Journal of Water Process Engineering 10 (2016) 39–47

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Journal of Water Process Engineering

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

A review on potential usage of industrial waste materials for binding

heavy metal ions from aqueous solutions
Md. Juned K. Ahmed, M. Ahmaruzzaman ∗
Department of Chemistry, National Institute of Technology Silchar, Silchar 788010, India

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

Article history: Presence of toxic and recalcitrant heavy metal ions in industrial effluents is a major environmental con-
Received 12 August 2015 cern. These fatal metal ions are not only hazardous in exceeding concentrations but due to the property of
Received in revised form 21 January 2016 biomagnification it is urgent to look for the plausible solutions. This review article is an attempt to gather
Accepted 26 January 2016
the research findings attempted in yester years for the removal of such metals from aqueous solutions
Available online 8 February 2016
by using waste materials from industries, such as blast furnace sludge, slag and flue dust, fly ash, black
liquor lignin, and red mud. Studies have been complied keeping various efficiency influencing parameters
Keywords:
such as optimum dose, contact time, initial concentration of metal ions, and many more in consideration.
Adsorption
Industrial wastes This article also tries to summarize the various problems and shortcoming of the work carried so far and
Heavy metals attempts to explore the feasible suggestions.
Sludge © 2016 Elsevier Ltd. All rights reserved.
Fly ash
Lignin
Red mud

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2. Treatment techniques for heavy metal–laden wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3. Utilization of industrial wastes for the elimination of heavy metals from wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4. Summary of adsorption of heavy metals on industrial wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.1. Sludge, blast furnace slag, and flue dust . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.2. Fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.3. Lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.4. Red mud . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5. Influencing parameters of heavy metal adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.1. Effect of solution pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.2. Effect of initial concentration and interaction time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.3. Effect of ionic strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
5.4. Effect of particle size of industrial waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
6. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

∗ Corresponding author.
E-mail addresses: md a2002@rediffmail.com, md a2002@yahoo.com (M. Ahmaruzzaman).

