Materials Today: Proceedings 38 (2021) 1088–1101

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Facile synthesis of halloysite-bentonite clay/magnesite nanocomposite

and its application for the removal of chromium ions: Adsorption and
precipitation process
V. Masindi a,b, S. Foteinis c, M. Tekere b, M.M. Ramakokovhu d
a
Magalies Water, Scientific Services, Research & Development Division, Erf 3475, Stoffberg Street, Brits 0250, South Africa
b
University of South Africa, College of Agriculture and Environmental Sciences, Department of Environmental Sciences, P. O. Box 392, Florida 1710, South Africa
c
3School of Engineering, Institute for Infrastructure and Environment, University of Edinburgh, Edinburgh EH9 3JL, United Kingdom
d
Tshwane University of Technology, Institute of NanoEngineering Research, Department of Chemical, Metallurgical and Materials Engineering, Private Bag X680, Pretoria 0001,
South Africa

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

Article history: Here we report the synthesis of halloysite-bentonite clay/magnesite nanocomposite, using ball milling
Received 21 May 2020 and calcination. It was identified that the synthesized nanocomposite enjoys the synergistic properties
Received in revised form 31 May 2020 of both materials, i.e. clays and magnesite, and hence was assessed in terms of chromium ions removal
Accepted 5 June 2020
from real tannery wastewater. To identify the optimum conditions for chromium ions removal the one
Available online 7 July 2020
factor-at-a-time (OFAT) method was applied in the design of the batch experiments. The examined
parameters include mixing time, dosage, concentration, and pH, while state-of-art analytical techniques
Keywords:
were used. Specifically, to identify the morphological properties and the elemental composition of the
Nanocomposite
Adsorption
synthesized nanocomposite, before and after it reacted with the chromium ions, HR-SEM-EDS was used.
Synthesis XRD was used to identify mineralogical compositions, while BET was used to determine surface areas.
Chromium ions ICP-MS and multi-parameter probe were employed for water quality analyses. The removal of chromium
Characterization ions, post the adsorption process, was confirmed using HR-SEM-EDS. The optimum conditions for chro-
mium ions removal were identified as 60 min contract, 0.5 g of dosage at 0.5 g: 500 mL S: L ratio, and
300 mg L
1 chromium ions concentration. The reaction was observed to be independent of pH (1–10).
At optimum conditions, the nanocomposite practically removed chromium ions from all examined water
matrices, i.e. real tannery wastewater, fortified tap water, groundwater, mine water, and synthetic solu-
tion. The adsorption capacity was observed to be 199 mg g
1. Regarding the regression analysis, the
adsorption kinetics seem to follow the pseudo-second-order (PSO) than the pseudo-first order (PFO)
model. In addition, the adsorption data better fitted the Langmuir than the Freundlich adsorption iso-
therm. In a nutshell, the synthesized nanocomposite was found to be very promising for chromium ions
removal from wastewater and possibly for other contaminants, such as heavy metals, which will be
examined in future works of our group.
Ó 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Sympo-
sium on Nanostructured, Nanoengineered and Advanced Materials.

1. Introduction
Due to the excellent properties of clay minerals in contaminant
sorption, their application in wastewater depollution appears very
promising [1]. This is attributed to their stable mechanical and
chemical structure that enables them to effectively adsorb contam-
inants under different environmental conditions. In particular, clay
minerals are characterized by high surface areas, water holding
and cation exchange capacities, and basic nature [2]. These, com-
bined with their abundance, high availability, and their cost-
effectiveness suggest that clay mineral utilization in the wastewa-
ter industry can be economically viable. Specifically, bentonite clay
and halloysite nanotubes have been widely employed for the
removal of contaminants, including chromium ions, from wastew-
ater [3]. Bentonite clay is characterized by lamella and leafy-like
structures, whereas halloysite clay naturally occurs in tubular

