ChemBioEng Reviews - 2017 - Azimi - Removal of Heavy Metals From Industrial Wastewaters A Review

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Removal of Heavy Metals from Industrial Wastewaters:
A Review
Arezoo Azimi[1], Ahmad Azari[1],*, Mashallah Rezakazemi[2], Meisam Ansarpour[1]
Abstract
Heavy metals like arsenic, copper, cadmium, chro- may accumulate in the human body by means of
mium, nickel, zinc, lead, and mercury are major the food chain. Various methods have been devel-
pollutants of fresh water reservoirs because of their oped and used for water and wastewater treatment
toxic, non-biodegradable, and persistent nature. to decrease heavy metal concentrations. These tech-
The industrial growth is the major source of heavy nologies include membrane filtration, ion-exchange,
metals introducing such pollutants into different adsorption, chemical precipitation, nanotechnology
segments of the environment including air, water, treatments, electrochemical and advanced oxidation
soil, and biosphere. Heavy metals are easily processes. In this review, the methods as well as
absorbed by fishes and vegetables due to their high their mechanisms and efficiency are discussed.
solubility in the aquatic environments. Hence, they
Keywords: Heavy metal, Recycle, Reuse, Wastewater
Received: July 01, 2016; revised: December 14, 2016; accepted: December 15, 2016
DOI: 10.1002/cben.201600010
1 Introduction ting high because of increased industrial wastes [5]. The toxic
ions enter the food chain and then the human body [11–13].
Fresh potable water resources are the most vital reservoirs in Once they accumulate in an organ to more than standard lim-
the world. It is important for all living organisms on earth to its, they may cause serious health-related diseases [14]. For
have access to adequate clean water. Available water resources example, too much Zn may cause health problems like skin ir-
are decreasing due to world population growth, developing ritations, vomiting, and stomach cramps [15, 16], high concen-
industries, and long-time droughts. Besides over-exploitation, tration of Ni bring cancer of lungs and kidney [15, 17]. Since
contamination of natural water resources with refractory pollu- wastewater is the main source of diseases and hinders the sus-
tants discharging from industries make the water shortage tainable growth for the human population, it needs to be
worse even in rich water areas [1–3]. It is possible to store rain- treated to degrade the pollutants to less toxic forms [18–20].
fall streams or storm water to control water shortage for a short Heavy metals remain in the human body persistently for a long
time, but the best way is to treat and reuse wastewaters (pol- time since they are not biodegradable [21, 22]. The standard
luted water coming from industries, businesses, and residences) concentration limits regulated by the United States Environ-
[4]. mental Protection Agency (EPA) are shown in Tab. 1.
Wastewaters almost always contain toxic pollutants coming
from any anthropogenic industries, such as mining or agricul-
tural plants that lack environment-friendly techniques, or natu-
ral forces such as volcanoes, earthquakes or storms [5, 6]. The-
ses pollutants are categorized into three major groups: organic,
inorganic, and biological particles [5]. The focus of this study is
on inorganic groups containing heavy metal ions. Removing —————
[1]
Arezoo Azimi, Dr. Ahmad Azari (corresponding author), Meisam
heavy metals is necessary because they are toxic substances
Ansarpour
with carcinogenic nature that should not to be discharged Department of Chemical Engineering, Faculty of Oil, Gas and
directly into the environment [5, 7, 8]. Petrochemical Engineering, Persian Gulf University, Bushehr
Heavy metal ions are elements from the fourth period of the 7516913817, Iran.
periodic table, mostly chromium (Cr), cobalt (Co), nickel (Ni), Email: azari.ahmad@gmail.com, azari.ahmad@pgu.ac.ir
copper (Cu), zinc (Zn), arsenic (As), and sometimes lead (Pb), [2]
Dr. Mashallah Rezakazemi
mercury (Hg) [9, 10]. Heavy metal ions can naturally be found Department of Chemical Engineering, Shahrood University of
in the environment, but these days their concentration is get- Technology, Shahrood, 3619995161, Iran.
www.ChemBioEngRev.de ª 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ChemBioEng Rev 2017, 4, No. 1, 37–59 37
21969744, 2017, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cben.201600010 by Indian Institute Of Tech - Roorkee, Wiley Online Library on [13/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Table 1. Drinking water contaminants, their MCL, and toxicities [23, 24].
Contaminants MCLa) or TTb)[mg L–1] Potential health effects from long-term exposure above the MCL (unless specified as short term)
Cd 0.005 Kidney damage
Cr(total) 0.1 Allergic dermatitis
Cu TT action level = 1.3 Short-term exposure: Gastrointestinal distress; long-term exposure: liver or kidney damage
As 0.010 Skin damage or problems with circulatory systems and may have increased risk of getting cancer
Pb TT action level = 0.015 Infants and children: delays in physical or mental development, children could show slight deficits in
attention span and learning abilities; adults: kidney problems; high blood pressure
Ni 0.20 Dermatitis, nausea, chronic asthma, coughing, human carcinogen
Zn 0.80 Depression, lethargy, neurological signs, and increased thirst
Hg 0.00003 Rheumatoid arthritis, and diseases of the kidneys, circulatory system, and nervous system
a)
Maximum contaminant level (MCL): the highest level of a contaminant that is allowed in drinking water; MCLs are enforceable standards; b)treatment
technique (TT): a required process intended to reduce the level of a contaminant in drinking water.
Many researchers have worked on developing efficient treat- 2 Conventional Methods