http://dx.doi.org/10.1016/j.jwpe.2016.01.014
2214-7144/© 2016 Elsevier Ltd. All rights reserved.
40 Md.J.K. Ahmed, M. Ahmaruzzaman / Journal of Water Process Engineering 10 (2016) 39–47
1. Introduction
Environmental pollution of water and its control is an emerging
global issue that need to be addressed for healthy environment.
In recent years, the rapid growth of industries such as fertilizer,
metal plating, tanneries, mining, and textile industries [1,2] have
increased the discharge of toxic heavy metals into water streams,
particularly in developing countries. Dyes, paints, printing, photog-
raphy, paper, and petroleum refining industries also contributes to
the presence of heavy metals in effluents. Elements with atomic
weights in the range 63.5–200.6 and specific gravity greater than
5.0 comes under the purview of heavy metals. Unlike organic
contaminants, heavy metals are not biodegradable and tends to
accumulate in living organisms. Many heavy metal ions are known
to be toxic and carcinogenic; and causes various diseases and dis-
orders in human, animals, and aquatic life. Hence, they need to be
removed prior to their discharge in water streams. In the treatment
of industrial wastewaters, the toxic heavy metals of utmost con-
cern include chromium (Cr), cadmium (Cd), and lead (Pb), zinc (Zn),
copper (Cu), and nickel (Ni), arsenic (As) mercury (Hg). Therefore,
stringent regulations are adopted worldwide and several regula-
tory bodies have set the maximum limits for the discharge of toxic
heavy metals into natural water bodies. However, in actual prac-
tice such norms are often violated and consequently the ecosystem
gets affected. Table 1 displays the permissible limits of various toxic
heavy metals and their corresponding health effects [3–5].
The effective treatment of wastewater contaminated with toxic
heavy metal ions has grown into an important research area. Chem-
ical precipitation followed by coagulation has been widely used for
the elimination of heavy metals from wastewater. However, this
practice generates large volumes of sludge comprising minor quan-
tity of heavy metals. Membrane filtration can remove metal ions but
its use is limited due to high cost [6]. Adsorption is one of the most
effective wastewater treatment technique that industries practice
for the sequestration of toxic metals from the effluents. Activated
carbon is the most widely used adsorbent and it shows good metal
ion adsorption capacities [7–11]. However, the high cost of prepara-
tion limits its use in wastewater treatment. Over the last few years,
a large number of researchers have investigated the utilization of
industrial wastes for the uptake of heavy metals from wastewater
[12].
This review article focuses on a summary of information relating
to the utilization of industrial waste materials as adsorbents for
the sequestration of heavy metals from wastewater. The review
also discusses some critical issues and shortcomings on the use of
industrial wastes as low-cost adsorbents.
2. Treatment techniques for heavy metal–laden wastewater
There are numerous techniques available for the treatment of
heavy metal contaminated wastewater, such as microbial system,
electrochemical process, and chemical precipitation, coagulation,
photocatalytic degradation, and ion-exchange, adsorption, mem-
brane filtration, etc. These techniques can be broadly divided into
three categories: biological, chemical, and physical. Currently, no
single process is capable of effective treatment due to the com-
plex nature of the effluents. In real-time usage, a combination of
various techniques are generally used for the treatment purpose.
The advantages and disadvantages of different techniques adopted
for the treatment of heavy metal–laden wastewater are shown in
Table 2 [13].
3. Utilization of industrial wastes for the elimination of
heavy metals from wastewater
In recent times, the removal of heavy metals from wastewater
is gaining widespread attention among researchers. Amid various
available techniques, the adsorption process can be considered as
a simple and effective process for the removal of heavy metals.
Industrial wastes are one of the low-cost adsorbents utilized for the
remediation of heavy metal contaminated wastewaters. Industrial
waste materials are generated as by-products or left-over materials
in industrial processes. They often requires minimal processing to
enhance their adsorptive capacities. Due to their abundant local
availability, inexpensive nature, and high performance they are a
good alternative to commercial adsorbents. Industrial wastes such
as blast furnace slag, sludge, fly ash, lignin, and red mud have been
utilized for the removal of toxic heavy metals from wastewater.
4. Summary of adsorption of heavy metals on industrial
wastes
Herein, the important aspects and overview of some of the
industrial wastes for the sequestration of toxic metals from
wastewater is presented. Table 3 illustrates the summary of heavy
metal adsorption on industrial wastes.
4.1. Sludge, blast furnace slag, and flue dust
Sludge is a dried waste produced in electroplating and effluent
treatment plants, which consists of insoluble metal hydroxides and
salts. Blast furnace slag and flue dust are industrial by-products
from steel plants. These industrial wastes have been widely used by
researchers for the removal of heavy metals from aqueous media.
Bhatnagar et al. compared the potential of various indus-
trial wastes such as carbon slurry, blast furnace slag, dust,
and sludge for the removal of Pb(II) from aqueous solutions
[14]. The adsorption of Pb(II) follows the order: blast furnace
sludge > dust > slag > carbonaceous adsorbent. The adsorption of
Pb(II) and Hg(II) on non-viable activated sludge biomass were stud-
ied in batch and fixed-bed system [15]. The sorption data well-fitted
to pseudo-second order kinetics and Langmuir isotherm models.
The highest adsorption equilibrium, optimum pH, and tempera-
ture for Pb(II) were 0.387 mmol g−1 (Co = 1.206 mM), pH of 3.5, and
30 ◦ C; while for Hg(II) were 0.097 mmol g−1 (Co = 0.099 mM), pH
of 5.8, and 20 ◦ C, respectively. Continuous-flow column data well-
fitted to Thomas kinetic model. The basic oxygen furnace waste
generated in steel plant has been used as a low cost adsorbent
for the removal of Pb(II) from aqueous solution [16]. The effect of
pH, adsorbent dosage, and initial metal ion concentration, contact
time, and temperature on adsorption process was studied in batch
experiments. Results of the equilibrium experiments showed that
the solution pH was the key factor affecting the adsorption char-
acteristics. Optimum pH for the adsorption was found to be 5 with
corresponding adsorbent dosage level of 5 g L−1 . The equilibrium
was achieved within 1 h of contact time. Kinetics data were best
described by pseudo-second order model. The maximum uptake
was 92.5 mg g−1 .
The blast furnace sludge (BFS), by-product and waste mate-
rial of steelmaking industry was utilized as an adsorbent for
Ni(II) ions removal from aqueous solution [17]. The equilib-
rium data were found to follow the Freundlich isotherm slightly
better than Langmuir isotherm. The thermodynamic parameters
revealed spontaneous and favorable adsorption of Ni(II) on BFS.
The observed adsorption capacity was 90.91 mg g−1 , which indi-
cates a good potential of BFS for its use in aqueous sorption
system. In another investigation with sewage sludge, adsorbents
were produced by two different procedures via microwave irra-
diation: (1) by one single pyrolysis stage (SC); (2) by chemical
activation with ZnCl2 (SZ) [18]. Subsequently, they were used for
adsorption of Cu(II) from aqueous solutions. The effects of various
experimental parameters such as pH and temperature were inves-
 Md.J.K. Ahmed, M. Ahmaruzzaman / Journal of Water Process Engineering 10 (2016) 39–47 41

Table 1
Permissible discharge limits of industrial effluents and health hazards of toxic heavy metals [3–6].

Metals Permissible limits for industrial effluents discharge (mg L-1 ) Health hazards

Indian std. WHO std.

Inland surface water Public sewers Inland surface water

Arsenic 0.2 0.2 – Carcinogenic, causes liver tumours, and gastrointestinal effects
Mercury 0.01 0.01 – Excess dose may cause headache, abdominal pain, and diarrhoea, paralysis,
and gum inflammation, loosening of teeth, loss of appetite, etc.
Cadmium 2 1 0.1 Carcinogenic, cause lung fibrosis, and dyspnoea
Chromium (total) 2 2 – Suspected human carcinogen, may cause lung tumors
Copper 3 3 0.05–1.5 Long term exposure causes stomach ache, irritation of nose, and mouth, eyes,
headache, etc.
Nickel 3 3 – Causes chronic bronchitis, reduced lung function, and cancer of lungs
Zinc 5 15 5.0–15.0 Causes short-term illness called “metal fume fever” and restlessness
Lead 0.1 1 0.1 Suspected carcinogen, anaemia, muscle and joint pains, kidney problem, and
high blood pressure

Table 2
Technologies/techniques available for heavy metal−laden wastewater treatment [13].