https://doi.org/10.1016/j.matpr.2020.06.084
2214-7853/Ó 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Symposium on Nanostructured, Nanoengineered and Advanced Materials.
 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101
shaped nanotubes, hence the name nanotube [1,4]. They are both
aluminosilicate clay minerals, since they include in their matrices
elevated levels of Al and Si [2,3].
Furthermore, chromium is a naturally occurring mineral, which
is abundantly present in the geosphere. It is used in a wide range of
industrial applications and is primarily mined from chrome rich
ore deposits. As a result, leaching of chromium from soil contami-
nated by mining activities, along with discharges from metallurgi-
cal or industrial processes, are often responsible for high chromium
ions releases to the receiving environment [5,6]. The World Health
Organization (WHO) guidelines for drinking-water quality suggest
that the maximum chromium concertation in potable water should
be 0.5 mg L
1 (total Cr) [7]. However, chromium releases in indus-
trial wastewaters are typically many order of magnitudes higher,
since they are at the range of 2656–5420 mg/L or even higher
[8]. These industrial sources include tannery, mining, and metal-
lurgical wastewaters. Exposure to chromium has been associated
with carcinogenic, teratogenic, and mutagenic toxicological effects,
among other ecotoxicological effects [9]. Therefore, its removal
from wastewater effluents is imperative to safeguard human
health and the environment. When released to the environment,
chromium is typically encountered as Cr(III), when the pH < 5.5,
or Cr(VI), when the pH > 5.5. As such, the water pH will dictate
the type (oxidation state) of chromium to be removed [7,9–11].
It should be mentioned that Cr(III) is amongst the essential trace
elements for living organisms, which only impacts them when
found at high concentrations. However, this is not the case for Cr
(VI), which is both toxic and carcinogenic, and therefore its exis-
tence in natural waters can present an environmental and health
problem [12]. Given that the pH of natural water bodies is typically
higher than 5.5, this suggests that Cr(III) will be oxidized to of Cr
(VI), thus making its removal imperative.
As such, a wide range of technologies have been developed for
the removal of chromium ions from water and these include
adsorption, filtration, precipitation, ion exchange, and phytoreme-
diation [5,13,14]. Amongst these, adsorption has emerged as a par-
ticularly promising technology, owing to its robustness and
versatility since it can employ low-cost and locally available mate-
rials, such as clay minerals that exhibit excellent adsorption capac-
ities [13]. Precipitation has also received a fair amount of attention,
due to its ability to treat concentrated solutions and at the same
time recovering valuable minerals (i.e. wastewater beneficiation).
Popular precipitants include Ca- (limestone and lime), Mg- (mag-
nesite, brucite, periclase and dolomite) and Na-rich (soda ash,
and caustic soda) minerals [15–17]. On the other hand, filtration
and ion exchange can be expensive and also pose secondary eco-
logical challenges, due to the production of retentate (brine) and
regenerants [18]. Phytoremediation requires large areas, depends
on many local factors, and typically has limited efficacy since chro-
mium can be toxic to flora [19,20].
In this work, the synergistic effect of adsorption and precipita-
tion on the removal of chromium ions from real and synthetic
wastewater matrices is examined. To this end, a nanocomposite,
based on an adsorbent (clay) and a precipitating agent (magnesite),
was synthesized using a facile process. Specifically, facile
approaches for materials synthesis include pillaring, mechano-
chemical synthesis, grafting, co-precipitation, thermal activation,
organo-modification, mechano-chemical synthesis via vibratory
ball milling and thermal activation [21,22]. Among them, vibratory
ball milling can lead to the fragmentation, distortion, and breakage
of crystalline networks and cobwebs, reduce particle size, increase
surface area, and lead to exfoliation and lattice expansion, as well
as to amorphization of clay minerals [2]. As a result, the capacity of
the milled material in removing pollutants, through adsorption
from aqueous solutions, is grossly enhanced [2,21–23]. In addition,
base minerals, such as magnesite, can be added to the clay’s
1089
matrix, thus increasing the basicity and by extension the neutral-
ization capacity of the combined material [2,22].
This study was therefore developed with the aim of synthesiz-
ing a multifunctional nanocomposite for the removal of chromium
ions, and possibly of other contaminants such as heavy metals,
from aqueous solutions. Vibratory ball miller was used to synthe-
size the nanocomposite and calcination was used to remove the
carbonates and volatile materials. Thence, the efficacy of the syn-
thesized nanocomposite was examined in terms of chromium ions
removal from both real and synthetic wastewater.
2. Materials and methods
2.1. Raw material collection and preparation
Commercially available, high quality chemicals were used
throughout this work. Specifically, halloysite was procured from
Protea chemical, Pty (Ltd). In addition, Ecca Pty (Ltd) donated the
bentonite clay. Raw magnesite was collected from Folovhodwe
magnesite mine, in Limpopo, South Africa. Following Masindi,
et al. [22], these minerals were then grinded and milled by means
of a Retsch RS 200 vibratory disc mill at 1500 rpm. After vibratory
ball milling, magnesitewas calcined at 1000 °C while bentonite and
halloysite clays were calcined at 500 °C. Subsequently, all minerals
were brought together and milled again, using the same Retsch RS
200 mill at 1500 rpm. As such, thermal activation and vibratory
milling were adopted for the synthesis of the nanocomposite at
1:1:1 ratio for bentonite clay, cryptocrystalline magnesite, and hal-
loysite clay. Finally, to maintain uniformity and homogeneity, the
synthesized nanocomposite was sieved using a 32-mm perforated
sieve. After preparation, the powdered material was packed into
a safe container until use for the removal of chromium ions from
aqueous solutions.
2.2. Preparation of synthetic solutions for batch experiments
A stock solution of 1000 mg L
1 chromium concentration was
procured from Merck. Synthetic solutions containing different
chromium concentrations, as shown in Table 1, were then pre-
pared in a 1000 mL volumetric flask. Specifically, the concentrated
solution was diluted in ultrapure to prepared the synthetic solu-
tions (Table 1), which were kept at 4 ℃ as the experiments
progress.
2.3. Batch optimization experiments
The examined parameter ranges that were used to identify the
optimum conditions for chromium ions removal from aqueous
solution are shown in Table 1. It should be mentioned that for
pH adjustment 1 M of NaOH and HCl were used, accordingly. Over-
head stirrers were used for mixing. All the experiments were per-
formed in triplicate and the results are reported as average values.
Parameters with high standard deviations were repeated for qual-
ity control purposes. Finally, to identify the optimum conditions
the one-factor-at-a-time (OFAT) method was used, which implies
Table 1
The examined parameter ranges and their variables.
Parameters Variables
Mixing time (min) 0, 5, 10, 15, 30, 60, 120, 180, and 360
Adsorbent dosage (g) 0.1, 0.5, 0.8, 1, 3, 4, and 4
Adsorbate concentration (mg L
1) 20, 50, 100, 150, 200, 300, 400, and 600
pH 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10
1090 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101

