Environmental Nanotechnology, Monitoring & Management 16 (2021) 100562

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Environmental Nanotechnology, Monitoring & Management

journal homepage: www.elsevier.com/locate/enmm

Copper modified activated bamboo charcoal to enhance adsorption of

heavy metals from industrial wastewater
Roshan Thotagamuge a, *, Muhammad Raziq Rahimi Kooh a, Abdul Hanif Mahadi a, *,
Chee Ming Lim a, Masanizan Abu a, Abigail Jan b, Alifatul Haziqah Abu Hanipah b,
Yong Yung Khiong b, Amanina Shofry b
a
Centre for Advanced Material and Energy Sciences, Universiti Brunei Darussalam, Jalan Tungku Link, Gadong BE1410, Brunei Darussalam
b
CIC Environmental Services Sdn Bhd, Lot 5159, Simpang 144, Jalan Maulana, Kuala Belait, KA 1531, Brunei Darussalam

A R T I C L E I N F O A B S T R A C T

Keywords: The chemical composition of industrial wastewater is complex which requires complicated chemical processes
Industrial wastewater before its discharge to environment. In this study, industrial wastewater is used to systematically evaluate the
Activated charcoal adsorption properties of 15 heavy metals using Copper modified activated charcoal (MAC) as an adsorbent. The
Modified charcoal
MAC is derived from locally available bamboo species named Gigantochloa genus. The adsorbent was prepared by
Cu coated
Heavy metals
CuCl2⋅2H2O impregnation with HCl activated bamboo charcoal. The physicochemical properties of MAC were
Adsorption characterised by FTIR, XRD, SEM, EDX and BET. The collected industrial wastewater sample was spiked with
inductively coupled plasma spectrometry standard solution prior to the performance tests. In addition, we have
compared the adsorption performance of commercial activated charcoal (CAC) with MAC. The adsorption tests
were conducted at different contact times, three different pHs and four different concentrations of heavy metals.
The results revealed the adsorption of most elements in the multi-element wastewater reached equilibrium
within 3 hrs with MAC and CAC. The optimum pH of adsorption for MAC is at 5.83. The MAC outperform CAC in
terms of having a higher adsorption capacity, qe and it has more effective in removal rate over a wider range of
pH. It is also noted that the removal of Cd, Pb, As and Cr by MAC is significant. The present study provides
prospective and effective adsorbent for multiple heavy metals removal in industrial wastewater

1. Introduction wastewater (Soliman and Moustafa, 2020; Fu and Wang, 2011;

Heavy metals are highly toxic to living organisms even at trace
amounts (Soliman and Moustafa, 2020; Maneechakr and Mongkoller­
tlop, 2020; Feng, 2020; Rosli et al., 2018). In general, elements with a
specific gravity of more than 5 and atomic weights within the range of
63.5–200.6 are characterised as heavy metals (Soliman and Moustafa,
2020). Arsenic (As), lead (Pb), cadmium (Cd), manganese (Mn), chro­
mium (Cr) and nickel (Ni) are examples of the common heavy metals
found in the environment (Soliman and Moustafa, 2020; Maneechakr
and Mongkollertlop, 2020; Feng, 2020). These heavy metals are mainly
produced from industrial activities such as oil and gas industry, where
they are discharged as waste in the forms of either gas, liquid, or solids.
The management of industrial waste has become a significant issue due
to high concentration of multiple heavy metals found in industrial
Adeyemo et al., 2017). Thus, there is necessity to find the most cost
effective and efficient routes to remove heavy metals from the waste­
water. There are many conventional approaches reported for the
removal of heavy metals such as electrocoagulation, electrodialysis,
photocatalysis, solvent extraction etc. (Soliman and Moustafa, 2020;
Barrera-Díaz et al., 2012; Mejáre and Bülow, 2001; Cechinel et al., 2014;
FENG et al., 2007). However, these methods often involve expensive
instrumentation and chemicals in the wastewater treatment process,
which are not economically viable (Soliman and Moustafa, 2020;
Maneechakr and Mongkollertlop, 2020; Cechinel et al., 2014; Cui et al.,
2015; Huang et al., 2016).
Adsorption is known as one of the conventional methods for waste­
water treatment which is more viable and advantageous compared to
the other methods. Easy operational conditions, low-cost fabrication,