Treatment technologies Advantages Disadvantages

Biological treatment
Electrochemical treatment
Coagulation/flocculation
Photochemical degradation
Ion exchange
Adsorption
Membrane filtration
Feasible in removing few metals Technology need to be established and commercialized
Rapid process but effective for particular metal ions High energy cost and generation of by-products
Economically feasible High sludge formation
No sludge formation Generation of by-products
Good removal of wide range of heavy metals Absorbent material requires regeneration and disposal
problems
Flexibility and simplicity of design, ease of operation, and Adsorbent requires regeneration
insensitivity to toxic pollutants
Good removal of heavy metals Sludge production and very expensive

tigated in a batch-adsorption technique. The results showed that
the adsorption of Cu(II) was maximal at pH 5.0. The kinetic study
demonstrated that the adsorption process followed the pseudo-
second order kinetics. The experimental adsorption isotherm data
were well-fitted with Langmuir model and the maximum adsorp-
tion capacity of Cu(II) were found to be 3.88 and 10.56 mg g−1 for
SC and SZ respectively, in the solution of pH 5.0.
Oh et al. had studied the removal of As(III) and As(V) by steel
making slag under acidic conditions [19]. The low-cost adsorbent
shows 95–100% removal efficiencies at pH 2. Around 75–80% of
arsenic adsorbed was bound to amorphous iron oxide of the slag.
The bounded arsenic have lower chances of desorption unless
subjected to reducing and complex condition. Thus, these met-
allurgical waste are good alternative to carbonaceous adsorbents
for the removal of toxic heavy metals ions. Adsorptive removal of
Cu(II) from aqueous solution by basic oxygen furnace slag (BOFs)
which was activated by the mechanochemistry process was also
investigated [20]. Results showed that in low concentration, the
optimum condition for removal was found to be 0.5 g adsorbent
on the treatment of 1000 mg L−1 adsorbate. The Cu(II) removal rate
could reach 99.9% by the precipitation and adsorption effect. Lang-
muir isotherm and pseudo-second order kinetics more accurately
describe the adsorption process. When the pH of solution was less
than 3.5, it was thought that hydrogen bond and dipole force on
the surface of adsorbents dominated the Cu(II) removal.
Coal dust was utilized for the competitive sorption of Cu(II) and
Ni(II) ions from aqueous solutions [21]. Variation of the working
parameters such as pH, contact time, and adsorbent dose, metal
ion concentrations and temperature were done in a range to opti-
mize ideal conditions for the adsorption of ions from a binary metal
solution containing Cu(II) and Ni(II) in a batch mode. Second order
kinetics was fitted well for bi-component adsorption and Lang-
muir isotherm strongly supported the mechanism. Co-existence
of the ions affected the adsorption capacity and showed antago-
nistic manner in comparison to the single-metal. Waste gas sludge
(BOS sludge), which is an end-waste from steel making process was
employed as a novel adsorbent to study adsorption phenomena on
real acid mine drainage (AMD) [22]. Batch experiments were con-
ducted as function of initial solution pH and adsorbent loading to
study the performance of BOS sludge in removing copper and zinc. A
high pH-promoted adsorption and removal of the heavy metal ions
was not only due to ion-exchange or adsorption, but also partly due
to co-precipitation effect. The treatment of AMD demonstrated that
about 100% of Cu and 97% of Zn were removed from solution.
4.2. Fly ash
Fly ash are residues generally obtained from combustion of
coal. It has potential applications as an adsorbent for wastewa-
ter treatment and can be an alternative to commercial adsorbents.
However, its performance is governed by its origin and chemical
treatment. Fly ash constitutes high percentage of silica (60–65%),
alumina (25–30%), magnetite and maghemite (6–15%). In general,
the low adsorption capacity of raw fly ash is enhanced by physi-
cal and chemical treatment [23]. The removal of heavy metals by
utilizing fly ash have been established by various researchers. The
exploitation of fly ash for the sequestration of heavy metals from
wastewater was reported way back in 1975 by Gangoli et al. [24].
Mohan and Gandhimathi performed the removal of Zn(II), Pb(II),
Cd(II), and Cu(II) ions from municipal solid waste leachate using
coal fly ash [25]. The fly ash concentration required to achieve max-
imum heavy metal removal was found to be 2 g L−1 with removal
efficiencies of 39, 74, 42, and 71% for Cu, Pb, Zn, and Cd, respectively.
Cancrinite-type zeolite synthesized from fly ash (ZFA) were utilized
for the removal of Pb(II), Cu(II), Ni(II), and Zn(II) from aqueous phase
[26]. It is found that the maximum exchange level (MEL) follows
the order: Pb(II) (2.530 mmol g−1 ) > Cu(II) (2.081 mmol g−1 ) > Ni(II)
(1.532 mmol g−1 ) > Zn(II) (1.154 mmol g−1 ). Comparison with pre-
vious studies shows that the MEL of ZFA is higher than the
commonly used natural zeolites; and it is also comparable to (or
higher than) several synthetic zeolites and ion exchange resins.
42 Md.J.K. Ahmed, M. Ahmaruzzaman / Journal of Water Process Engineering 10 (2016) 39–47

Table 3
Summary of adsorption of heavy metals on industrial wastes.