that while optimizing one parameter, the other parameters were ðC 0
C t Þ

%remov al ¼  100 ð3Þ
fixed. C0

Where, C0 the initial contaminant (chromium ions) concentration

2.4. Characterization of the nanomaterial before and after the
adsorption
The morphological properties and elemental composition of the
synthesized nanocomposite, before and after chromium ions
adsorption, were identified using state-of-art analytical instru-
ments. Specifically, the mineralogical composition was determined
using X-ray diffraction (XRD) (Philips PW 1710 Diffractometer;
graphite secondary monochromatic source). The morphological
and elemental compositions were identified using HR-SEM-EDS
(The Auriga Cobra FIB-FE-SEM – Model: Sigma VP FE-SEM with
Oxford EDS Sputtering System, Make: Carl Zeiss, Supplier: Carl
Zeiss, USA). The surface area (SBET) and pore size distribution of
raw and reacted materials were ascertained using the Brunnet-
Emmett-Teller (BET), using a Micromeritics Accelerated Surface
Area and Porosimetry (ASAP) 2010 analyzer. Prior the SBET deter-
mination, the degassing of approximately 10 g of raw and reacted
materials were performed at 120 °C for 24 h, using a Micromeritics
TriStar 3000 automated gas adsorption analyzer, equipped with a
SmartPrep degasser.
2.5. Characterization of the water matrices before and after the
adsorption
The characteristics of the wastewater and the nanocomposite
treated water matrices were determined using ICP-MS (XSeries 2,
supplied by Thermo Fisher Scientific (Bremen) GmbH). The ICP-
MS was coupled to ASX-520 Auto sampler. The HANNA
Multi-parameter probe (model HI-9828 Multi-Parameter Water
Quality Portable Meter). To ensure accuracy and quality, all mea-
surements were carried out in a laboratory that was certified by
the South African National Accreditation System (SANAS) for such
analyses.
2.6. Computing adsorption capacity and percentage removal
The adsorption capacity and the contaminant (chromium ions)
percentage removal efficacy were determined using Eqs. (1) and
(2) for the first and Eq. (3) for the latter [24–26].
ðC 0
C e Þv
qe ¼
m The surface area properties of the synthesized nanocomposite,
ðC 0
C t Þv
qt ¼
m Table 2.
(mg L
1), Ct the concentration at a given time, and Ce the equilib-
rium concentration; m is the mass (g) of the dry adsorbent
(nanocomposite); and v is the volume (L) of the solution
(adsorbate).
2.7. Modelling of the adsorption mechanisms
In this study, the most widely used adsorption kinetic models
were employed to assess the nanocomposite performance in chro-
mium ions adsorption. In addition, to gain insight on the mecha-
nism of adsorption and investigate the maximum adsorption
capacity, i.e. maximum mass adsorbed by the adsorbent, a series
of adsorption measurements were carried out, applying two widely
used two-parameter adsorption isotherms models. Specifically,
adsorption kinetics were performed using the pseudo-first-order
and pseudo-second-order kinetic models, whereas adsorption iso-
therms were quantified using the Langmuir and Freundlich adsorp-
tion isotherms [26].
In addition, the linear coefficient of determination (R2) was
employed to determine the error and the relationship between
the measured data [27]. The linear coefficient was computed using
Eq. (4):
P P P
n xy
ð xÞð yÞ
R2 ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P P
ffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P P ð4Þ
nð x2 Þ
ð xÞ2
ð y2 Þ
ð yÞ2
Where, R-squared ranges between 0 and 1, with lower values sug-
gesting poor fit and higher values implying good fit. The R2 value
denotes the variation of experimental data and this is duly eluci-
dated in the regression equation.
3. Results and discussion
The results for the physicochemical properties of the nanocom-
posite, before and after chromium ions adsorption, the water qual-
ity of the raw and treated wastewater matrices, as well as the
optimization studies are reported here.
3.1. Specific surface area and porosity
ð1Þ
as well as of the nanocomposite after it reacted with and adsorbed
ð2Þ chromium ions (Cr-reacted nanocomposite thereafter), are listed in

Table 2
The surface area properties of the synthesized nanocomposite and Cr-reacted nanocomposite.