* Corresponding authors at: Centre for Advanced Material and Energy Sciences, Universiti Brunei Darussalam, Jalan Tungku Link, Gadong, BE 1410, Brunei
Darussalam.
E-mail addresses: roshan.kumara@ubd.edu.bn (R. Thotagamuge), hanif.mahadi@ubd.edu.bn (A.H. Mahadi).

https://doi.org/10.1016/j.enmm.2021.100562
Received 11 December 2020; Received in revised form 24 July 2021; Accepted 22 August 2021
Available online 25 August 2021
2215-1532/© 2021 Elsevier B.V. All rights reserved.
R. Thotagamuge et al.
wide working range of pH and especially remarkable metal binding
capacity are amongst the advantages, whilst the production of solid
waste and low selectivity are the limitations (Fu and Wang, 2011;
Cechinel et al., 2014; Loganathan et al., 2013). The adsorption process
takes place on the surface as shown in Fig. 1 (Soliman and Moustafa,
2020) and the adsorbate and adsorbent either physically or chemically
contribute to the process. Atoms, ions, or molecules (adsorbate) from
any type of waste source which could be either gas, liquid or dissolved
solid, will stick to the active site of the adsorbent, developing a layer of
the adsorbate on the surface of the adsorbent. It can be a multilayer or a
monolayer depending on the properties of adsorbent and adsorbate
(Soliman and Moustafa, 2020; Dąbrowski, 2001). Moreover, there are
two main types of adsorption process according to the attraction force
between adsorbate and adsorbent, one is physical adsorption whereas
the other is chemical adsorptions, also known as physisorption and
chemisorption respectively (Dąbrowski, 2001). The adsorption process
is known to be heavily used in industrial applications including water
purification systems, catalysts industry, and synthesis of resins etc
(Soliman et al., 2019).
There are many reported adsorbents such as polymers, clay, carbon,
etc., and all these can be divided into either organic or inorganic ma­
terials (Adeyemo et al., 2017). To have an effective and a selective
adsorption, it is crucial to match the adsorbent properties with targeted
elements to be removed from the wastewater. The adsorbent’s physical
and chemical properties such as surface area, pore size, chemical
structure, and functional groups all play an important role in its func­
tionality (Soliman and Moustafa, 2020; Sankaran et al., 2010; Godwin
et al., 2019). Furthermore, the choice of adsorbent should be derived
from a practically feasible material. Charcoal or activated charcoal has
been proven to be an effective and easily producible material (Ahmed,
2017). However, its selectivity for the targeted element remains low
unless it is further processed via different modifications (Godwin et al.,
2019). Charcoal can be produced by pyrolysis of biomass including
bamboo, coffee bean, coconut shells, and sugarcane etc. by heating up to
a temperature of around ~700 ◦ C in presence of little or no O2 (Krasucka
et al., 2021).
To improve the adsorption, the adsorbent can be modified further via
Fig. 1. The process of the adsorption (Soliman and Moustafa, 2020).
2
Environmental Nanotechnology, Monitoring & Management 16 (2021) 100562
chemical or physical processes. The modifications enhance the selec­
tivity of the adsorbents towards the removal of elements from waste­
water. The chemical modifications may improve the area and charge of
the surface, increase the pore size, create new functional groups, and
remove impurities. Sun et al. reported a series of iron-charcoal produced
by impregnation method to remove toxic elements (Cu(II), Cr(VI), Zn(II)
and As(V)) from hydraulic fracturing wastewater and the modifications
improved its thermal stability compared to the charcoal and hence
increased its capacity to remove four elements simultaneously (Sun
et al., 2019). Feng. et at also reported a modification method to produce
iron impregnated charcoal and the modified version was tested in the
removal of As(V), As(III), Cr(VI) and Hg(II) from wastewater. The study
revealed that the element removal efficiency of iron-modified charcoal
has increased up to 99.9% due to its high adsorption rate and improved
redox reaction (Feng, 2020). Also, Maneechakr and Mongkollertlop
studied MnO2-modified charcoal for the removal of Cd(II), Cr(III), Pb(II)
and Hg(II) and its adsorption was increased with the aid of two-step
intra-particle diffusion processes (Maneechakr and Mongkollertlop,
2020). Charcoal can make strong electrostatic interactions in an aqueous
solution due to its high sensitivity to pH changes (Hu et al., 2018).
Previous studies have shown that the sensitivity of the adsorbents to the
pH of the solution can be effectively lowered by forming a complex
between adsorbent and the adsorbate (Hu et al., 2018; Hu et al., 2017).
Also, there are other studies that have shown that charcoal can form
complexes as a result of reactions with copper and perrhenate (Hu et al.,
2018; Cao et al., 2011). Thus, to reduce the electrostatic interactions of
charcoal, it is necessary to reduce its sensitivity to pH changes by
modifying the charcoal. Therefore, Cu-coated charcoal is one of the best
forms of modified charcoal with a low sensitivity to pH of the aqueous
dye solution, in order to recover the elements in an aqueous solution in
low concentrations (Hu et al., 2018). Even though there are many
studies reported on the modification of charcoal, there is an apparent
hindrance for modified charcoal to eliminate multiple elements simul­
taneously. As most industrial wastewater is complex, there is a strong
tendency for it to contain multiple elements. However, as of 2018, 64.38
% of all adsorption studies reported involved a single element system,
33.15 % for adsorption of organic chemical compounds, while only 2.47
R. Thotagamuge et al. Environmental Nanotechnology, Monitoring & Management 16 (2021) 100562