Heavy Industrial waste materials Adsorption capacity Ref.

metal (mg g−1 )
As such Modified

As(III) Slag 3.39 [19]

Ferric ion-loaded red mud 5.25 [54]
As(V) Slag 6.37 [19]
Fly ash-coated chitosan 19.10 [37]
Ferric ion-loaded red mud 7.92 [54]
Red mud-derived Fe3 O4 NPs 0.40 [55]
Cd(II) Coal fly ash 0.089 [25]
Lignin 0.226 mmol g−1 [39]
Lignin 137.14 [40]
Kraft lignin 0.073 mmol g−1 [44]
NaOH-treated fly ash 30.21 [30]
TiO2 /fly ash 35.80 [32]
Hydrothermally-modified fly ash 87.72 [35]
Iron oxide-activated red mud 0.116 [58]
Cr(VI) Kraft lignin 0.213 mmol g−1 [44]
Kraft lignin 0.227 mmol g−1 [45]
Fly ash porous pellets 0.440 mmol g−1 [28]
Fly ash-coated chitosan 36.22 [37]
Lignin-based resin 57.68 [47]
Cu(II) Coal dust 21.74 [21]
Sludge 0.028 [22]
Coal fly ash 0.048 [25]
Lignin 0.360 mmol g−1 [39]
Lignin 87.05 [40]
Kraft lignin 0.053 mmol g−1 [44]
Pyrolytic sludge 3.88 [18]
ZnCl2 -activated sludge 10.56 [18]
Zeolite from fly ash 2.081 mmol g−1 [26]
Hydrothermally-modified fly ash 221.0 [29]
TiO2 /fly ash 21.0 [32]
Hydrothermally-modified fly ash 56.50 [35]
Fly ash-coated chitosan 28.65 [37]
H3 PO4 -activated lignin 136.0 [43]
Amino and sulfonic-functionalized lignin 0.71 mmol g−1 [48]
Acid-treated red mud 5.35 [53]
Ni(II) Sludge 90.91 [17]
Coal dust 20.41 [21]
Coal fly ash 4.50 [31]
Lignin 0.102 mmol g−1 [39]
Zeolite from fly ash 1.532 mmol g−1 [26]
Lignin-derived activated carbon 14.02 [46]
HCl-treated red mud 6.76 [57]
Pb(II) Sludge 92.50 [16]
Coal fly ash 0.075 [25]
Fly ash 416.6 [36]
Lignin 0.432 mmol g−1 [39]
Activated sludge biomass 0.387 mmol g−1 [15]
Zeolite from fly ash 2.530 mmol g−1 [26]
Fly ash porous pellets 0.220 mmol g−1 [28]
NaOH-treated fly ash 2000.0 [30]
Ag–iron oxide/fly ash 526.50 [36]
Amino and sulfonic-functionalized lignin 0.260 mmol g−1 [48]
Alkaline methylamine lignin 60.50 [49]
Lignin−xanthate resin 64.90 [50]
HCl-activated red mud 6.03 [56]
Zn(II) Sludge 0.555 [22]
Coal fly ash 0.031 [25]
Lignin 0.172 mmol g−1 [39]
Kraft lignin 0.027 mmol g−1 [44]
Zeolite from fly ash 1.154 mmol g−1 [26]
Fly ash porous pellets 0.270 mmol g−1 [28]
NaOH-treated fly ash 18.87 [30]
Fly ash-coated chitosan 55.52 [37]