Parameters Synthesized nanocomposite Cr-reacted nanocomposite

2
1
Surface Area (m g )
Single point surface area (m2 g
1) 35.2 37.0
BET Surface Area (m2 g
1) 35.8 37.9
BJH Adsorption cumulative surface area (m2 g
1) 26.1 33.3
BJH Desorption cumulative surface area (m2 g
1) 44.8 79.6
Pore Volume (cm3 g
1)
Single point adsorption total pore volume (cm3 g
1) 0.1 0.2
BJH Adsorption cumulative volume of pores (cm3 g
1) 0.1 0.2
BJH Desorption cumulative volume of pores (cm3 g
1) 0.1 0.2
Pore Size (nm)
Adsorption average pore width (4 V/A by BET) (nm) 11.9 15.3
BJH Adsorption average pore diameter (4 V/A) (nm) 17.4 18.6
BJH Desorption average pore diameter (4 V/A) (nm) 11.3 9.3
 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101
As shown in Table 2, the specific surface area of the nanocom-
posite was reported to be 35.8 m2 g
1 and it was observed to
slightly increase to 37.9 m2 g
1 after the adsorption of chromium
ions from wastewater. An increase in surface area indicates that
the adsorbed chemical has the potential to increase the surface
area of the adsorbent. An increase in surface area also denotes
the potential of this material to be used for secondary uses, post
the adsorption of chromium ions. As such, results suggest that
the adsorption process has created more sites, which are possibly
suitable for adsorption. Furthermore, the pore size and volume of
the adsorbent were also observed to increase after chromium ions
adsorption. This may be linked to the radial diameter of chromium,
which increases the pore size and surface area of the adsorbent
(nanocomposite).
In addition, the nitrogen adsorption–desorption isotherms of
the synthesized nanocomposite and Cr-reacted nanocomposite
are shown in Fig. 1.
As shown in Fig. 1, the adsorbed quantities were observed to
increase with an increase in relative pressure. This could be
explained by the non-rigid nature of the adsorbent and the location
of the characteristic shoulder, which is consistent with the destabi-
lization of condensate at the p/p0 value that governs the entire pro-
cess. Furthermore, based on the IUPAC classification the curves for
both the synthesized and Cr-reacted nanocomposite showed a type
IV isotherm shape, with an adsorption step at relative pressure of
p/p0 = 0.5 and a hysteresis loop at p/p0 = 0.7–1.0, suggesting the
presence of mesopores. In addition, Fig. 1 is observed to be com-
prised of the H3-type hysteresis loops, according to the
Brunauer-Deming-Deming-Teller (BDDT) classification methodol-
ogy, indicating that the samples contain mesopores (2–50 nm).
This denotes that the synthesized nanocomposite is mesoporous.
Finally, it was identified that the quantity adsorbed, after the
adsorption of chromium ions, was higher compared to the quantity
before the nanocomposite reacted with the adsorbent, and this
attributed to the higher surface area after adsorption.
3.2. Morphology of raw minerals and of the synthesized and the Cr-
reacted nanocomposite
In Fig. 2a-j the FESEM images, which reveal the morphological
properties of milled and calcined bentonite clay, magnesite
nanosheets, halloysite nanotubes, and their facile synthesized
nanocomposite, before and after reaction with Cr-rich wastewater,
are shown. Specifically, as observed in Fig. 2a and b, bentonite clay
contains lamella and leafy-like structures. Furthermore, the mor-
phology of bentonite clay remained the same regardless of the
two different magnifications (100 and 200 nm) employed herein.
Fig. 1. The nitrogen adsorption–desorption isotherms of the synthesized nanocom-
posite and Cr-reacted nanocomposite.
1091
Fig. 2c and d presents the results for halloysite clay, where the
presence of tubular and rod-like structures on its matrices is
shown. Even though the rod-like structures are of different sizes,
their structure was the same over the two different magnifications
(100 and 200 nm). Similar results have been reported in the litera-
ture [28]. Furthermore, the calcined South African cryptocrys-
talline magnesite was observed to contain octagonal nanosheet
structures, of varying sizes and distribution (Fig. 2e and f). The
sheets were irregular in size. Similar results have been reported
in the literature [29,30]. When these materials are brought
together and milled by means of a vibratory ball miller, the
nanocomposite under study is synthesized, which is observed to
comprise matrices of bentonite clay, halloysite clay, and magnesite
nanosheets (Fig. 2g and h). However, the nanocomposite was
observed to contain leafy structures as well as rod-like structures,
which were more obvious when using the higher magnification
(100 nm), but in an irregular form. The change in morphology fur-
ther confirms that the synthesized nanocomposite has been trans-
formed into a new mineral. Finally, after the synthesized
nanocomposite contacted the Cr-rich effluent, in this case chro-
mium wastewater, structural changes were observed in the Cr-
reacted nanocomposite (Fig. 2i and j). These changes possibly
denote the dissolution of components from the nanocomposite
matrix and deposition of materials (in this case chromium ions)
into the surface of the nanocomposite. This further confirms that
the reaction of the nanocomposite with Cr-rich wastewater results
in a change in the morphological properties of the Cr-reacted
nanocomposite.
3.3. Electron dispersion spectroscopy spectra of the synthesized and
Cr-reacted nanocomposite
The electron dispersion spectroscopy (EDS) spectra of the syn-
thesized and the Cr-reacted nanocomposite are shown in Fig. 3a
and b, respectively.
As shown in Fig. 3a, the EDS spectrum of the synthesized
nanocomposite reveals that it is rich in C, O, Mg, Si, Al, Ca, and
Fe. These elements are typically encountered in the minerals that
were used for the nanocomposite synthesis. Specifically, bentonite
clay is rich in Al and Si, hence being an aluminosilicate clay miner-
als [2]. Furthermore, calcined magnesite is rich in Mg and O,
including traces of Si, Ca and other components [29]. Finally, hal-
loysite is rich in Al and Si as major elements, thus also being an alu-
minosilicate clay mineral [31]. Carbon is from the feed carbonate
minerals and the coating material for SEM-EDS analysis. However,
after the nanocomposite reacted with the chromium-rich water,
the EDS spectrum (Fig. 3b) revealed that the Cr-reacted nanocom-
posite contains Cr on its interlayers, in addition to base metals and
molybdenum. The existence of other elements suggest that the
synthesized nanocomposite has the potential to remove more con-
taminants from wastewater. Therefore, the obtained results verify
that indeed the synthesized nanocomposite is adsorbing Cr from
aqueous solutions.
3.4. SEM-EDS elemental compositions on selected points of the
synthesized and the Cr-reacted nanocomposite
The detailed high-resolution SEM-EDS image (Fig. 4a) and the
elemental composition of the selected points (Fig. 4b-e) for the
synthesized nanocomposite are shown 4 below.
Specifically, Fig. 4a shows the synthesized nanocomposite’s
point and shoot regions selected for analysis, while Fig. 4b-e show
the spectra from each of the four analysis regions (where 1, 2, 3,
and 4 regions correspond to b, c, d, and e spectra, respectively).
As observed from the results shown in Fig. 4, the synthesized
nanocomposite is rich in C, O, Mg, Ca, Si, and Al, as the main ele-
1092 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101

