atomic absorption spectrophotometer (AAS) model Ana-
lyst A 400 supplied by PerkinElmer, USA.
Nano-Calcium Silicate (NCS)
Nano-calcium silicate (NCS) was synthesized by employ-
ing a patented method of authors (Indian patent 2765/CHE/
2015). To describe briefly calcium and silica were com-
bined using combustion synthesis. The physical properties
of NCS nanopowder had a density of 890 kg/m3, with a
surface area of 0.000595 m2/Kg measured using BET
method [22]. The TEM image as shown in Fig. 1 gives the
grain size of the nanomaterial.
Method to Extract Heavy Metals From Different
Soil Phases
The following extraction procedure(s) was used to extract
sorbed heavy metals from soils under five different phases
or sequences [23–28].
Determination of Heavy Metals Bound to Soluble
and Exchangeable Phase (F1)
In this heavy metal ions embedded to soil extracted by
adding a solution of MgCl2 (1.0 M) maintaining a pH of
7.0, 20 mL of this solution was added to soil. This mixture
was subjected to mechanical shaking for a period of 1 h at
a temperature of 20 C. The solution was subjected to fil-
tration, and the filtered solution was sent for analysis of
heavy metal content. This gives the amount of heavy
metals bound to soluble and exchangeable phase. The
residue left was sent for the next phase and is termed as
bound to carbonates (F2).
Determination of Heavy Metals Bound
to Carbonates (F2)
A separate mixture combining 20 mL of sodium acetate
(1 M) with a pH adjusted to 5 using hydroxyl ammonium
chloride solution was added to the residue from previous

Table 1 Properties of sourced soils

Property S1 S2 S3 S4 Relevant standard

Color Red Red Red Red

Specific gravity 2.6 2.6 2.7 2.6 ASTM D854 (2014) [18]
Liquid limit (%) 30.5 34.1 28.6 38.1 ASTM D4318 (2017) [19]
Plastic limit (%) 17.3 18.4 16.2 20.4
Plasticity index (%) 13.3 15.7 12.1 16.7
Classification (USCS) CH CH CH CH ASTM D2487 (2017) [20]
Optimum water content (%) 16.8 17.2 16.3 15.2 ASTM D1557 (2012) [21]
Maximum dry density (kN/m3) 17.9 19.8 18.1 15.8