Itskos et al. carried out the comparative uptake study of
toxic elements from aqueous media by the different particle-size-
fractions of fly ash (FA) [27]. Each FA sample was separated into
six different size-fractions with a grain diameter range of: [(0–25),
(25–40), and (40–90), (90–150), (150–400), and (>400)] ␮m. The
different FA grain-fractions were evaluated in terms of their chem-
ical composition, pH, Loss on Ignition (LOI), and CaOf (%). Batch
adsorption experiments were then carried out, which indicate that
the various grain-fractions of the highly siliceous FA were more
efficient in precipitating Cr(VI), but less capable of retaining Cd, Cu,
and Ni, Pb and Zn ions. On the other hand, the high-Ca fly ashes were
proven to be more efficient in the uptake of Cd, Cu, and Ni, Pb and Zn,
but less in Cr(VI). The application of fly ash porous pellets as adsor-
bent for the removal of Pb(II), Zn(II), and Cr(III) ions from aqueous
 Md.J.K. Ahmed, M. Ahmaruzzaman / Journal of Water Process Engineering 10 (2016) 39–47
solution was also studied [28]. Adsorption isotherms were deter-
mined for agglomerated material using the Langmuir equation. The
adsorption capacity of fly ash pellets reached at 0.22 mmol Pb g−1
pellet, 0.27 mmol Zn g−1 pellet, and 0.44 mmol Cr g−1 pellet.
Mesoporous adsorbents were hydrothermally prepared from fly
ash in an alkaline condition with cetyltrimethylammonium bro-
mide as synthesis directing agent [29]. The removal of Cu(II) was
studied under equilibrium and dynamic conditions; and the influ-
ence of the Al:Si molar ratio were also considered. The equilibrium
data were fitted to Freundlich and Langmuir models and the models
parameters were evaluated. Class “F” fly ash (FA), collected from the
Central Heat and Power (CHP) Plant, Brasov (Romania) with oxides
composition SiO2 /Al2 O3 over 2.4 proved good adsorbent proper-
ties for the removal of Pb(II), Cd(II), and Zn(II) cations from mixed
solutions [30]. The optimum pH corresponding to the maximum
adsorption was found between 5.5 and 6.6. The results show high
efficiency, which follows the order Pb(II) > Zn(II) ≥ Cd(II).
The influence of pH (3–10), blend time (0.5–4 h), and the ini-
tial concentration of Cu(II) and Ni(II) ions (5–100 mg L−1 ) were
researched on adsorption/desorption of analyses elements from/to
the aqueous solutions by using coal fly ash [31]. Visa and
Duta developed a novel substrate (TiO2 /fly ash) for simultaneous
removal of heavy metals and surfactants [32]. The results indicate
efficient removal of Cu(II) and Cd(II), resulting waters that respect
the discharge regulations. The removal of heavy metals such as
Pb(II), Ni(II), and Cr(VI) from single and binary solutions have been
investigated onto thermal power plant fly ash [33]. Fly ash samples
(1:10 and 1:15) were prepared by CaCO3 and H3 PO4 treatment. The
adsorption process was performed for operational parameters such
as solution pH, adsorbent dose, contact time, and initial metal ion
concentration. The prepared fly ash samples demonstrate signifi-
cant metal removal capacities in the order Pb(II) > Ni(II) > Cr(VI).
Muñoz et al. studied the bonding of heavy metals, such as As(III),
Cu(II), and Cd(II), Hg(II), Ni(II), Pb(II), and Zn(II) ions on nitric acid-
etched coal fly ashes functionalized with 2-mercaptoethanol or
thioglycolic acid [34]. It was found that some metal(oid) ions (As, Ni,
Pb, and Zn) were coordinated through the mercaptan group, while
other metal(oid)s (Cd, Cu, Hg, and Mn) were apparently bonded to
oxygen atoms. Visa et al. [35] studied the effect of hydrothermally-
modified fly ash for the simultaneous removal of heavy metals
(Cu(II) and Cd(II)) and dyes (methylene blue). Class “F” fly ash
(oxide composition: SiO2 /Al2 O3 over 2.4) was modified with NaOH
and a cationic surfactant—hexadecyltrimethylammonium bromide
(HTAB). The kinetic and thermodynamic studies illustrate a good
adsorption capacity of the substrate based on the electrostatic
attractions between the substrate and Cd(II) and/or Cu(II) cations.
Fly ash-based composite (Ag–iron oxide/fly ash) were explored
for Pb(II) ion adsorption efficiency in a series of batch adsorption
experiments to study the effects of concentration, contact time, pH,
and adsorbent dose on the adsorption process [36]. Results indi-
cated that as-synthesized composite has high antibacterial capacity
and the metal ions uptake efficiency, as compared to fly ash parti-
cle. Furthermore, incorporation of Fe3 O4 NPs onto the fly ash make
it easily separable from a reaction system. Adamczuk and Kolodyn-
ska examine the effectiveness of fly ash coated by chitosan (FAICS)
as an adsorbent for the removal of Cr(III,VI), Cu(II), Zn(II), and As(V)
ions from aqueous solutions [37]. The adsorption capacities of FAICS
(8:1) for Cr(III,VI), Cu(II), Zn(II), and As(V) were 36.22, 28.65, 55.52,
and 19.10 mg g−1 , respectively.
4.3. Lignin
Black liquor is an industrial waste generated from paper and
pulp manufacturing industry. Lignin, extracted from black liquor,
is a natural amorphous cross-linked resin that has been utilized for
the sequestration of heavy metals from aqueous solutions. It is a
43
three-dimensional aromatic polymer containing functional groups
such as aldehyde, benzyl alcohol, and carboxyl, hydroxyl, methoxy,
and phenolic groups [38]. The percentage composition of Lignin
are: C = 60.8, H = 5.8, and N = 1.3, S = 2.1, Ash = 5.5, and K = 0.24,
Na = 1.4, Ca = 0.06, and Mg = 0.01, Fe = 0.007 and Al = 0.03 [39].
Mohan et al. [40] investigated the utilization of lignin from
black liquor for the adsorption of Cu(II) and Cd(II) from aque-
ous solutions. The maximum adsorption capacities were 87.05
and 137.14 mg g−1 for Cu(II) and Cd(II), respectively. An overview