Fig. 2. The FESEM images of bentonite clay (a-b), halloysite nanotubes (c-d), calcined magnesite nanosheets (e-f), the synthesized nanocomposite (g-h), and Cr-reacted
nanocomposite (i-j).
 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101 1093

Fig. 3. The electron dispersion spectroscopy (EDS) spectra of the synthesized nanocomposite (a) and Cr-reacted nanocomposite (b).

ments in its matrix. These results confirm the ones obtained in the
EDS analysis, shown above. The results further confirm that the
nanocomposite is synthesized from a combination of Mg, Al, and
Si dominated minerals. Amorphous structures are observed in
Fig. 4a, which suggests that the material underwent some mechan-
ical deformation.
Finally, the Cr-reacted nanocomposite point and shoot regions
selected for analysis (Fig. 5a), along with the spectra from these
regions (Fig. 5b-e) were also estimated by simultaneous SEM and
EDS analysis. The identified elemental compositions of the selected
points for the Cr-reacted nanocomposite are also listed in the
insets included in Fig. 5.
As shown in Fig. 5b-e, the Cr-reacted nanocomposite was found
to contain C, O, Mg, Ca, Si, and Al as its main elements. In addition,
the Cr-reacted nanocomposite was also found to contain Cr, along
with base metals and traces of molybdenum. These elements were
not included in the synthesized nanocomposite matrix, before it
reacted with the wastewater, which suggests that these elements
were adsorbed from the wastewater onto the Cr-reacted nanocom-
posite matrix. These results are in agreement with those of the EDS
analysis.
3.5. Mapping of the synthesized and the Cr-reacted nanocomposite
Elemental mapping, at the microstructural level, of the synthe-
sized and the Cr-reacted nanocomposite was obtained using HR-
SEM-EDS. Results are shown in Fig. 6a-h for the synthesized
nanocomposite and Fig. 7a-h for the Cr-reacted nanocomposite.
Specifically, as shown in Fig. 6a-h, the elemental mapping of
synthesized nanocomposite revealed that this material is rich in
1094 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101

Fig. 4. a) The SEM-EDS image of the synthesized nanocomposite and b-e) the elemental composition of the selected points for the synthesized nanocomposite.

C, O, Mg, Al, Si, Ca and Fe on its matrices. This confirms that this which is traced back to calcined magnesite. The elements were
material is a combination of aluminosilicates, which are traced evenly distributed across the nanocomposite’s surface, hence
back to the clay minerals (halloysite and bentonite) and MgO, denoting the homogeneity of this material and suggesting that it
 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101 1095

Fig. 5. The SEM-EDS image and the elemental composition of the selected points for the Cr-reacted nanocomposite (a-e).
1096 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101

Fig. 6. Mapping of the elemental distribution on the surface of the synthesized nanocomposite (a-h).
 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101 1097