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Fig. 1 TEM image of nano-calcium silicate (@ 100 nm resolution)
phase. This mixture to the residue is keep on shaking for
4 h at normal room temperature. Filter this mixture and the
filtrate was analyzed for heavy metals. This gives the
concentration of heavy metals bound to carbonates.
Determination of Heavy Metals Bound to Iron
and Manganese Oxides (F3)
Residue from F2 step was transferred to a mixture of
50 mL NH2OH (0.04 M), HCl and 25% hydroxyl ammo-
nium chloride solution. This mixture was subjected to
shaking for 5.5 h maintaining a temperature of 96 ± 3 C.
This mixture was cooled prior to filtering and collection of
residue. The solution was analyzed for heavy metal content
bound to iron and manganese oxides.
Determination of Heavy Metals Bound to Organic
Matter (F4)
Extracting liquid was first prepared by adding 7.5 mL
HNO3 (0.02 M) with 12.5 mL of H2O2 (30% solution)
which is transferred into a mechanical shaker and shake for
2 h maintaining a temperature of 85 C with a pH of 2.
After cooling this solution, a mixture comprising of
12.5 mL of ammonium acetate (3.2 M) with HNO3 (20%)
solution was added. Shake for 30 min, filter the solution
and the residue was sent for next step. The filtered solution
was analyzed for heavy metals bound to organics.
1073
Determination of Residual Fraction (F5)
Three batches of 2.5 g residue were taken quantitatively
from F4 phase and were dissolved in aqua regia consisting
of 7 mL HCl (10 M) and 2.3 mL HNO3 (15.8 M) in a
digestion vessel. Reflux conditions are maintained by
increasing the temperature and maintaining it for 2 h.
Dilutions were made with 2% HNO3 (v/v) up to 50 mL.
This was subjected to centrifuging at 5000 rpm for 15 min.
The supernatant was analyzed for metals. The residue
present in the centrifugal tubes was rinsed with deionized
double-distilled water (20 mL volume) followed by repe-
tition for 15 min prior to discarding the supernatant.
Percentage of heavy metal present in five different soil
phases was estimated by applying the following formula
Metal available in soil ð%Þ
Mass of contaminant in supernatant solution ðCl VL Þ
¼  100
Initial mass of contaminant in soil ðCs Ms Þ
ð1Þ
CL and Cs represent contaminant concentration in
supernatant (mg/l) and in soil (mg/kg), VL-supernatant
volume (in L) and Ms–mass of dry soil (in kg) [6]. The
blank tests were carried out on virgin soils, and the
concentrations of targeted metal ion(s) were found to be
below-detectable levels (BDL). Moreover, the
concentrations of targeted metal ions ‘Cd, Pb and Ni,’
were also found to be below-detectable levels.
Results and Discussion
Four soils representing various categories of pollution were
selected, and extensive sorption and leaching studies were
conducted. It was found that soils in combination with NCS
showed higher sorption efficiency and leaching tests over
long periods proved that NCS if used as an amendment in
small quantities makes the soil stable and the contaminants
are permanently encapsulated in the soil interstices. In
order to quantify the actual sorption mechanism taking
place and the behavior of heavy metals in the different
components of soil, in other words the significance of metal
species in various phases of soil sequential extraction
testing becomes essential. Also the selection of four soils
was done in order to represent contaminated field condi-
tions, and decontamination of these soil was done using an
amendment in the form of NCS. Considering brevity, the
soils are referred as S1, S2, S3 and S4 for uncontrolled
conditions which represent virgin condition, automobile
and battery waste-contaminated condition, sanitary dump-
site and steel mill plant site, respectively. These soils when
amended with NCS are considered as S1-NCS, S2-NCS,
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S3- NCS and S4-NCS and compartmentalized as controlled

conditions [28].
Sequential extraction procedure (SEP) gives a reliable
method of distinguishing various metallic entities embed-
ded in the interstices of soil, and it may be due to the
chemicals and is arbitrarily attracted to a definite phase
which may dissolve a phase completely. This technique of
sequential extraction provides useful knowledge on the
initiation of metal species, their basis of occurrence, be it
physical, chemical and biological data available, its ability
to be mobile and its capacity to transport metals in soils
and amended soils. Different forms of heavy metals
directly affect the biological toxicity, migration and
mobility of heavy metals in nature [29, 30]. Furthermore,
the stability of heavy metals in physical and chemical
speciation follows the sequence (from greatest to least),
residue fraction [ bound to organic matter frac-
tion [ bound to Fe–Mn oxides fraction [ bound to car- Fig. 3 Speciation of Cd, Ni and Pb in S2 for uncontrolled and
bonates fraction [ exchangeable fraction. Generally, controlled cases
water-soluble, ion-exchanged and carbonate-bound heavy
metals are active and may easily migrate to groundwater
and soil, while the organically bound state, the iron-man-
ganese oxidation state and the residual heavy metals are
relatively stable under rain, snow or acid rain conditions
[31].
The experimental data are presented in Figs. 2, 3, 4 and
5, the variation of extraction percentage for different pha-
ses is shown in Fig. 2 for S1 and S1-NCS combination, and
similarly, Figs. 3, 4 and 5 represent the data for S3 and S4
combinations. All the results are depicted in percentage
metal ion retained in all the five phases. Phase 1 (F1)
showcases weakly acidic condition; Phase 2 (F2) and Phase
3 (F3) constitute reducing and oxidizing conditions,

Fig. 4 Speciation of Cd, Ni and Pb in S3 for uncontrolled and

controlled cases

respectively. The dynamism of metals reduces propor-

tionally as the extraction process progresses in different
phases from F1 to F5 [32].