on the use of lignin, its conversion into chars and activated car-
bons for the mitigation of toxic pollutants from wastewater was
presented by Suhas et al. [41]. Lignin from black liquor was also
utilized for the sequestration of heavy metal ions, such as Pb(II),
Cd(II), and Cu(II), Ni(II) and Zn(II) [39]. The adsorption of metal ions
on lignin is in the order: Pb(II) > Cu(II) > Cd(II) > Zn(II) > Ni(II). The
adsorption of metal ions on deprotonated acidic sites (carboxylic
and phenolic) best explain the adsorption phenomena [39]. Several
processes including ion exchange, surface adsorption, and com-
plexation have been suggested by various researchers to explain
the mechanisms of metal adsorption by lignin. However, detailed
studies on understanding the exact mechanism of adsorption are
yet to be reported. The relative metal sorption ability of kraft
and organosolv lignins was examined as a function of solution
chemistry (pH, ionic strength, and sorbate-to-sorbent ratio) and
reaction time for the sorption of Cu(II) and Cd(II) ions [42]. Sorp-
tion of Cu and Cd increased with increasing pH and decreasing ionic
strength. Sorption capacity varied in the following order: softwood
organosolv lignin < hardwood organosolv lignin < hardwood kraft
lignin < softwood kraft lignin with sorption maximum of 21.5, 40,
66.7, and 80.6 ␮mol g−1 , respectively, for Cu; and 8.2, 18.3, 25.2,
and 28.7 ␮mol g−1 for Cd.
Kriaa et al. explored the removal of Cu (II) from water pollutant
with Tunisian activated lignin prepared by phosphoric acid activa-
tion [43]. It was found that the maximum surface area reached at
the carbonization temperature of 500 ◦ C in H3 PO4 activation; and
the prepared activated lignin showed a surface area of 463 m2 g−1 .
The adsorption capacity of copper by these carbons (activated
lignin), of order 136 mg Cu g−1 for the important target compound
used as a water toxic pollutant (Cu (II)) compares well and even
favorably for other activated carbons and adsorbent materials. The
ability of Kraft lignin, a waste product of paper production, for
removing copper, zinc, cadmium, and chromium ions from water
was investigated [44]. The studies were conducted by a batch
method to determine equilibrium parameters. The adsorbed heavy
metal ions followed the order: Cr(VI) » Cd(II) > Cu(II) > Zn(II). The
influence of other ions such as Ni(II), Cd(II), and Pb(II) on Cu(II)
adsorption by Kraft lignin was also evaluated. In another equilib-
rium study, the sorption of Cr(VI) onto Kraft lignin as an adsorbent
was performed [45]. The best two-parameter isotherm is equally
Langmuir and Dubinin–Radushkevich isotherm. From three param-
eter isotherms Redlich–Peterson isotherm proved to be the best.
Generally, Redlich–Peterson isotherm was found to be the best
representative for Cr(VI) adsorption on the sorbent.
The activation of lignin by KOH (lignin:KOH = 3:1) with
pre-carbonization method (activation temperature = 750 ◦ C and
activation time = 1 h) produced low-cost activated carbon with high
surface area [46]. Lignin-derived activated carbon was utilized
for the removal of Ni(II) from aqueous solution and the adsorp-
tion capacity as predicted by Langmuir model was 14.02 mg g−1 .
The increase in solution pH favored the adsorption phenomena.
Adsorption of hexavalent chromium on a lignin-based resin (LBR)
was carried out by Liang et al. [47]. Isotherm modeling studies
demonstrated that the Freundlich isotherm model gave a better fit
to the experimental data, and the maximum adsorption capacity
was 57.681 mg g−1 . A three-step removal mechanism of Cr(VI) by
LBR was proposed, including electrostatic attraction of acid chro-
44 Md.J.K. Ahmed, M. Ahmaruzzaman / Journal of Water Process Engineering 10 (2016) 39–47
mate ion by protonated LBR, reduction of Cr(VI) to Cr(III), and bond
formation of Cr(III) with the oxygen-containing functional groups.
Ge et al. synthesize bi-functionalized lignin with amino and sulfonic
groups (ASL) and utilized it for the adsorption of Cu(II) and Pb(II)
ions [48]. Results indicated that the biosorbent showed excellent
performance for metals even from low pH solutions. The adsorption
kinetics and isotherms could be described well with pseudo-second
order and D–R model, respectively.
A Mannich base biosorbent (AML) was prepared by graft-
ing alkaline lignin (AL) from black liquor with methylamine and
formaldehyde for the removal of Pb(II) ions [49]. Kinetic adsorption
suggested AML possessed fast adsorption for Pb(II) and followed a
second-order model. Adsorption equilibrium results indicated AML
had a maximum uptake of 60.5 mg g−1 for Pb(II), which was 4.2-fold
higher than AL. In a different research, a new lignin−xanthate resin
(LXR) was synthesized by a two-step reaction from alkaline lignin
and carbon disulfide [50]. Batch adsorption including equilibrium
isotherms, kinetics, and the effects of pH, dosage and temperature
on the adsorption of Pb(II) ions by LXR were systematically stud-
ied. LXR shows a 4.8 times higher adsorption capacity than alkaline
lignin at 30 ◦ C that is attributed to the incorporation of xanthate
groups and porous structure.
4.4. Red mud
Red mud is an industrial waste material (bauxite processing
residue) generated in the production of alumina. It is formed when
bauxite ores are subjected to caustic leaching. 1–2 t of red mud
is generated per ton of alumina produced in a typical Bayer pro-
cess plant [51]. The chief constituents of red mud are fine particles
of silica, alumina, and calcium, iron, titanium oxides, and hydrox-
ides. Because of high surface reactivity of red muds, they have been
exploited for the removal of toxic heavy metals from wastewater.
Batch experiments were conducted to investigate the competi-