ment technologies. Treatment technologies are mainly based for Wastewater Treatments
on physicochemical, electrochemical or advanced oxidation
processes. Physicochemical processes include membrane filtra- For many years, researchers have used different methods for
tion, chemical precipitation, ion-exchange, and adsorption. removing heavy metals from different wastewaters that can be
Electrocoagulation, electroflotation, and electrodeposition are classified as electrochemical treatments (electrocoagulation,
categorized under the name of electrochemical methods. elector-floatation, and electrodeposition), physicochemical pro-
Photocatalysis is one of the advanced oxidation processes. cesses (chemical precipitation, Ion exchange), adsorption (acti-
Beside all these, nanotechnology is a practical approach in vated carbon, carbon nanotubes, and wood sawdust adsorb-
treating wastewaters, too. Among all these possible methods, ents), or current methods (membrane filtration processes,
those with cost-effective, environment-friendly and no further photocatalysis processes, and nanotechnology). These methods
pollutants features are the favorites. and their advantages as well as limitations in industrial applica-
On the other hand, there are biological processes such as the tions are outlined in this section.
activated sludge process that are widely used in the treatment
of industrial and municipal waste-
waters. Biological processes are
Wastewater
mostly considered to be cheaper
treatment
than physical and chemical meth- methods
ods. Biological processes are usu-
ally aimed at removing the readily
Electrochemical treatments Physicochemical
biodegradable chemical oxygen de- processes
mand (COD), or relatively readily
hydrolysable substances, but are
Electrocoagulation
not specifically designed to remove Chemical
heavy metals [25]. Precipitation Ion Exchange
In this article, first all the men- Electroflotation Electrodeposition
tioned methods except biological
processes were reviewed and then
their procedure, industrial applica- Adsorption Current methods
tion as well as pros and cons are
mentioned. Finally, some case
studies are added that have used Activated Carbon Nano Wood Membrane Photocatalysis
filtration processes Nanotechnology
these methods before. All the Carbon Tubes Sawdust
mentioned methods are summar-
ized in Fig. 1. Figure 1. Tree diagram for wastewater treatment methods.
2.1 Electrochemical Treatments Al3 þ þ 3OH Ð AlðOHÞ3 (3)
Electrochemical treatments of wastewaters have not received Al(OH)3 acts as adsorbent and/or trap to separate heavy
great attention so far because of the need of large capital metal ions [33]. Fig. 2 shows the SEM (scanning electron
investments and expensive electricity supply [26, 27]. The microscopy) image of metallic sludge for the removal of Mn2+
electrochemical technologies are in a situation that they are and Co2+ ions from aqueous solutions using EC with Al elec-
not only comparable with other technologies in terms of trodes [37]. Fig. 3 shows the SEM images of the anode after
costs, but they also are more efficient and more compact. In electrocoagulation using AC (alternative current) and DC
some cases, the electrochemical technologies may be an (direct current) for the removal of cadmium from water using
essential step that cannot be neglected in treating waste- zinc as anode and cathode [35]. In Fig. 4, the SEM images of
waters containing refractory pollutants [28]. In this review,
three major electrochemical treatment technologies including
electrocoagulation (EC), electroflotation (EF) and electrode-
position are studied.
2.1.1 Electrocoagulation
Electrocoagulation (EC) is a simple and productive technology

used in wastewater treatment industries [29]. It was never
accepted as a reliable method due to its poor systematic reactor
design and problems of electrode reliability [26]. Recently, EC
became known as a small-scale wastewater treatment method
with improved technical strategies [28]. A wide variety of dis-
turbing pollutants is removed by electrolysis [30].
EC with aluminum and iron electrodes was first patented in
the United States in 1909 [31]. The whole EC process was con-
ducted by applying a low electric current to the waste solution.
Figure 2. SEM image of metallic sludge for the removal of Mn2+
In the simplest form, the EC reactor is an electrolytic cell which and Co2+ ions from aqueous solutions using EC with Al elec-
has one anode and one cathode which are commonly known as trodes [37].
sacrificial electrodes [29, 32]. These electrodes may be made of
similar or different kinds of materials. Iron and aluminum are
among the most popular materials [30]. At the beginning, pol- a)
lutants such as heavy metal ions are retained in the wastewater
by their surface electrical charges or hydrogen bond. After
introducing the electric field, the electrostatic charges holding
the suspended or emulsified pollutants together are neutralized
and they will then be coagulated from the aqueous phase.
Heavy metal particles bond together like small magnets to form
a mass that is called sludge or floc [30, 32]. The flocs produced
through EC compared with those of other techniques are large
with less bound water and are more stable. The advantage is
that these flocs can easily be removed by further processing like
filtration which sometimes are cost-intensive but easily oper-
ated [27, 28]. The procedure can be summarized as follows: b)
– Anode dissolution;
– OH– and H2 generation at the cathode;
– Electrolytic reactions at electrode surfaces;
– Coagulant adsorption on colloidal pollutants;
– Colloids removal by sedimentation or flotation [28].
For Al electrodes, the main reactions include:
Anode: Al Ð Al3 þ þ 3e (1)
3
Cathode: 3H2 O þ 3e Ð H2 þ 3OH (2)
2
Figure 3. SEM images of the anode after electrocoagulation (a)
Al3+ and OH– ions formed at the electrode surfaces react in by AC and (b) by DC for the removal of cadmium from water
the wastewater: using zinc as anode and cathode [35].
metal ions with hydroxide iron and steel flocs as absorbents. In
a) this study, an electrochemical cell with thirty iron and stainless
steel rods with 50 mm length and 5 mm diameter was used.
The electrodes were connected serially and only the two outer
ones had contact to the positive and negative poles. The results
showed that at current densities of 6 and 8 mA cm–3, optimum
lead removal was 96.7 and 95.2 %, respectively. At the same
current densities, optimum zinc removal was 93.8 % and
93.3 %, respectively. It was showed that the removal efficiency
increases with an increase in current density due to the increas-
ing formation rate of hydroxide and steel flocs.
EC is known as an environment-friendly technique because
it uses electrons as reagents that are clean and eliminate the
b) need of adding new chemical additives. Since there is no need
of chemical additives, the possibility of formation of further
pollutants and generation of flocs is largely reduced [28]. Note
that EC cannot remove infinitely soluble particles, but is has
the advantage of removing even small colloidal particles
because the applied electric field sets them into faster motion
[27, 28]. Tab. 2 shows the removal efficiency and energy con-
sumption that are influenced by some parameters such as met-
al’s concentration, type of electrode, pH, etc.
2.1.2 Electro-Floatation
Figure 4. SEM images of the Al alloy anode (a) before and (b)
after EC process to remove chromium [36]. Electroflotation (EF) has recently been applied to wastewater to
remove heavy metal pollutants [53–62] since other methods
the Al alloy anode before and after the EC process to remove for treating wastewaters usually do not operate efficiently for
chromium are presented [36]. The results showed that the opti- very dilute solutions (concentrations below 50 mg m–3) [63].
mum removal efficiency of 98.2 % was achieved using an Al Elmore reported the very first usage of EF in mineral ores in
alloy anode at a current density of 0.2 A dm–2 at a pH of 7.0 1904 [64–66]. EF became popular because of its adaptability,
[36]. Furthermore, Fig. 5 illustrates the SEM image of the simplicity in design and operation, environmental compatibil-
sludge produced in the batch and continuous EC process to ity, low running costs, and its small and compact units [67].
remove zinc from rinse water [34]. Because of its various features, EF can be used in a wide range
of industries, e.g., treating oil from oil-water emulsions
[68–73], groundwater disinfection [74], apple juice and food
processing effluents [75–77], colloidal and suspended particles
[78–80], swage water and pit waters [81, 82].
EF separates pollutants by floating them to the surface of the
liquid phase. The separation occurs through three basic parts.
First, pollutants are attracted to a cell or reactor that has two
electrodes and a power supply [83]. The overall reaction hap-
pening in the cell will be water electrolysis that releases oxygen
and hydrogen into the solution:
2H2 O2 fi O2 þ 2H2 (4)