% involved multi-element system which is considerably low (Neris et al., produced. The bamboo powder was then pyrolysed using a furnace
2019). (Thermconcept HTK 16/18, Germany) at 500 ◦ C for 4 hrs with heating
In this study, locally available bamboo was used (Gigantochloa) as rate set at 4 ◦ C min− 1 and under constant nitrogen flow (flow rate of
starting material which was turned into charcoal via pyrolysis. The 20 mL min− 1) (Rosli et al., 2018). After pyrolysis, the charcoal was
bamboo charcoal (BC) was chemically modified by using HCl activation activated using 1 M HCl at a ratio of 1:2 (W/W) and refluxed at 80 ◦ C for
and then impregnated with copper. The modified activated bamboo 4 hrs (Chiang and Yeh, 2014; Alguacil et al., 2018). The activated
charcoal was named as MAC in this study. Characterisations of the MAC charcoal was centrifuged at 4000 rpm using a TD58 centrifuge machine
includes the functional group analyses, consistency, surface (YingTai Instrument), and this was followed by multiple washing with
morphology, and surface area. Thereafter, the sample was subjected to distilled water. The HCl-activated charcoal was then treated with 10 %
batch adsorption to treat industrial wastewater, targeting 15 elements at weight CuCl2⋅2H2O in aqueous medium, sonicated for 4 hrs, followed by
once. The performance of MAC was quantified and compared with multiple distilled water washing. Lastly, the copper-treated HCl-acti­
currently commercially available charcoal for industrial wastewater vated charcoal was heated in a furnace at 400 ◦ C for 2 hrs and this
treatment. copper-impregnated HCl-activated charcoal is abbreviated as MAC. The
main reason of heating the copper-impregnated activated carbon at
2. Materials and method 400 ◦ C is to convert the copper ions to copper oxide. (Manasrah et al.,
2018).
2.1. Preparation of wastewater sample The samples were characterised using a Fourier-transform infrared
spectroscopy (Agilent Cary 630 FTIR spectrometer, 16 scans, resolution
The sample used in this experiment was treated industrial waste­ 2 cm− 1) and a BET machine (Micrometrics ASAP 2020 surface area and
water obtained from a wastewater treatment facility in the Belait district porosity analyser, US). Powder X-ray diffraction (XRD) pattern was
of Brunei Darussalam. The source of the wastewater is from cleaning collected from 20 to 800 in 2-theta using a Shimadzu XRD-7000 Maxima,
activities in the oil and gas industry. The collected wastewater was pale Japan with Cu Kα as radiation (wavelength of λ = 1.54 Å) at 40 kV and
yellow in appearance, with strong odour caused by the fouling of sur­ 30 mA, respectively. The surface morphology and element compositions
factants and hydrocarbons. were studied by JEOL JSM7610 FSEM-DEX machine.
The industrial wastewater was characterised by the parameters of
pH, COD, BOD5 and suspended solids before spiked with the standard 2.3. Brief experimental procedures for batch adsorption
and the results were 7.93, 44.0 ppm, 82.3 ppm and 112.0 ppm, respec­
tively. The heavy metal content of the wastewater is shown in Table 1. All experiments were carried out using 0.1 g adsorbent per 50 mL of
The two elements Mn and Fe identified to be significantly high. The wastewater sample in Erlenmeyer flask, and the mixture was subjected
wastewater was spiked with Inorganic Ventures multi analyte custom to shaking at 150 rpm for 3 hrs (unless stated otherwise) using an orbital
grade 21-elements ICP standard solution (100 ppm for each of the ele­ shaker (MIULab GS-20). The effects of pH (2.2 – 8.3), initial concen­