tive removal of water-borne Cu, Zn, and Cd by a CaCO3 -dominated
red mud [52]. The results show that the water-borne Cu had a
higher affinity to the red mud, as compared to the water-borne
Zn and Cd. The major mechanism responsible for the preferential
retention of Cu by red mud was the formation of atacamite. Red
mud waste material was also utilized in the remediation of Cu(II)
ions polluted water [53]. The experimental investigation shows
that activated red mud has a adsorption capacity of 5.35 mg g−1
for Cu(II) ion. A laboratory study was conducted to investigate
the ability of ferric ion-loaded red mud (FRM) for the removal of
arsenic species from water [54]. For an initial arsenic concentra-
tion lower than 0.3 mg L−1 , the FRM with a dosage of 1 g L−1 was
able to reduce As(III) at pH 7 below 10 ␮g L−1 , the maximum con-
taminant level (MCL) of arsenic in drinking water set by the World
Health Organization. In the case of As(V) removal, FRM was also
particularly effective in reducing the initial arsenic concentration
value of 1 mg L−1 at pH 2, below the MCL requirement of arsenic for
drinking water.
Akina et al. [55] have utilized waste red mud for the synthe-
sis of Fe3 O4 nanoparticles and its implication for As(V) removal
from both synthetic and natural (underground) water samples. The
investigation revealed the influence of pH, contact time, and ini-
tial concentration of As(V) in the adsorption process. The natural
(underground) water sample containing 1570 ␮g L−1 of As(V) and
280 ␮g L−1 of As(III) was efficiently reduce to total arsenic con-
centration of 15.30 ␮g L−1 . Batch adsorption study was conducted
to investigate the removal efficiency of Pb(II) from the aqueous
solutions by using HCl-activated red mud (ARM) [56]. Adsorp-
tion experiments were conducted as a function of adsorbent dose,
equilibrium pH, contact time, and initial lead concentration. The
percentage removal was found to increase gradually with decrease
of pH and maximum removal was achieved at pH 4. The adsorption
process was best described by pseudo-second order kinetics and
Langmuir isotherm with higher R2 values.
In another study, red mud (RM) sorbents (RM0.05–RM1),
obtained by varying HCl concentration (0.05–1 mol L−1 ), were
tested for the removal of Ni(II) ions [57]. Ni(II) sorption increased
with the increase of initial pH from 2 to 4, while at pH > 4
it depended only on sorbent material. A radical drop of max-
imum sorption capacities was associated with the increase of
acid concentration to 0.25 mol L−1 , whereas additional rise to
1 mol L−1 caused minor fluctuations. In another study, iron oxide
activated red mud was used for the removal of Cd(II) from
aqueous solution [58]. The optimized adsorption parameters for
Cd(II) were: pH = 6.0, dose = 6.0 g L−1 , contact time = 90 min, initial
concentration = 400 ␮g L−1 , and temperature = 300 K. The Lang-
muir monolayer adsorption capacities were 117.64, 116.28, and
107.53 ␮g g−1 ; and the Freundlich adsorption capacities were 3.83,
3.68, and 3.07 ␮g g−1 at 293, 298, and 308 K, respectively.
5. Influencing parameters of heavy metal adsorption
5.1. Effect of solution pH
The pH of metal solution has a distinct impact on the uptake
of metal ions onto various industrial wastes. It has been observed
that with the increase in solution pH adsorption increases up to
a certain limit, and thereafter, it decreases. The effect of pH can
also be explained in terms of pHzpc (point of zero charge) of the
adsorbent. The surface of the adsorbent is positively charged at
pH < pHzpc , negative at pH > pHzpc , and neutral at pH = pHzpc . Even
though the adsorbent surface is negatively charged at pH > pHzpc ,
still the adsorptive uptake of metal ions increases provided the
metal species are positively charged or neutral. However, when
both the adsorbent surface and metal species become negatively
charged, there will be a distinct decrease in the adsorption. Fig. 1
illustrates the effect of solution pH on the uptake of Ni(II) from
aqueous solutions [46].
5.2. Effect of initial concentration and interaction time
The effect of initial metal ion concentrations on the adsorp-
tion capacities of various industrial wastes have been explained by
several researchers. Usually, with the increase in initial metal ion
concentration, adsorption capacity is increased due to enhanced
driving force that overcome all mass transfer resistance between
the liquid and solid phases. However, a decrease in the percent-
age removal of the metal ion is observed due to larger extent of
competing metal ion in comparison to limited active sites of the
adsorbents. Interaction time between the industrial waste and the
metal ion also influences the removal efficiency of heavy metals.
The effect of initial concentrations (100–500 ␮g L−1 ) on Cd(II)
adsorption by iron oxide activated red mud (IOARM) is shown
in Fig. 2 [58]. The maximum adsorptive removal was 94.12% for
100 ␮g L−1 , which decreased to 87.50% for 400 ␮g L−1 . The interac-
tion time was optimized for the maximum uptake of Cd(II) in the
range 15–150 min. The adsorption of Cd(II) onto IOARM comprised
of two stages (Fig. 3). At the initial stage, instantaneous adsorption
takes place by external surface adsorption and in the final stage
the adsorption rate diminishes (diffusion into pores). The percent
removal of Cd(II) increased from 36.77 to 94.12% with the increase
in interaction time from 15 to 90 min. Further increase in time up
to 150 min, percent removal increased to 97.06%.
5.3. Effect of ionic strength
Ionic strength is a property of the solution by the virtue of which
the affinity between the solute and the solution phase gets affected.
 Md.J.K. Ahmed, M. Ahmaruzzaman / Journal of Water Process Engineering 10 (2016) 39–47 45