Figure 5. SEM image of the sludge produced in the batch and
Heavy metals will adhere or adsorb on the oxygen and
continuous EC process to remove zinc from rinse water [34].
hydrogen molecules whereby the emulsified particles will be
destabilized and flocs will be formed [63, 68]. The second step
Ganesan et al. [38] once used an electrolyte cell consisting of is a separation for settling or flotation of generated foam and
a 1.0-L Plexiglas vessel with magnesium as the anode and four settled flocs. The third step is removing collected pollutants by
stainless steel (commercial grade) sheets of the same size as a filtration methods [67, 84].
cathode. In all the experiments 2 mg L–1 of Mg was used. The The performance of an EF cell is evaluated by the pollutant
optimal removal efficiency of 97.2 % was achieved at a current removal efficiency and the power consumption, where the pol-
density 0.05 A dm–2 at pH 7.0. lutant removal efficiency is dependent on the size of the bub-
An experiment conducted by Mansoorian et al. [39] showed bles formed during electrolysis and the power consumption
that electrocoagulation can effectively reduce high amounts of depending on the cell design ,electrode materials as well as the
Table 2. Removal efficiency of heavy metals treatment by EC.
Metal Initial metal Type of Electrode pH Contact time Removal Current density Ref.
concentration [mg L–1] electrode configuration [min] [%]
Cr 17.1 Fe-S 304 N.A 6.9 30 97 50 A m–2 (DC) [40]

–2
Cr 50 Al-S 304 N.A 5 30 15 50 A m (DC) [40]
–2
Ni 17.1 Fe N.A 6.9 30 98 50 A m [40]
Cr, Cu 50 Al-Al-Al Parallel 4 15 99.9 0.8 A [41]
Zn 50 Al-Al-Al Parallel 4 15 83 0.8 A [41]
Cr 50 Al-Al-Al N.A 8 15 58 0.8 A [41]

–2
Cu, Ni, Zn 250 Fe Vertical 5.5–5.7 50 96 15 mA cm (DC) [42]
–2
Mn 250 Fe Vertical 5.5–5.7 50 72.6 15 mA cm (DC) [42]
–2
Cr, Cu, Ni Cu:45; Cr:44.5; Ni:39.4 Fe-Al N.A 3 20 100 10 mA cm [43]
–2
Cu, Zn Cu:33.3; Zn: 20.4 Fe-Fe Vertical 9.56 45 96 4 mA cm (DC) [44]
–2
Ni 57.6 Fe-Fe Vertical 9.56 45 98 4 mA cm (DC) [44]
–2
Cr 93.2 Fe-Fe Vertical 9.56 45 100 4 mA cm (DC) [44]
Cr 100 Al-Al N.A 5 24 90.4 [45]
Cu, Zn, Ni Cu: 12; Zn: 20; Ni: 20 Al-Fe N.A N.A 60 > 95 N.A [46]
Fe 25 Al-Al N.A 7.5 35 99.2 0.4 A m–2 (DC) [47]
Cr 8000 Mild S Parallel 5.91 50–60 99 1000 mA [48]
Cr N.A Fe-Fe N.A 8 5 100 7.94 mA cm–2 [49]
Cu, Zn 1000 Al-Al Vertical >7 5 100 N.A [33]
Ni 1731 Al-Fe N.A N.A 180 52 N.A [50]
Cu 1530 Al-Fe N.A N.A 180 90 N.A [50]
Cr 400 Al-Fe N.A 4 180 99 N.A [50]
N N.A Fe Parallel 3 15 97.8 60 A m2 (DC) [37]
Zn N.A Al Parallel 5 25 96.7 60 A m2 (DC) [37]

–2
Cr 204 N.A 2.5 25 h 99.5 1600 mA m [51]
–2
Zn 3.2 Fe-Fe Serial N.A 30 95.2 6 mA cm [39]
–2
Pb 9 Fe-Fe Serial N.A 30 96.7 6 mA cm [39]
–2
Zn 3.2 Fe-Fe Serial N.A 40 93.3 8 mA cm [39]
–2
Pb 9 Fe-Fe Serial N.A 40 93.8 8 mA cm [39]
Cr 14.70 SSS N.A 1.84 70 100 7.4 A (DC) [52]