Fig. 7. Mapping of the elemental distribution on the surface of Cr-reacted nanocomposite (a-j).
1098 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101
has been successfully synthesized through the proposed facile pro-
cess. Concentrated elements were observed to be C, Mg, O, Al, and
Si, which are the main elements of the raw materials used for the
nanocomposite’s synthesis. Furthermore, Fig. 7a-j shows the ele-
mental mapping of the Cr-reacted nanocomposite.
Specifically, as shown in Fig. 7a-j, the elemental mapping of the
surface of the Cr-reacted nanocomposite revealed that this mate-
rial is rich in C, O, Mg, Al, Si, and Ca. In addition, traces of K, Cr,
and Fe were also observed. This confirms that this material has
adsorbed chromium ions in its matrices, along with other base
metals and molybdenum, which were scavenged from the wastew-
ater matrix, in this case from tannery wastewater. Even though, the
intensity of the Cr distribution was fade, result suggest that it was
distributed across its surface.
3.6. Mineralogical composition by XRD analysis
The mineralogical compositions of the synthesized and Cr-
reacted nanocomposite were estimated by means of XRD, and are
shown in Fig. 8.
As shown in Fig. 8, there is no change in the mineralogical com-
position of the synthesized and Cr-reacted nanocomposite. This
suggests that only adsorption rather than chemisorption, i.e.
adsorption along with a chemical reaction between the adsorbent
and the adsorbate, took place, thus no change in the mineralogical
Fig. 8. The mineralogical compositions of the synthesized nanocomposite and Cr-reacted nanocomposite.
composition of the synthesized nanocomposite, after the Cr
adsorption, was observed. In addition, the mineralogical composi-
tion revealed the presence of periclase, quartz, kaolinite, calcite,
gibbsite, halloysite, montmorillonite and brucite. These minerals
are a genesis of Al, Si, Mg and Ca-based mineral phases. This fur-
ther confirms that the synthesized nanocomposite has acceptable
mechanical and chemical stability during the adsorption process.
The obtained results also correspond to the ones reported in the
HR-SEM-EDS section. Furthermore, similar mineral compositions
were observed by the EDS technique.
3.7. Optimization studies and modelling
The optimization studies and modelling results for the removal
of chromium ions from aqueous solutions, using the synthesized
nanocomposite, are shown in Fig. 9. Specifically, batch experimen-
tal studies were carried out using the simulated solution, as the
chromium-rich water matrix, and examining the effect of contact
time (mixing), adsorbent dosage, adsorbate concentration, and
pH of chromium removal efficacy.
Effect of contact time: As shown in Fig. 9a, a rapid increase in
the removal of chromium ions from wastewater, when using the
synthesized nanocomposite, was observed with increasing in con-
tact time. Specifically, a logarithmic growth in chromium ions
removal is observed in the contact time 0–60 min. However, after
 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101
Fig. 9. Optimization and modelling results for the removal of chromium ions from the simulated aqueous solution using the synthesized nanocomposite.
contact time 60 min, it is observed that equilibrium is archived,
since it appears that the adsorbed amount has reached a plateau.
Therefore, the optimum contact time for chromium ions removal
is 60 min, which was used in the subsequent experiments. On that
note, the high neutralization and cationic exchange capacity of the
synthesized nanocomposite are key factors that influence chro-
mium ions removal from water. This is primarily attributed to
the presence of base minerals, primarily Mg and Ca, in its matrices
along with clay, which exhibit a high adsorption capacity, thus
bestowing this material with the synergistic effects of precipitation
and adsorption towards chromium ions removal from wastewater.
Effect of adsorbent dosage: The variation in the removal of chro-
mium ions from wastewater, as a function of the nanocomposite
dosage, is examined here and shown in Fig. 9b. Similar to contact
time, a very steep increase in chromium ions removal is also
observed, however in this case the plateau region begins at a very
low nanocomposite dosage, i.e. 0.5 g. Specifically, an logarithmic
growth in chromium ions removal is observed from the 0.1 g to
the 0.5 g dosage. A very small increase in chromium ions removal
1099
was observed in the next examined dosage, i.e. 0.8 g. However, a
steady state is reached in 1 g dosage, since no further change in
the removal efficacy was observed for higher dosages. In general,
with higher dosages more sites are available for adsorption, hence
a higher removal efficacy at higher dose was observed. Nonethe-
less, the synthesized nanocomposite was found to exhibit an excel-
lent efficacy in terms of chromium ions removal, since its efficacy
is grossly improved in dosage 0.5 g, then a very small increase is
observed in dosage 1 g and thereafter equilibrium has been
reached. Therefore, the optimum conditions for chromium ions
removal were observed to be reached at 0.5 g: 500 mL (S: L).
Effect of chromium ions initial concentration: As shown in Fig. 9c,
a higher removal efficacy for chromium ions was observed at lower
concentrations, but this decreased with an increase in chromium
ions initial concentration. This could be explained by limited
adsorption sites being available when the concentration of chro-
mium ions increases. Specifically, from 20 to 300 ppm, the removal
efficacy was >99%. However, after 300 ppm, the adsorption capac-
ity was observed to decrease. This may be explained by the deple-
1100 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101
Table 3
The comparison of the removal efficacy of chromium species from different water matrix using the synthesized nanocomposite at optimized conditions.
Parameters Tannery Synthetic
Co 60 200
Ce 0.05 0.001