ments: Sb, Be, Ca, Co, Fe, Li, Mn, Ni, Sr, Ti, Zn, As, Cd, Cr, Cu, Pb, Mg, tration, and contact time (1 – 6 hrs) were investigated. The pH of the
Mo, Se, Tl and V). The final concentration of the spiked wastewater is samples was adjusted using 0.1 M HNO3 and 0.1 M NaOH, and pH
summarised in Table 1 and this table was used for the adsorption measurement was obtained using Jenway 3310 digital pH meter. It was
experiment as a reference. The pH of the spiked wastewater was at 2.1. noted that some heavy metals can precipitate out of aqueous solution at
alkaline pH while this behaviour also depends on the concentration of
2.2. Preparation of adsorbents the cation. One such example is the complete precipitation of 1 ppm Fe
at pH of 4.5, while Cu can remain soluble at pH 7 up to 4 ppm (Pavlović
Two types of adsorbents were investigated in this study. Firstly, a et al., 2007). These are due to the formation of metal hydroxide, where
commercial activated charcoal, CAC was obtained by CIC whereas the the solubility is limited. Due to this precipitation phenomenon, the
second modified activated charcoal, MAC, was produced in the labora­ adsorption data of Fe (pH at 5.7 and 8), Cu (pH 8), Cr (pH 8) and Be (pH
tory. A local species of bamboo belonging to the genus of Gigantochloa 8) were omitted as adsorption experiment could not be determined
was used as the starting material to produce MAC. The outer skin of the accurately at these pHs while the rest of the elements are soluble at their
bamboo was peeled, cut into smaller pieces (dimension of 2 cm × 2 cm), level of the initial concentration (Pavlović et al., 2007; Santos et al.,
dried in an oven at 80 ◦ C until constant weight was obtained. A grinding 2012; Smedley and Kinniburgh, 2017; Kretzschmar, 2015; Boukhobza
machine (Retsch SM2000/695 Ups, Germany) was used for milling the and Crans, 2020; Veselý et al., 1989; Gad et al., 2016; Azhar et al.,
bamboo and coarse powder with particle size below 500 µm was 2017).
After adsorption, the adsorbent was separated from the mixture by
using a benchtop centrifuge (GMI HNSII Plus TD 51) spun at 4000 rpm.
Table 1
Concentration of heavy metal present in the wastewater and spiked wastewater. The supernatant was digested using the EPA 3015 test method. The
supernatant (45 mL) was digested in 5 mL of HNO3 in a digestion vessel
Concentration (ppm)
and loaded into the Microwave Reaction System (Anton Paar Multiwave
Element Wastewater Spiked wastewater 3000). After the digestion process, the samples were filtered using
Cd 0.00037 1.00037 Whatmann No.4 filter paper into a volumetric flask prior to analysis. The
Pb 0.00774 1.00774 heavy metal content was determined based on the APHA 3120 test
As 0.01107 1.01107 method using inductively coupled plasma (ICP) spectrometer (Thermo-
Cr 0.00430 1.00430
Cu 0.00396 1.00396
Scientific iCAP 7400 Duo MFC). Multiple wavelengths were initially
Fe 0.45907 1.45907 selected for the ICP analysis. Only the wavelengths that resulted in
Ni 0.00780 1.00780 calibration curves with correlation of determination (R2) between
Se 0.00480 1.00480 0.9989 and 0.9994 were used in identifying the elements. The selected
Zn 0.02230 1.02230
wavelengths for Cd, Pb, As, Cr, Cu, Fe, Ni, Se, Zn, Mn, Li, Be, Co, Mo and
Mn 3.34730 4.34730
Li 0.06022 1.06022 V were 228.802, 182.205, 193.759, 267.716, 327.396, 259.837,
Be 0.00000 1.00000 231.604, 196.090, 213.856, 257.610, 670.784, 313.042, 228.616,
Co 0.00037 1.00037 202.030 and 292.464, respectively.
Mo 0.00554 1.00554 The performance of the activated charcoals was quantified by using
V 0.01219 1.01219
the adsorption capacity, qe (mg g− 1), and the percentage removal (% R).