–2
Cd 20 Zn N.A 7 N.A 94.1 0.1 A dm (AC) [35]
–2
Cd 20 Zn N.A 7 N.A 97.8 0.2 A dm (AC) [35]
–2
Cd 20 Zn N.A 7 N.A 98.0 0.3 A dm (AC) [35]
–2
Cd 20 Zn N.A 7 N.A 98.1 0.4 A dm (AC) [35]
–2
Cd 20 Zn N.A 7 N.A 98.3 0.5 A dm (AC) [35]
–2
Cr 5 anode: Al alloy N.A 7 N.A 99.6 0.5 A dm (DC) [36]
cathode:
galvanized iron
operating conditions [83]. Operating conditions are mostly results obtained from some research works using EF to remove
affected by current density, pH, and type of electrode. The heavy metals from wastewater are shown in Tab. 3.
Table 3. Removal of heavy metals by EF.
Metal Initial metal concentration [mg L–1] pH Contact time [min] Removal [%] Solution Ref.
Cu 50 5 60 99 Without electrolyte [85]

–1
Cu 500 5 60 99 Sodium sulfate (2 g L ) [85]
Ni 100 6 300 37 Without electrolyte [85]

–1
Ni 100 6 300 81 Sodium sulfate (5 g L ) [85]
Cu 3.5 5.5 N.A 98.26 Chabazite [86]
Ni 2 5.5 N.A 98.6 Chabazite [87]
Zn 2 5.5 N.A 98.6 Chabazite [87]
Cu 474 8–10 N.A 99.99 CTABr [87]
Ni 3.3 8–10 N.A 98.50 CTABr [87]
Zn 167 8–10 N.A 99.97 CTABr [87]
Cu 12.7 6.7 N.A 85 Trien [88]
Ni 5.87 7 N.A 70 Trien [88]
Cr 58.8 N.A. N.A 95 Hydrotalcite [89]
Cu 60 8–10 N.A 97 Zeolite [90]
Zn 50 6 N.A 99 Zeolite [91]
Zn 50 9 N.A 96 Zeolite [91]
Cu 500 5 N.A 97 Zeolite [91]
Cr 50 4 N.A 98 Surfactin-105 [92]
Zn 50 4 N.A 100 Lycheny-sin-A [92]
Zn 50 7-9 N.A 100 SDS [93]
Fe 50 7.8 15 98 Sulfates [54]
Pb 50 7.8 15 >98 Sulfates [54]
Ni 50 7.8 5 98 Sulfates [54]
Cu 50 7.8 15 98 Sulfates [54]
Zn 600 7.8 10 93 Sulfates [54]
Zn 50 7.8 10 > 99 Sulfates [54]
Cd 50 15 99.5 Sulfates [54]
Ni 100 7.8 10 99.7 Polymetallic solution [54]
Cu 100 7.8 10 98.8 Polymetallic solution [54]
Zn 100 7.8 10 99 Polymetallic solution [54]
Cd 100 7.8 5 98.8 Polymetallic solution [54]
Pb 100 7.8 ~2 100 Polymetallic solution [54]
Pb 100 7.8 15 > 81 Acetates [54]
Zn 100 7.8 15 99.5 Acetates [54]
To overcome the limitations of the processes mentioned some technical issues in the way of commercialization of non-
above, some investigators combined EC and EF, so it leads to aqueous solutions like low current efficiency, cell heat balance
higher removal efficiency compared with using one alone. This and corrosion of cell components [101]. Electrodeposition of
combined method is a more safe and effective way to remove aqueous solutions containing chelating agents like EDTA, NTA
pollutants [28]. The combination of EC and EF is called elec- and citrate is another interesting case [94]. These chelating
trocoagulation-flotation (ECF). This method reaches better agents are useful because they bind with heavy metals cations
removal percentages. Different experiments were carried out to to reduce the formation of insoluble salts [94] and increase
investigate the effects of the operating conditions on the recovery efficiency due to producing stronger complexes with
removal of heavy metals. Da Mota et al. [63] used ECF to metal ions [96]. So there will be no need of traditional separa-
remove heavy metals from synthetic solutions. The experimen- tion methods [94]. An experiment was conducted by Wulan
tal results revealed that it was feasible to remove up to 97 % of and Hariyadi [102] in a batch system using two types of elec-
the Pb and Zn by ECF with a total energy consumption of trodeposition reactors (partitioned reactor and single chamber
14 KWh m–3 under optimum conditions of pH = 10.0 and a reactor), a copper plate cathode size, a graphite anode, and
current density of 350 A m–2. applied DC of 5 V. The results showed that the partitioned
reactor performed better than the single chamber reactor with
a 26.892 % decrease of the nickel concentration in catholyte, a
2.1.3 Electrodeposition current efficiency of 88.17 %, and a specific energy of
5.2 kWh kg–1 nickel.
Electrodeposition is a practical and efficient method among the Different removal percentages achieved by changing operat-
electrochemical processes for the recovery of heavy metals ing parameters are shown in Tab. 4.
[94, 95]. Electrodeposition is advantageous because no further
reagents are necessary, no sludge will be produced during the
process, it is highly selective and low-cost as well [96, 97]. It 2.2 Physico-Chemical Processes
transforms dissolved metal ions into solid particles by deposi-
tion on ionic conductors (cathode and anode) [96] to protect 2.2.1 Chemical Precipitation
them from corrosion [98]. Electrodeposition is a one-step clean
method [99] based on reduction and Oxidation of heavy metal Chemical precipitation is a simple, easily automated treatment
ions in a cell consisting of one anode, a cathode, an electrolyte method. This treatment method is widely used in removing
cell, and a current source [96, 98]. Heavy metals are reduced heavy metals from wastewaters [104]. Chemical precipitation
and electroplated onto the cathode [98, 100]. The reaction is as needs a lot of chemicals to reduce metal ions to an acceptable
follows [95, 99]: limit for discharge [105], but it sometimes fails to reach this
point [106, 107]. These chemicals will be a large source of fur-
Mn þ þ ne fi M (5) ther pollution.
In chemical precipitation processes, chemical precipitant
The final size and distribution of electrodeposits depends on agents react with heavy metal ions and change them into
the nucleation of deposits and their growth [98]. The anodes insoluble solid particles [15, 108]. The solid phase will be sepa-
are preferred to be insoluble or inert [96, 98], otherwise they rated from the solution by sedimentation or filtration [91, 93].
will interfere with the recovery process of heavy metals [96]. A The reason that EC may be preferred to chemical precipitation