Fig. 1. Effect of solution pH on Ni(II) adsorption; Co = 10 mg L−1 , T = 30 ± 1 ◦ C [46].

In most of the cases, there is a decrease in adsorption with increas-

ing ionic strength of aqueous media. This may be due to changes in
metal activity or in the properties of electrical double layer. When
two phases (industrial wastes and metal species) in aqueous solu-
tion are in contact, they are sure to be enclosed by an electrical
double layer due to electrostatic interaction. This is in accordance
with the theory of surface chemistry. The effect of different com-
petitive ions like phosphate (PO4 3− ), nitrate (NO3 − ), and sulphate
(SO4 2− ) on Cr(VI) adsorption was investigated under varying metal
concentrations [59]. It was inferred that percentage removal of
Cr(VI) decreased with the increase in concentrations of competitive
ions. The affinity of these anions for activated red mud followed the
order: PO4 3− > SO4 2− > NO3 − . The influence of ionic strength on the
sequestration of Zn(II) from aqueous media using fly ash was also
studied. It was reported that at a lower ionic strength and under
same solution pH, higher percent removal of Zn(II) was achieved
Fig. 2. Effect of initial concentration on Cd(II) adsorption [58].
[60].

5.4. Effect of particle size of industrial waste

The particle size of the industrial waste employed also effects

the adsorption rate. With the decrease in particle size there will
be an increase in surface area of the material, and consequently,
adsorption may increase. The effect of particle size of tea waste on
the adsorption capacity of Cu(II) was investigated [61]. A Cu(II) per-
cent removal of 41, 53, and 57% was observed for tea waste particle
mean sizes of 1250, 925, and 575 ␮m, respectively. Batch adsorp-
tion experiments were performed to study the influence of particle
size of bagasse fly ash on the sequestration of Pb(II) and Cr(VI) from
aqueous solutions [62]. The particle sizes under examination were,
100–150, 200–250, and 300–350 ␮m. The operational parameters
were: adsorbent dose = 10 g L−1 , temperature = 30 ◦ C, pH 6 and 5,
Fig. 3. Effect of interaction time on Cd(II) adsorption [58].
shaking time = 80 and 60 min, for Pb(II) and Cr(VI), respectively.
The percentage removal of Pb(II) and Cr(VI) were 99.9, 95.0, and
46 Md.J.K. Ahmed, M. Ahmaruzzaman / Journal of Water Process Engineering 10 (2016) 39–47
88.0%, which corresponds to particle size, 100–150, 200–250, and
300–350 ␮m, respectively.
6. Discussion
The utilization of industrial wastes as an adsorbent for the
removal of heavy metal ions from wastewater have been exten-
sively studied. However, authors found several problems and
shortcomings that need to be addressed. In majority of research
articles, the characterization results are not interpreted in co-
relation with the adsorptive performance. Adsorption of metal ion
is pH dependent and therefore, the change in solution pH dur-
ing the adsorption process need to be studied, apart from effect of
initial pH. The equilibrium data were usually co-related with con-
ventional adsorption isotherms, such as Langmuir, Freundlich, and
a few others. Nowhere in literature, has any attempt been made
to formulate new isotherm based on experimental findings. The
kinetic data were fitted as usual to pseudo-first order equation or
its variant ignoring the practical utility of the kinetic parameters
for the design of pilot plant. Literature survey shows that most
of the studies investigate the adsorption of heavy metal in batch
mode, a few studies highlight in fixed-bed system. A smaller num-
ber of studies have reported the competitive adsorption of heavy
metal on various industrial wastes. The competitive metal adsorp-
tion should also be addressed in presence of organic and other toxic
contaminants for wide scale commercial applications. Advanced
studies should be directed towards the discovery of components in
the precursor responsible for the development of active functional
groups, porosity, and effective surface area. Moreover, combina-
tion of treatment methodologies should also be encouraged to
cater the need of hybrid wastewater treatment. A comprehensive
cost-benefit analysis of the adsorbents developed from industrial
wastes, which considers all aspects of costing (related to raw mate-
rials processing, labor cost, etc.) is still awaited.
The key features essential for the selection of an industrial waste
need to be formulated so as to develop better adsorbents for max-
imum heavy metal removal efficiency. In this regard, inputs on the
treatment techniques and process design for achieving the desir-
able characteristics of the adsorbent are also vital. Hence, extensive
research in this direction needs to be explored for better utility in
practical applications. A detail study on the binding mechanism
of heavy metals onto industrial waste is essential for proposing
a convincing adsorption mechanism. Extensive research in this
regard will explore a new dimension of adsorption studies. Regen-
eration and disposal of heavy metal-loaded waste material in a
greener way is encouraged in an attempt to safeguard the envi-
ronment. For better wastewater treatment technologies, the use
of nanomaterials and nanocomposites for hybrid functions, such
as oxidation/reduction, catalytic activity, and adsorption may be
investigated. Besides, the use of magnetic nanocomposites should
be encouraged, which will facilitate separation from aqueous solu-
tions in wide scale applications. However, the issues of secondary
pollution (due to use of nanomaterials) also need to be checked in
an eco-friendly way for a clean ecosystem.
7. Conclusion
Herein, the utilization of industrial wastes for the sequestration
of heavy metals from wastewater have been explored. Indus-
trial wastes such as sludge, fly ash, lignin, and red mud have
been proved to be promising material for the treatment of heavy
metal–laden wastewaters. The adsorptive uptake of metal ions
could be modelled by Langmuir, Freundlich, Redlich–Peterson, and
Dubinin–Radushkevich isotherms. The factors such as adsorbent
dose, particle size, and interaction time, initial metal ion concen-
tration, ionic strength of competitive ions, and solution pH affects
the adsorption process. Usually, the percent removal of metal ions
increases with the increase in adsorbent dose, interaction time,
and pH whereas, it decreases with the increase in particle size and
ionic strength. However, the above trend may change depending
on the different metal ions and waste materials. There is a favor-
able pH range for every heavy metal in which maximum adsorption
takes place. An attempt to develop highly efficient adsorbents from
industrial wastes with all the desirable characteristics may be con-
sidered as the best alternative to expensive commercial adsorbents.
This in turn will also facilitate waste minimization. Advanced stud-
ies in this regard will pave the way for the realization of heavy
metal–laden wastewater treatment in commercial scale.
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