Phase 1 (F1) and Phase 2 (F2) Fractions

The soluble and exchangeable fraction consists of metals

Fig. 2 Speciation of Cd, Ni and Pb in S1 for uncontrolled and
controlled cases
which are precipitated or co-precipitated with carbonate. In
this component, the metal ions get precipitated or co-pre-
cipitated with carbonate and remain as soluble. The
exchangeable fractions carbonates are loosely bound and
are in an unstable state which are influenced by changes in
surrounding environmental conditions. The acid-soluble

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Fig. 5 Speciation of Cd, Ni and Pb in S4 for uncontrolled and
controlled cases. F1—soluble and exchangeable, F2—bound to
carbonates, F3—bound to Fe/Mn oxides, F4—bound to organic
matter, F5—bound to soil matrix/residual
fraction generally contains a comparatively less percentage
of the total metal content. The mobility of metals is rep-
resented by an exchangeable fraction. Among the three
metals studied, Pb gave the lowest exchangeable fraction,
whereas the highest exchangeable fraction was observed
for Cd, the percentages of all the three metals were in the
range of 4 to 16%, S1 had the highest range, whereas all the
other soils from S2 to S4 had a range of 3–8%, but in
controlled condition, the addition of NCS further reduced
to a range of 0.8–4% for all the soil mixtures from S1-NCS
to S4-NCS. Retention in these phases has occurred for a
temporary period.
Phase 3 (F3) Bound to Oxides of Manganese
and Iron
This fraction represents the conduct of metal ions when
subjected to reducing conditions for the metal ions bound
to iron and manganese oxides, which are released in these
conditions. These oxides are found in plenty in soils and
sediments and hence play a crucial role in intake of metals.
Nickel was found to be maximum in this phase followed by
lead and cadmium for all the soils and soil mixtures con-
sidered (see Figs. 2, 3, 4 and 5 for comparison). It was also
observed that in the uncontrolled conditions, soils have
been active in retaining more ions than compared to con-
trolled soils which may be due to redox reaction by calcium
and silicate ions in NCS. The Fe and Mn ions of soils have
become stable precipitates as iron and manganese
hydroxides.
1075
Phase 4 (F4) Bound to Organic Matter
Organic fractions are less mobile and do not release the
bound metal ions. These fractions have stable high
molecular weight humic substances and release metals over
long periods in very small amounts. Therefore, the metal
ions remain with oxidizable fractions for a very long time.
The degradation of organic matter due to various other
reasons such as oxidizing conditions may lead to release of
these bound metal ions; therefore, an oxidation process
releases the metal ions connected to this phase. These
organic substances have high selectivity for divalent
cations than monovalent. Since all the three elements
considered in this study are divalent, their release amounts
were of the order Cd \ Pb \ Ni for most of the soils. It
was also observed that there has not been any marked
difference or improvement in retention capacity between
uncontrolled and controlled conditions which may be due
to the constant organic fraction in both the cases as NCS
does not have any organic compound and hence does not
contribute for retention [32].
Phase 5 (F5) Residual Fraction Bound to Soil Matrix
In order to ascertain that metal ions are permanently
embedded in the soil matrices is the most desirable attri-
bute of remediation technique; hence, the residual fractions
would indirectly give an indication of the efficacy of var-
ious soil amendments used and it can be observed in all the
figures. In the residual fraction bound to soil matrix, it was
found that soils under controlled conditions had retained
maximum amount of metal ion on an average of 21.16%,
20.18% and 12.53% for Pb, Cd and Ni, respectively, and in
the same sequence uncontrolled soils on an average had
retained 5.88%, 4.23% and 2.18%. This shows that con-
trolled soils had increased retention by 72%, 79% and 82%
than uncontrolled soils.
Diffusion of heavy metals takes place in the crystal of
soil particles; this enhances encapsulation and takes place
due to the addition of NCS. It may be due to aggregation of
soil particles, and the Ca and Si present enclose immobile
salts. These salt products react with the atmospheric CO2
and moisture present in the vicinity. This reaction gener-
ates products similar to pozzolanic cement, pressure and
hydraulic control. As a result, the heavy metal gets into Ca
and Si immobile salts and entraps itself permanently in an
inert state. This is the most promising phase as the intro-
duction of controlled conditions in soils enhances its
retention capacity by the phenomenon as discussed above,
and this is the only phase where maximum permanent
retention takes place with very high efficiency [32]. This