common side reaction at the anodes is [95, 96]: is that EC doesn’t need the addition of chemicals, leads to high-
er efficiencies, produces less sludge, and removes species that
4OH fi O2 þ 2H2 O þ 4e (6) chemical precipitation cannot remove [28]. The adjustment of
the pH is really important in this process; basic conditions with
Some competing reactions occur during the process. One of pH = 11 are preferred to improve the heavy metal removal
them is a reduction of H+ into hydrogen gas [96]: [14, 15].
After fine-tuning pH, the soluble metal ions are changed to
1
Hþ þ e fi H2 (7) the dissolved solid through reacting with a precipitant agent.
2
Some components should be reduced or oxidized to a valence
The efficiency of the whole process is influenced by the ini- to be precipitated directly. Phosphate can be separated by pre-
tial concentration of the waste solution, physical operational cipitation as aluminum or iron salts, and calcium chloride can
parameters such as temperature and pH and the presence of be used to separate fluorine. The method changes the ionic
complexing and chelating agents [95, 96]. Electrodeposition is equilibrium to form dissolved precipitates which can be simply
mainly used because it can be applied to non-aqueous solutions separated by sedimentation [15].
or solutions containing chelating agents as well. Either of these
2.2.1.1 Hydroxide Precipitation
solutions yields better removal of a pollutant than aqueous sol-
utions. Conventional aqueous solutions face some problems In this process, the incorporation of coagulants like iron salts,
like the liberation of hydrogen gas molecules, low thermal alum, and some polymers may improve heavy metal separation
stability, and narrow electrochemical window. Therefore, some- from wastewater. Soluble metal can precipitate as hydroxide by
times non-aqueous solutions are preferred. However, there are filtration or sedimentation. Alkaline agents can be used to
Table 4. Removal efficiency by electrodeposition.
Metal Deposition system Initial concentration [mg kg–1] pH Removal [%] Time [min] Current efficiency Ref.
Ni(II) Single chamber reactor 2402.19 mg L–1 4.87 21.925 4h 66.49 [102]
–1
Ni(II) Partitioned reactor 2402.19 mg L 4.2 26.892 4h 88.17 [102]
–1
Cu(II) N.A 110 mg L 3 79.18 220 24.88 [100]
–1
Cu(II) N.A 110 mg L 7 56.09 220 34.94 [100]
Cr Single cell 100 2.16 23 240 N.A [103]
Cu Single cell 1554 2.16 46.7 240 0.5 [103]
Ni Single cell 156 2.16 44.9 240 N.A [103]
Pb Single cell 74 2.16 21.4 240 N.A [103]
Zn Single cell 407 2.16 75.7 240 N.A [103]
Cr Single cell 100 1.89 12 240 N.A [103]
Cu Single cell 1554 1.89 92.1 240 0.65 [103]
Ni Single cell 156 1.89 48.1 240 N.A [103]
Pb Single cell 74 1.89 35.1 240 N.A [103]
Zn Single cell 407 1.89 77.8 240 N.A [103]
increase the pH of the water. Alkaline agents decrease the solu- M2 þ þ 2ðOHÞ Ð MðOHÞ2 (11)
bility of metal ions and therefore precipitate out of the solvent.
The hydroxide precipitation reaction is: M2+ and OH– represent the metal ions and the precipitant,
respectively [9, 13]. A variety of chemicals is used as precipi-
M2 þ þ 2OH Ð MðOHÞ2 (8) tants for chemical precipitation. The most common ones
employed are lime and calcium hydroxide which are available
M(OH)2 is insoluble. When the pH is less than the optimum in the most countries [14]. Lime (CaO) is usually preferred to
condition, a soluble metal complex forms: other precipitants, but a considerable high dosage is required
and it may not be successful to reduce heavy metals to the
M2 þ þ OH Ð MðOHÞ þ (9) standard limits due to inadequate settling and dissolution of
precipitates [110–112].
M2 þ þ OH þ nR Ð MðRÞn OH þ (10) Calcium hydroxide once was applied to a wastewater con-
taining Cd(II), Zn(II), and Mn(II) cations with an initial con-
centration of 150, 450 and 1085 mg L–1, respectively, and an
The existence of organic radicals affects the hydroxide pre- almost complete removal percentage (up to 99.5 %) was
cipitation. Moreover, some reagents usually are employed to achieved for the pH = 11 [113].
improve the hydroxide precipitation such as alkaline com- Research conducted by Chen et al. [110] was successful in
pounds [108]. removing Cu (II), Zn(II), Cr(III) and Pb (II) with an initial
concentration of 100 mg L–1 under optimum conditions
2.2.1.2 Sulfide Precipitation
(pH = 7–11) to reach the removal efficiencies of 99.37 to
The concept of sulfide precipitation is similar to hydroxide pre- 99.6 %.
cipitation. Both solubles and insolubles can be used to precipi- Ozverdi et al. [107] worked on Cu, Pb, and Cd removal from
tate metal ions. Sulfide is used to precipitate the heavy metal wastewater using Pyrite and synthetic iron sulfide SIS as
ions as metal sulfides and the sludge produced is removed from adsorbents. Tab. 5 shows the results achieved by changing pH,
the solution by gravity settling or filtration. The sulfide precipi- contact time, the initial concentration of metal and adsorbent,
tation process needs pre- and post-treatment and accurate con- and its dosage as parameters that affect adsorption. It was also
trol of reagent additions due to the toxicity of the sulfide ion observed that increasing adsorbent dosage and decreasing ini-
and H2S. The precipitation methods is conducted by tuning tial metal concentration for both kinds of adsorbents increases
compositions and other circumstances so that the ionic constit- the removal percentage.
uents that are to be separated alter from a soluble ionic to a sol- Besides all the advantages of this method, its expensive
id phase [108]. sludge production, increased costs of sludge disposal, poor set-