3
R. Thotagamuge et al. Environmental Nanotechnology, Monitoring & Management 16 (2021) 100562

These quantities are defined by equations (1) and (2), respectively.

V(Ci − Ce )
qe = (1)
m

Ci − Ce
%R = × 100 (2)
Ci

where Ci is the initial adsorbate concentration (ppm), Ce is the adsorbate

concentration at equilibrium (ppm), V is the volume (L), and m is the
mass of adsorbate (g).
The qe indicates the number of adsorbates adsorbed per gram of
adsorbent at equilibrium, while % R indicates the overall removal of
adsorbates based on the adsorbent dosage and adsorbate volume ratio at
a particular adsorbate concentration.

3. Results and discussion

3.1. Characterisation of the adsorbent

The functional group analysis of MAC is shown in Fig. 2a. The FTIR
spectra revealed twin peaks at 3444 cm− 1 and 3309 cm− 1, which are due
to the presence of Cu co-planarity, indicating an ionic interaction be­
tween the copper and activated charcoal, and thus confirms the
impregnation of copper (Chen et al., 2010; Majumdar et al., 2008). The
other functional groups that were observed were at 1561 cm− 1 (C– –C
stretching of alkenes and aromatic), 1367 cm− 1 (aromatic CH),
1237 cm− 1 (–OH stretching of alcohol group), 987 cm− 1 (– – CH
− 1
bending), and 659 cm (Cu O stretching vibration) (Chen et al., 2010;
–
Daffalla et al., 2010).
The XRD spectrum is shown in Fig. 2b. The broad diffraction peak at
20-30◦ is attributed to the amorphous nature of the charcoal structure
commonly observed in activated charcoal (Liu et al., 2010). The
appearance of two strong peaks at 32.3◦ and 39.7◦ correspond to the
(0 0 2) and (1 1 1) crystal lattice of CuO (Majumdar et al., 2008; Zhu,
2019; Basu et al., 2019). Hence, XRD results confirmed the Cu impreg­
nation with activated charcoal.
The SEM micrograph (Fig. 2c) shows that there were pores
throughout the particle and the bright dots represent the Cu on the
surface. According to the SEM data, the Cu is unevenly spread on the
activated charcoal.
As shown in Fig. 2d, the EDX results also confirm that Cu element
was present on the surface of MAC. The elemental composition of C, O,
Cl and Cu by mass were at 68.11, 11.60, 8.87 and 11.06 % respectively
and this confirms that the targeted impregnation percentage of 10 % by
mass was achieved in MAC whereas the element composition of charcoal
(inactivated and uncoated charcoal) presented only C and O with 85.46
and 14.54% by mass.
N2 adsorption–desorption (BET measurement) was carried out to
evaluate the surface area and porous details of the MAC. The BET
analysis revealed that the surface area, pore volume and pore size of
MAC are 5 m2 g− 1, 0.0082 cm3 g− 1 and 6.47 nm, respectively whereas
the BET results of CAC are 712 m2 g− 1, 0.4077 cm3 g− 1 and 2.26 nm,
respectively.