study truly dissected the actual retention mechanism in
soils under uncontrolled and controlled conditions and
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1076
gives us a fair idea as to how the addition of a nanocom-
pound contributes to improvement in the attenuation of
heavy metals. Since our aim was to enhance the maximum
retention to take place in the F5 phase, by looking at the
data available in all the figures from Figs. 2, 3, 4 and 5, the
following highest ranking of soil mixtures has been ranked
as S2NCS [ S3NCS [ S1NCS [ S4NCS. This implies
that soil at local urban setup has better permanent retention
capacity followed by the soil at the sanitary dumpsite,
whereas the soil at the steel plant with a rural setup gave
the least retention capacity. The mechanism for entrapment
in the soil NCS mixtures can be thought of by the accu-
mulation of soil particles that bind and enclose calcium and
silica-affiliated immobile salts. Metal complexes diffuse
into the crystalline reticulum of soil particles leading to
efficient entrapment of heavy metals in the comportment of
NCS. It is able to produce immobile salts in the presence of
moisture and atmospheric carbon dioxide leading to prop-
erties similar to pozzolanic cement. Interactions of
nanoparticles with soil minerals are likely to be a function
of particle size, shape and surface properties (specific
surface area and surface charge); grain size, the porosity of
sand, mineral content (ionic strength and ionic species) and
moisture in soil are also equally important.
Conclusions
Four soils exhibiting different properties were selected, and
extensive leaching studies were conducted after spiking
them with selected metal ions in the presence of NCS. It
was found that all four soils retain heavy metals in the short
term and leached them in the long term due to difference in
binding energies of contaminants. In this study sequential
extraction process was used to evaluate the fate of metals
present in different matrices of soil and to quantify the
amount of metals encapsulated. The following specific
conclusions are drawn from the study:
1. S1 was a virgin soil which gave better retention,
whereas S2, S3 and S4 were contaminated soils rep-
resenting different contamination routes. Based on
initial tests it was found that the three contaminants
considered Cd, Ni and Pb were within permissible
limits under natural conditions for these soils, and
hence to undertake this study, soils were artificially
spiked with 3000 mg/kg of contaminants to represent
worst-case scenario for all the soils.
2. The soluble and exchangeable fraction F1 and bound to
carbonates F2 gave the least values for heavy metal
retention and is classified as a temporary phase.
Among the three metals studied, Pb gave the lowest
exchangeable fraction, whereas the highest exchange-
able fraction was observed for Cd. Under the F3 phase
123
Indian Geotech J (October 2021) 51(5):1069–1077
it has been observed that in the uncontrolled condi-
tions, soils have been active in retaining more ions than
compared to controlled soils. The calcium and silicate
ions in NCS have reduced respective oxidizing and
reducing capacity in soils. The Fe and Mn ions of soils
have become stable precipitates as iron and manganese
hydroxides after reacting with the active components
of NCS.
3. It was also observed that for the F4 phase there has not
been any marked difference or improvement in reten-
tion capacity between uncontrolled and controlled
conditions; they are almost equal; it may be that the
organic fraction remains the same in both the cases
derived only from soils since NCS does not have any
organic compound and therefore does not contribute
for retention. The residual fraction (F5) had the highest
retention for controlled conditions and retained to the
tune of 70%–80% more than uncontrolled conditions
due to encapsulation of metal ions in the interstices of
soil matrix.
4. The order of retention between different phases
corroborated well with the literature and followed the
sequence (from greatest to least) residue frac-
tion [ bound to organic matter fraction [ bound to
Fe–Mn oxides fraction [ bound to carbonates frac-
tion [ exchangeable fraction. The addition of NCS
encapsulated the heavy metals and retained them
permanently in the interstices of soil matrices. It was
found that among selected five fractions, the residual
fraction retained more than 50% of metals for soils
under controlled conditions than uncontrolled soils
proving the efficacy of NCS encapsulation.
Acknowledgements The authors would like to thank Science and
Engineering Research Board (SERB), Department of Science and
Technology (DST), Govt. of India, Project No. SR/S3/MERC/0111/
2012, for providing financial support to carry out work. The authors
would like to thank the reviewers for their constructive comments
which helped the cause of the manuscript.
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