Heavy metal ions precipitate mostly in the form of hydroxide tling, and slow metal precipitation make it an impractical
[14, 109]: method [114–116].
Table 5. Removal of different metals with chemical precipitation using various adsorbents.
Metal Initial metal concentration [mg L–1] Initial pH Contact time [min] Adsorbent Dose adsorbent [g L–1] Removal [%] Ref.
Cu(II) 100 6 120 Pyrite 5 45.2 [107]
Cd(II) 100 6 120 Pyrite 20 34.2 [107]
Pb(II) 100 5 60 Pyrite 3 94.2 [107]
Cu(II) 100 6 45 SIS* 5 99.1 [107]
Cd(II) 100 6 120 SIS 20 68.5 [107]
Pb(II) 100 5 45 SIS 3 99.8 [107]
*Synthetic iron sulfide.
2.2.2 Ion Exchange ferred, such as styrene-divinylbenzene [129]. Another option are
gel-like ones that are sometimes more efficient and cost less.
Ion exchange treatment is based on a reversible interchange of Macropore resins have a sponge-like structure that provides bet-
ions between the solid and liquid phases [14]. The whole pro- ter physical stability and leads to more stress relief [119].
cedure begins with ion-exchange reactions, then the heavy met- Gel-like cation exchange resins like Lewatit S 100 are
al ions will be physically absorbed, and a complex is formed strongly acidic with beads of uniform size. Gode et al. observed
between the counterion and the functional group. At the end, that his kind of resin has a maximum ion-exchange capacity of
hydration occurs at the surface of the solution or pores of the 0.39 mmol g–1 of Cr(III) under optimum conditions and
adsorbent [117]. Different factors such as pH, anions, tempera- pH = 3.5 [119]. Also, Dowex HCR S/S resins are mostly in
ture, the initial concentration of the adsorbent and sorbate, and sodium form that is economically beneficial because of their
time of contact affect the ion-exchange operation [118, 119]. regeneration properties. Results showed that when this resin is
In ion exchange, a reversible exchange of ions between the used, Ni and Zn are removed about 98 % at optimal conditions
two phases (solid and liquid) occurs. In this method, a resin re- pH = 4 [129].
moves ions from an electrolytic solution and releases other ions Ambersep 132 is a strong basic resin with an adsorption
of similar charge in a chemically equivalent amount. In this capacity of about 92.10 mg g–1 used to remove Cr(VI) [130]. A
process, any structural change of the resin occurs [120, 121]. cation exchange resin called IRN-77 helps to absorb the total
Recovery of valuable heavy metals from inorganic effluents amount of Cr(III) with an initial concentration of 100 mg L–1
can also be conducted by ion exchange [122]. The metal is under the optimum pH of 3.5 [121].
recovered in a more concentrated form by elution with suitable
reagents, after separation of the loaded resin.
Resin with acidic functional groups contains sulfonic acid in 2.2.3 Adsorption
its structure; hence, it can be supposed that during metal ions
capturing, the physicochemical interactions may take place: Another physicochemical method for removing heavy metals
from wastewaters is adsorption, which has been successful in
nRSO 3 H
þ
þ Mnþ Ð nRSO3 Mnþ þ nHþ decreasing metal concentration. Adsorption is based on mass
(12)
ðresinÞ ðsolutionÞ ðresinÞ ðsolutionÞ transfer between the liquid phase and the solid phase called
adsorbent [131]. For sorption of pollutant onto an adsorbent,
three key stages are involved: (i) the penetration of the pollu-
where n refers to a constant of the reaction species, relating to
tant from the bulk solution to the adsorbent surface; (ii)
the oxidation state of metal ions and –RSO3– denotes the an-
adsorption of the pollutant on the adsorbent surface; and (iii)
ionic group linked to the ion exchange resin [122].
penetration in the adsorbent structure [24].
Ion exchange has a very specific place in treating wastewaters
These adsorbents provide large surface areas and high
and removing heavy metals [123–125]. When an ion-exchange
adsorption capacity. The good point is that the process can run
cell with strong acidic cation exchangers is employed, heavy
in reversible mode and the adsorbents will be regenerated by
metals can be efficiently removed [118]. It is usually preferred
desorption. Adsorbents can be derived from agricultural waste,
to other methods like chemical precipitation due to its high
industrial by-products, or natural materials. Some of the most
efficiency, low cost, less sludge volume, recovery of metals’ val-
used adsorbents in this process are activated carbon (AC), car-
ue and high selectivity [121, 126–128].
bon nanotubes (CNT), and sawdust. All of these adsorbents are
In this process, an insoluble resin is used to remove heavy met-
discussed further below.
al ions from the wastewater and release other ions of similar
charge without any structural change of the resin itself [120]. Ion
2.2.3.1 Activated carbon
exchange resins are a good choice in treating wastewaters in
order to eliminate or separate heavy metal ions [118, 119]. Activated carbons (AC) are generally prepared from agricul-
Among all the available kinds, synthetic polymer resins are pre- ture by-products when K2CO3 is used. Its maximum surface
area is in the range of 1266–
3256 m2g–1 in the literature a) b)
[132–134]. Adsorption by activated
carbon is widely used for the
removal of toxic metals and has
been studied extensively [135–137].
Studies show that carbon pre-
pared at 900 C is more effective for
removal of Ni(II) from aqueous
solution when the adsorbent con-
centration is 0.25 g. The effect of
the pH value on the adsorption was
investigated and 100 % Ni(II)
c) d)
removal was achieved in the range
of pH 2–5, which are optimum pH
values for cation adsorption [138].
2.2.3.2 Carbon nanotubes