3.2. Effect of contact time

The effect of contact time is important for determining the duration

of the contact time require to achieve removal closed to equilibrium, and
Fig. 2. Characterisations of MAC by using (a) FTIR spectroscopy, (b) XRD, (c)
whether there is significant increase in removal performance at a unit of SEM and (d) EDX.
time interval. This information is particularly valuable to the industrial
treatment plant. The kinetics data is summarised in Fig. 3, where it can
be observed that 3 hrs contact time is sufficient for the adsorption of

4
R. Thotagamuge et al. Environmental Nanotechnology, Monitoring & Management 16 (2021) 100562

Fig. 3. The effect of contact time on the removal of heavy metals from 50 mL spiked multi-elements wastewater using 0.1 g of (a) MAC and (b) CAC, while pH
adjusted to 5.7.

5
R. Thotagamuge et al.
most elements to achieve near-equilibrium adsorption condition for
MAC, while some elements (Mn, Pb, As, V, Mo & Li) did not reach
equilibrium for CAC, even after 6 hrs. In this case, MAC has better speed
performance when compared to CAC. The longer contact time for CAC to
reach near-equilibrium would imply an increase in the operating cost of
water treatment process at industries.
3.3. Effect of initial concentration
The effect of initial concentration was investigated by using a spiked
solution that has a slightly lower in concentration than the original so­
lution. This was achieved by diluting the spiked solution up to 2.5 times.
The effect of the initial concentration of the heavy metal is summarised
in Fig. 4, where dilution of the spiked solution did not result in any large
changes in qe for both MAC and CAC. However, there is an exception
with the adsorption of Mo using MAC, where dilution (DF = 2.5x) re­
duces the qe from 0.316 mg g− 1 to 0.162 mg g− 1, this is most likely due to
the slight increase of pH with dilution.
3.4. Effect of initial pH
The effect of pH is one of the most influential factors in adsorption
study, and the result is summarised in Fig. 5. Overall, MAC was observed
to give higher qe, for most of the elements, when compared to CAC.
Among the three pHs (2.1, 5.8 and 8.2), the best performance was
Fig. 4. The effect of the initial heavy metals concentration on the adsorption of 50 mL spiked multi-elements wastewater using 0.1 g (a) MAC and (b) CAC at
unadjusted pH at ~ 2.1.
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Environmental Nanotechnology, Monitoring & Management 16 (2021) 100562
observed at pH of 5.8. The order of qe in the removal of heavy metal (at
pH 5.8) was Mn > As > Cr > Pb > V > Be > Zn > Se > Cd > Ni > Co >
Cu > Mo > Li, where highest qe for adsorption of Mn was at
1.031 mg g− 1. This observation was most likely due to their higher
initial concentrations when compared to the rest of the heavy metals. A
higher value of qe means higher adsorbate loaded into the adsorbent that
is measured as per unit gram of adsorbent. The qe for highly hazardous
Cd, Pb, As, Cr and V were at 0.250, 0.460, 0.480, 0.467 and
0.391 mg g− 1, respectively. The lower qe of Cd is due to the competition
with Pb for the active sites on the surface of the adsorbent particles,
thereby reducing the uptake of Cd. Srivastava et. al. reported similar
behaviour in an adsorption study involving the use of kaolinite as an
adsorbent in a multi-element system (Srivastava et al., 2005). Srivastava
et. al. also reported the presence of Cu can induce similar suppression
effect for Cd uptake. At pH 5.8, Cu was also observed to be adsorbed by