WHO limit 0.05 0.05
DWAF 1 1
EPA 0.1 0.1
% removal 99.92 99.99
tion of the active sites for the adsorption of chromium ions. A
higher dosage could address this problem, however chromium ions
concentrations above 300 ppm are not typically encountered at
real wastewater effluents. Thenceforth, 200 ppm was taken as
the maximum optimum concentration, when using 0.5 g of the
synthesized nanocomposite as dosage. This was used in the subse-
quent experiment (effect of initial pH).
Effect of pH: As shown in Fig. 9d, the efficacy for chromium ions
is observed to be independent of the initial pH (examined pH range
1–10). This could be explained by the fact that the nanocomposite
rely on three mechanisms for the removal of chromium ions, i.e.
adsorption, cation exchange, and precipitation. Furthermore, the
presence of magnesite in the nanocomposite matrix will raise the
supernatant pH. Therefore, even when wastewaters with very
low pH are targeted, the addition of the nanocomposite will largely
increase its pH thus assisting chromium ions removal. As such, the
ambient pH of the wastewater, if this is below 10, will be the opti-
mal pH value. Here, this pH value was assumed to be neutral to
slightly basic, i.e. 8, to account for a typical pH values in chromium
ions rich wastewaters, such as tannery wastewater.
Adsorption kinetics and isotherms: As shown in Fig. 9e-f, the
adsorption kinetics conformed to the pseudo-second-order (PSO)
than the pseudo-first order (PFO) kinetic model. This was based
on the regression analysis, which denoted 0.23 (23%) and 1
(100%) for PFO and PSO, respectively. Contrary, the adsorption iso-
therm conformed to Langmuir than the Freundlich adsorption iso-
therm hence conforming the mono-site adsorption process. The
regression analysis showed 0.99 (99%) and 0.44 (44%) for Langmuir
and Freundlich adsorption isotherms, respectively.
3.8. Removal of chromium ions at optimized conditions
The comparison of the removal efficacies of chromium ions
from different water matrices, when using the synthesized
nanocomposite at optimized conditions, are shown in Table 3.
The examined matrices include real wastewater, i.e. tannery and
mine water, as well as synthetic matrices, i.e. synthetic and forti-
fied solutions along with spiked groundwater and tap water. As
shown in Table 3, a wide array of real and synthetic wastewater
matrices were examined to assess the robustness and versatility
of the synthesized nanocomposite. It was found that the nanocom-
posite can be used to reclaim water that meets various standards,
guidelines and specifications [7,9–11] from various wastewater
matrices. Specifically, the efficacy of the nanocomposite against
the different water matrices examined herein was observed to be
>99% in all examined cases (Table 3). Therefore, this study con-
firmed that the nanocomposite could be used to remove chromium
ions from aqueous samples of different origins.
4. Conclusions
This study successfully demonstrated the facile synthesis of
halloysite-bentonite clay/magnesite nanocomposite using vibra-
tory ball milling and calcination. The synthesized nanocomposite
maintain the properties of both its main components, i.e. of clay
Mine Water Fortified solution Groundwater Fortified tap water
5 200 10 100
0.03 0.09 0.01 0.78
0.05 0.05 0.05 0.05
1 1 1 1
0.1 0.1 0.1 0.1
99.40 99.96 99.90 99.22
(adsorption) and magnesite (precipitation) and hence was
employed for the removal of chromium ions from a wide array of
different wastewater matrices. These include real wastewater (tan-
nery and mine water) and synthetic matrices (synthetic and forti-
fied solutions along with spiked groundwater and tap water). The
optimized conditions for chromium ions removal were also identi-
fied and these were 60 min of mixing, 0.5 g of dosage at 0.5 g:
500 mL (S:L ratio), 200 ppm of initial chromium concentration,
and ambient pH. Adsorption kinetics followed the pseudo-
second-order (PSO) over the pseudo-first order (PFO) model. Fur-
thermore, adsorption isotherms conformed to Langmuir than Fre-
undlich adsorption isotherm. The maximum adsorption capacity
of activated cryptocrystalline magnesite was observed to be
199 mg g
1. At optimized conditions, chromium ions were success-
fully removed from all examined water matrices. HR-SEM-EDS
confirmed the fate of chromium ions post adsorption. Adsorption,
ion exchange and precipitation were the principal mechanisms
governing the removal of chromium ions.
CRediT authorship contribution statement
V. Masindi: Conceptualization, Methodology, Investigation,
Writing - original draft, Funding acquisition. S. Foteinis: Valida-
tion, Writing - original draft. M. Tekere: Validation, Writing - orig-
inal draft. M.M. Ramakokovhu: Validation, Writing - original
draft.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors of this manuscript would like to convey their sin-
cere gratitude to the University of South Africa, Magalies Water,
WRC (K5/2756), NRF, and Tshwane University of Technology
(TUT) for their profound support towards the fulfillment of this
study. Their support significantly contributed in realizing the goals
of this study.
References
[1] B. Mu, A. Wang, Adsorption of dyes onto palygorskite and its composites: A
review, J. Environ. Chem. Eng. 4 (2016) 1274–1294.
[2] V. Masindi, M.W. Gitari, H. Tutu, M. DeBeer, Efficiency of ball milled South
African bentonite clay for remediation of acid mine drainage, J. Water Process
Eng. 8 (2015) 227–240.
[3] C.V. Lazaratou, D.V. Vayenas, D. Papoulis, The role of clays, clay minerals and
clay-based materials for nitrate removal from water systems: A review, Appl.
Clay Sci. 185 (2020) 105377.
[4] H. Han, M.K. Rafiq, T. Zhou, R. Xu, O. Mašek, X. Li, A critical review of clay-based
composites with enhanced adsorption performance for metal and organic
pollutants, J. Haz. Mat 369 (2019) 780–796.
[5] M.A. Islam, M.J. Angove, D.W. Morton, Recent innovative research on
chromium (VI) adsorption mechanism, Environ. Nanotechnol. Monit.