Carbon nanotubes (CNTs) are fa-
mous for their excellent properties
and applications. Heavy metals
sorbs to CNTs by a very compli-
cated mechanism [139].
Some studies [140–143] showed
that CNTs have a great potential
for removing heavy metals. CNTs
immobilized by calcium alginate
(CNT/CA) reduce the risks caused
by discharging a lot of CNTs into e) f)
the water environment.
Li et al. worked on Cu(II) ab-
sorption via CNTs and CNTs/CA.
The results showed that at pH 5.0
74.8 % removal efficiency by using
CNTs and 83.3 % by using CNTs/
AC is achieved under experiment
conditions (Dosage of adsorbents:
0.05 g, concentration of Cu(II):
20 mg L–1) [144].
2.2.3.3 Wood Sawdust

Wood sawdust – a solid waste
product obtained from mechanical Figure 6. TEM images of the initial CeO2 nanoparticles (a, b); control CeO2 nanoparticles in deio-
wood processing – can be used as a nized water (c); CeO2 nanoparticles after adsorption of chromium (VI) at different amplifications
low-cost adsorbent of heavy metals, (d, e); CeO2 nanoparticles after desorption with 0.1 M NaOH eluent (f) [147].
largely due to its lignocellulosic
composition. It is mainly composed of cellulose (45–50 %) and of CeO2 nanoparticles at different states for the removal of dis-
lignin (23–30 %), both with a capacity for binding metal cat- solved Cr(VI) in pure water [147].
ions due to hydroxyl, carboxylic, and phenolic groups present
in their structure [145]. Interest has risen recently in removing
heavy metals from solution by binding with agricultural mate- 3 Current methods
rials such as waste wool, nut wastes, tree barks, modified cot-
ton, and sawdust [146]. 3.1 Membrane Filtration Process
Marina et al. worked on such heavy metal removal by saw-
dust. The maximum removal efficiency observed for Cu(II), 3.1.1 History and Definition:
Zn(II) and Cd(II) were 76.2 %, 37.5 %, and 31.9 % at 10, 20 and
20 g L–1, respectively [145]. Some studies on heavy metals Development of membrane filtration processes was very fast
adsorption are reported in Tab. 6. Fig. 6 shows the TEM images during 1979s to 1980s [151–162]. These processes were devel-
Table 6. Removing metals with the adsorption method using various adsorbents.
Metal Initial concentration of metal [mg/L] Initial PH Contact time [h] Adsorbent Dose adsorbent [g L] Removal [%] Ref.
Ni(II) 10 5 1 AC-K9a) 0.7 100 [138]
Cu(II) 20 5 N.A CNT 0.05 74.8 [144]
Cu(II) 20 3.6 N.A CNT 0.05 18.2 [144]
Cu(II) 5 7 24 Sawdust 5 85.2 [146]
Cu(II) 5 7 24 Sawdust 40 94.8 [146]
Cu(II) 50 7 24 Sawdust 5 58.6 [146]

b)
Hg(II) 200 5 7 SS-C 10 83.4 [148]
Hg(II) 200 5 7 SS-C 14 100 [148]

c)
Hg(II) 200 5 7 SS-S 8 100 [148]
d)
Hg(II) 200 5 7 SS-P 6 100 [148]
e)
Hg(II) 200 5 7 SS-Z 4 100 [148]
Ni(II) 6 3.5 N.A MWCNT/ ~ 10 [149]

Iron oxide
Ni(II) 6 8 N.A MWCNT/ ~ 80 [149]

Iron oxide
Cr(VI) 1 2.85 ~ 30 Oxidized 1 ~ 100 [150]

MWCNT
Cr(VI) 3 2.85 ~ 280 Oxidized 1 ~ 100 [150]

MWCNT
Cr(VI) 5 2.85 ~ 280 Oxidized 1 ~ 50 [150]