MAC at qe of 0.093 mg g− 1. The ability of MAC to adsorb some Cu,
despite having Cu as its modifying agent is an advantage. At pH 8.2,
MAC performed moderately well with the qe for Pb, As and V at 0.431,
0.335 and 0.391 mg g− 1 respectively, while a huge decrease for Mn to
0.170 mg g− 1 was observed. A peculiar behaviour was observed for the
absorption of Mo, where qe is highest at pH of 2.1 (0.316 mg g− 1), and it
eventually drops at pH 5.7 (0.035 mg g− 1) and then increases again at
pH 8 (0.195 mg g− 1). This can be explained by the behaviour of Mo
being predominantly monomeric below pH 3, while it became dimeric
and polymeric in nature between pH of 3 to 7, and it reverts back to
R. Thotagamuge et al.
Fig. 5. Graphs showing the effect of pH on the qe of various heavy metals using (a) MAC, and (b) CAC (data of Cu, Cr and Be at pH 8, and Fe at pH 5 and 8
were omitted).
monomeric above pH of 7 (Tkac and Paulenova, 2008). Monomeric
species may diffuse through the pores and they are captured by the
active sites on the adsorbent when compared to the dimeric and poly­
meric forms.
As for CAC, it performed poorly at a pH below 8.1. At the pH of 8.1
the qe of CAC is lower than MAC, with exception to Zn and Co.
The qe of selected heavy metal using MAC and CAC are compiled in
Table 2 and compared with those reported in literature. There is no
adsorbent that is best in adsorption of all elements at once. One such
example is the Na-modified montmorillonite clay may be better in Pb
and Cu adsorption than MAC, however MAC has higher qe in adsorption
of Cd.
Although qe is a good performance indicator of the AC, however, it
does not reveal much about the residual heavy metal when the
adsorption is at equilibrium. This data is useful for wastewater man­
agement purposes to ensure that the target pollutants in the treated
water are within the discharge limit set by government agencies.
Therefore, the performance indicator (% R) is equally important because
it gives insights on the total amount of adsorbates that are removed from
an overall adsorption system. The effect of pH on the % R of the
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Environmental Nanotechnology, Monitoring & Management 16 (2021) 100562
adsorption system is shown in Fig. 6. The % R of As, Cr and Pb using
MAC (at pH 5.83) were above 96%, followed by Zn and V at 81.3 and
91.2% respectively. The CAC performed moderately well, however, only
at pH 8. The ability of MAC to perform moderately well at a wider range
of pH is an advantage over CAC.
4. Conclusion
This study has successfully fabricated modified-activated bamboo
charcoal, MAC, by impregnation and chemical activation, and the ma­
terial was characterised to evaluate its physicochemical properties. The
adsorbent, MAC was used in the investigation of the removal of multi-
element industrial wastewater sourced from cleaning activities in the
oil and gas industry.
The overall performance of MAC was then compared with commer­
cial activated charcoal, CAC. The MAC was observed to remove 9 out of
15 elements in the multi-element wastewater, and it reached near-
equilibrium within 3 hrs and longer contact time did not resulted in
significant increase in removal. The adsorption for CAC is slower and
some elements has not achieved equilibrium for CAC even after 6 hrs.
R. Thotagamuge et al. Environmental Nanotechnology, Monitoring & Management 16 (2021) 100562

Table 2
Comparison of selected multi-element adsorption using different adsorbents.
Experimental condition qe (mg/g) ref