Manage. 12 (2019) 100267.
 V. Masindi et al. / Materials Today: Proceedings 38 (2021) 1088–1101
[6] E. Kalita, J. Baruah, 16 - Environmental remediation, in: S. Thomas, A. Tresa
Sunny, P. Velayudhan (Eds.) Colloidal Metal Oxide Nanoparticles, Elsevier,
2020, pp. 525-576.
[7] World Health Organization, Guidelines for drinking-water quality: fourth
edition incorporating first addendum, 4th ed + 1st, add ed., World Health
Organization, Geneva, 2017.
[8] M.A. Hashem, A. Islam, S. Mohsin, M.S. Nur-A-Tomal, Green environment
suffers by discharging of high-chromium-containing wastewater from the
tanneries at Hazaribagh, Bangladesh, Sustainable Water Resources Manage. 1
(2015) 343–347.
[9] U.S. Environmental Protection Agency (EPA). Water Quality Standards
Handbook, in: Chapter 3: Water Quality Criteria. EPA-823-B-17-001, EPA
Office of Water, Office of Science and Technology, Washington, DC,https://
www.epa.gov/sites/production/files/2014-10/documents/handbook-chapter3.
pdf, 2017.
[10] SABS Standards Division., South African National Standard (SANS), in: Drinking
water - Part 2: Application of SANS 241-1 2015.
[11] Department of Water Affairs and Forestry, South African Water Quality
Guidelines (first edition), Field Guide, Department of Water Affairs and
Forestry, Volume 8 (1996).
[12] M. Shahid, S. Shamshad, M. Rafiq, S. Khalid, I. Bibi, N.K. Niazi, C. Dumat, M.I.
Rashid, Chromium speciation, bioavailability, uptake, toxicity and
detoxification in soil-plant system: A review, Chemosphere 178 (2017) 513–
533.
[13] V. Dimos, K.J. Haralambous, S. Malamis, A review on the recent studies for
chromium species adsorption on raw and modified natural minerals, Crit. Rev.
Environ. Sci. Technol. 42 (2012) 1977–2016.
[14] H.N. Tran, D.T. Nguyen, G.T. Le, F. Tomul, E.C. Lima, S.H. Woo, A.K. Sarmah, H.Q.
Nguyen, P.T. Nguyen, D.D. Nguyen, T.V. Nguyen, S. Vigneswaran, D.-V.-N. Vo,
H.-P. Chao, Adsorption mechanism of hexavalent chromium onto layered
double hydroxides-based adsorbents: A systematic in-depth review, J. Haz.
Mat 373 (2019) 258–270.
[15] V. Akinwekomi, J.P. Maree, V. Masindi, C. Zvinowanda, M.S. Osman, S. Foteinis,
L. Mpenyana-Monyatsi, E. Chatzisymeon, Beneficiation of acid mine drainage
(AMD): A viable option for the synthesis of goethite, hematite, magnetite, and
gypsum – Gearing towards a circular economy concept, Miner. Eng. 148 (2020)
106204.
[16] V. Akinwekomi, J.P. Maree, C. Zvinowanda, V. Masindi, Synthesis of magnetite
from iron-rich mine water using sodium carbonate, J. Environ. Chem. Eng. 5
(2017) 2699–2707.
[17] A.M. Awad, S.M.R. Shaikh, R. Jalab, M.H. Gulied, M.S. Nasser, A. Benamor, S.
Adham, Adsorption of organic pollutants by natural and modified clays: A
comprehensive review, Sep. Purif. Technol. 228 (2019) 115719.
[18] V. Masindi, M.S. Osman, A.M. Abu-Mahfouz, Integrated treatment of acid mine
drainage using BOF slag, lime/soda ash and reverse osmosis (RO): Implication
for the production of drinking water, Desalination 424 (2017) 45–52.
1101
[19] H. Ali, E. Khan, M.A. Sajad, Phytoremediation of heavy metals—Concepts and
applications, Chemosphere 91 (2013) 869–881.
[20] S.A. Asad, M. Farooq, A. Afzal, H. West, Integrated phytobial heavy metal
remediation strategies for a sustainable clean environment - A review,
Chemosphere 217 (2019) 925–941.
[21] A. Djukić, U. Jovanović, T. Tuvić, V. Andrić, J. Grbović Novaković, N. Ivanović, L.
Matović, The potential of ball-milled Serbian natural clay for removal of heavy
metal contaminants from wastewaters: Simultaneous sorption of Ni, Cr, Cd
and Pb ions, Ceram. Int. 39 (2013) 7173–7178.
[22] V. Masindi, M.W. Gitari, H. Tutu, M. DeBeer, Synthesis of cryptocrystalline
magnesite–bentonite clay composite and its application for neutralization and
attenuation of inorganic contaminants in acidic and metalliferous mine
drainage, J. Water Process Eng. 15 (2017) 2–17.
[23] A.B. Ðukić, K.R. Kumrić, N.S. Vukelić, M.S. Dimitrijević, Z.D. Baščarević, S.V.
Kurko, L.L. Matović, Simultaneous removal of Pb2 +, Cu2 +, Zn2 + and Cd2 +
from highly acidic solutions using mechanochemically synthesized
montmorillonite–kaolinite/TiO2 composite, Appl. Clay Sci. 103 (2015) 20–27.
[24] A. Mavhungu, R. Mbaya, V. Masindi, S. Foteinis, K.L. Muedi, I. Kortidis, E.
Chatzisymeon, Wastewater treatment valorisation by simultaneously
removing and recovering phosphate and ammonia from municipal effluents
using a mechano-thermo activated magnesite technology, J. Environ. Manage.
250 (2019) 109493.
[25] H.N. Tran, F. Tomul, H.T.H. Nguyen, D.T. Nguyen, E.C. Lima, G.T. Le, C.-T. Chang,
V. Masindi, S.H. Woo, Innovative spherical biochar for pharmaceutical removal
from water: Insight into adsorption mechanism, J. Haz. Mat (2020) 122255.
[26] H.N. Tran, S.J. You, A. Hosseini-Bandegharaei, H.P. Chao, Mistakes and
inconsistencies regarding adsorption of contaminants from aqueous
solutions: A critical review, Water Res. 120 (2017) 88–116.
[27] V. Masindi, W.M. Gitari, T. Ngulube, Kinetics and equilibrium studies for
removal of fluoride from underground water using cryptocrystalline
magnesite, J. Water Reuse Desalination 5 (2015) 282–292.
[28] V.B. Yadav, R. Gadi, S. Kalra, Clay based nanocomposites for removal of heavy
metals from water: A review, J. Environ. Manage. 232 (2019) 803–817.
[29] N. Magagane, V. Masindi, M.M. Ramakokovhu, M.B. Shongwe, K.L. Muedi,
Facile thermal activation of non-reactive cryptocrystalline magnesite and its
application on the treatment of acid mine drainage, J. Environ. Manage. 236
(2019) 499–509.
[30] V. Masindi, Recovery of drinking water and valuable minerals from acid mine
drainage using an integration of magnesite, lime, soda ash, CO<inf>2</inf> and
reverse osmosis treatment processes, J. Environ. Chem. Eng. 5 (2017) 3136–
3142.
[31] T. Ngulube, J.R. Gumbo, V. Masindi, A. Maity, Evaluation of the efficacy of
halloysite nanotubes in the removal of acidic and basic dyes from aqueous
solution, Clay Miner. 54 (2019) 197–207.