Adsorbent Pb As Cr Cd Cu Zn Mn Mo V Co

MAC 0.1 g dose, pH 5.83, 0.460 0.480 0.467 0.250 0.093 0.392 1.031 0.035 0.453 0.226 This study
50 mL ~ 1 ppm multi-element
adsorbate, 3hrs shaking
At pH 2.17 0.012 0.023 0.004 0.009 0.000 0.000 0.048 0.316 0.131 0.009
At pH 8.33 0.431 0.335 0.000 0.042 0.000 0.001 0.170 0.195 0.391 0.027
CAC 0.1 g dose, pH 5.09, 0.049 0.000 0.000 0.000 0.020 0.001 0.032 0.000 0.046 0.000 This study
50 mL ~ 1 ppm multi-element
adsorbate, 3hrs shaking
At pH 2.27 0.055 0.045 0.055 0.052 0.263 0.076 0.000 0.080 0.024 0.036
At pH 8.08 0.427 0.377 0.000 0.324 0.413 0.451 0.875 0.010 0.289 0.291
Montmorillonite 0.1 g dose, pH 2.0, 10 mL 100 ppm 0.673 – – 0.058 0.055 – – – – - (Abdellaoui et al.,
multi-element adsorbates, 3hrs 2019)
shaking
Na-modified 1.894 – – 0.202 0.144 – – – – - (Abdellaoui et al.,
montmorillonite 2019)
Ca-modified 1.888 – – 0.084 0.067 – – – – - (Abdellaoui et al.,
montmorillonite 2019)
Urban soil deposit 5.0 g dose, pH 2, 250 mL of 0.579 – 1.618 0.246 0.280 – – – – - (Markiewicz-
5–20 ppm multi-element Patkowska et al.,
adsorbates, 16 hrs shaking 2005)
Urban soil deposit 5.0 g dose, pH 7, 250 mL of – – – 2.294 – 0.718 – – – - (Markiewicz-
5–20 ppm multi-element Patkowska et al.,
adsorbates, 16 hrs shaking 2005)

Fig. 6. The effect of pH on the % R of heavy metal from a 50 mL spiked multi-elements wastewater using 0.1 g of (a) MAC, and (b) CAC (data of Cu, Cr and Be at pH
8, and Fe at pH 5 and 8 were omitted).

8
R. Thotagamuge et al.
The optimum pH for adsorption for the MAC is at 5.83, in which MAC
outperformed CAC in terms of higher qe at about the same pH. The MAC
also perform moderately well at pH ~8, while CAC only performing well
at pH ~8. This highlights the effectiveness of MAC a wider range of pH
over CAC. The four most concerning heavy metals (Cd, Pb, As and Cr)
were also removed at appreciated rate by the MAC. With consideration
of the performance in term of speed and effectiveness over wider range
of pH, it is concluded that the overall performance of the MAC is higher
than CAC, and MAC exhibits its strong potential as industrial adsorbent
for removal of heavy metals in wastewater treatment.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
Authors are grateful to chemical sciences and environmental life
sciences in Universiti Brunei Darussalam for the assist in terms of the
usage of machines for experimental work in this study.
The work described in this paper was supported by University Brunei
Darussalam research grants (Grants no: UBD/RSCH/1.9/FICBF/2021/
010, UBD/RSCH/1.9/FICBF/2021/008, UBD/RSCH/1.9/FICBF(b)/
2018/02, and UBD/RSCH/URC/NIG/2.0/2019/001).
Author contributions
Roshan Thotagamuge, Abdul Hanif Mahadi, Chee Ming Lim, M.R.R.
Kooh, Amanina Shofry, Yong Yung Khiong designed the work and wrote
the paper. Abigail Jan, Masanizan Abu, Alifatul Haziqah Abu Hanipah
carried out the experimental work under supervision of Roshan Thota­
gamuge, Abdul Hanif Mahadi, Chee Ming Lim, M.R.R. Kooh and Yong
Yung Khiong. All the authors reviewed the manuscript.
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