MWCNT
a)
Prepared at 900 C; b)No activation treatment carbon; c)H2SO4-activated carbon; d)H3PO4-activated carbon; e)ZnCl2-activated carbon.
oped and used due to their higher removal efficiency, no pollu- [182, 183]. A membrane literally is a selective layer with a
tion loads and sometimes lower energy consumption than con- porous or non-porous structure that is used to make contact
ventional methods [163–169]. These advantages help mem- between two homogeneous phases to remove the different size
brane processes find a wide range of applications including of pollutants [182, 184]. There are different parameters that
food and beverage industries, biotechnology, water filtration can affect the membrane performance. The most important
and after a while, treating wastewaters containing heavy metals parameters are materials in use, membrane pore size, and com-
[170–176]. Membrane processes are used in treating water and position [184–186]. These features lead to high efficient and
wastewater because of the simple separation method [177–179]. economic separation [185–187].
This simple procedure is shared between different membrane Materials should be chosen in a way that helps the production
processes with minor differences. In all processes, rejection is not of membranes with great chemical resistance and low imperfec-
achieved by flowing through the membrane physical pores, but tion in a structure like fouling. Many different kinds of materials
due to a higher trans-membrane pressure [180] the separation are used in membrane fabrication like metallic, ceramic, and
occurs through a semi-permeable membranes with different pore composite materials [177, 184, 185]. Furthermore, some other
size that make contact between desirable phases and control novel membranes include nano-based, reactive or catalytic and
the passage of particles by letting solvent go and catching the biologically modified materials in the membrane structure [185].
solute [180, 181]. The membranes that are used in these separa- One of the composite materials are polymers that are a
tion processes have many different aspects in type, fabrication, famous choice in membrane production because of their low-
and structure and will be reviewed in next section. cost features and porous structure [184, 185]. These polymers
can be applied in various filtration processes from microfiltra-
tion (MF) to reverse osmosis (RO) membranes [177]. Fre-
3.1.2 Membrane Characteristics quently used polymeric membrane materials are cellulose ace-
tate, polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN),
In general, three kinds of membranes are used in separation polypropylene (PP), polyethersulfone (PES) and polysulfone
processes called liquid, pressure-driven, and hybrid membranes (PSU) [177, 184, 185].
Ceramic materials are superior to polymeric ones in some dielectric effects [187, 188]. Steric hindrance mechanism helps
cases because of their narrow pore size distribution, high to remove neutral solutes [187]. Charged components are
mechanic, thermal, and chemical stability. Various materials rejected because of the existing Donnan potential and ion size.
have been used to produce ceramic membranes including alu- When a charge is applied due to adsorption of charged particles
mina, zirconia, silica, titania, oxide mixtures, and sintered met- and dissociation of surface particles a Donnan potential is cre-
als [177, 185]. ated between the charged anions in the NF membrane and the
co-ions in the effluent. The ionic components are rejected due
to these charge interactions [193, 194]. The third and the last
3.1.3 Major Membrane Processes step is post treatment [184, 185].
Toxic heavy metals can be effectively removed by using AFC-
Membrane filtration technology includes five major treatment 80 membranes when treated by NF aqueous solutions contain-
processes: reverse osmosis (RO), ultrafiltration (UF), microfil- ing lead in a very wide concentration range. AFC 80 mem-
tration (MF), nanofiltration (NF), and electrodialysis (ED). branes can suitably be applied in the heavy metal industry to
These processes are basically the same, but have some major recover strongly polluting heavy metals such as lead and cad-
differences in the pore structure (pore size, pore size distribu- mium and reclaim wastewaters. The lead rejection was found
tion, and porosity), membrane permeability, and applied oper- to be very high (> 98 %) even for concentrated feed solutions
ating pressures [178]. containing 250 mgPbL–1 [182].
MF and UF membranes are porous membranes that can be
operated at low pressures [184]. The pore sizes of typical MF 3.1.3.2 Reverse Osmosis
membranes cover a range of 0.05 to 10 mm and pressures of
RO was first studied in the 1920s, but it did not become practical
about 0.1 to 2 bar. However, UF membranes have pores with
until 30 years later [195]. RO can be applied in many different in-
sizes ranging from 1 to 100 nm and an operating pressure of
dustries like desalination, food processing, water reclamation, bi-
about 1 to 5 bar [180, 184]. RO membranes are not porous
otechnology, pharmaceuticals, pulp and paper, textiles [196, 197].
[184] and work under low operating pressures of about 10 to
RO is now a fundamental separating technology in the treatment
20 bar with sub-nanometer pore membranes [180, 184, 185].
of a wide variety of wastewaters [198–200]. This method is
Among these processes, NFs are mediocre in size between UF
categorized as pressure-driven membrane process and is used
and RO membranes [184]. NF is operated at pressures between
for removing heavy metal ions. RO works under hydraulic op-
10 to 20 bar and pore sizes of 1 nm [180].
erating pressure [195, 196] and uses a semi-permeable mem-
brane that does not have any distinct pores to let the particles
3.1.3.1 Nanofiltration
flow through, so the transition has to occur by diffusion [201].
Nanofiltration is a relatively new technology. NF was developed Note that, both monovalent and multivalent particles can be
to make separation of large molecules possible by really small removed by RO membranes, but removal of multi-valent ions
pores [180] and to overcome operational deficiencies of con- is better [195, 201].
ventional techniques. Membrane fabrication and modification Separating solutes dissolved in water through an RO mem-
are important factors in NF processes because they affect the brane occurs through three basic principles. First, the water
solvent permeability [187]. Creation of better NF membranes from a concentrated solution of heavy metal ions absorbs onto
is possible through some technologies like interfacial polymer- the membrane surface. The second step is diffusion through
ization (IP), nanoparticles (NPs), and incorporation ultraviolet the membrane due to the concentration gradient. The water
(UV) treatments [187]. NF is used in environment-friendly molecules move down the gradient to the permeate side of the
and energy-efficient applications like ground water, surface membrane. After all, water molecules desorb from the semi-
water, and wastewater treatment purposes [188]. Treating permeable membrane and build up a nearly pure solution.
wastewaters including heavy metals with NF is increasing dur- When the separation is done, there will be a concentrated
ing the last two decades [189]. heavy metal solution on the feed side and a treated solution on
The whole process is known as a liquid phase filtration the permeate side [202]. Both the pollutants and concentrates
because it separates a wide range of organic (uncharged) and have to be eliminated and purified according to environmental
inorganic particles from solutions [181]. Notice that separation regulations, or else it would have adverse effects [203]. Separa-
process is based on the molecular weight cut-off (MWCO) or tion efficiency relates to the solute properties like size, charge
300 to 500 Da [190–192]. exclusion, and physical-chemical interactions happening
There are three basic steps in removing heavy metals by NF between solute, solvent, and membrane [195, 196].
processes. The first one is a pre-treatment step. Feed water These days integrated membrane bioreactors (MBR) and RO
needs to be treated before entering the system to decrease fur- systems are becoming more widely used for the removal of
ther possible fouling. Some of the pretreatment methods are emerging contaminants from wastewater [203]. Malamis [204]
pre-filtration, coagulation and filtration, in-line coagulation, used a combined MBR-RO system which enhanced metal
coagulation-sedimentation process, coagulation-adsorption removal from municipal wastewater to the levels from > 90.9 %
process, flocculation and filtration, ion exchange, and chemical to > 99.8 %, while for wastewater spiked with heavy metals the
conditioning [185]. The second part is the main membrane removal efficiencies were > 98.4 %. The results of an experi-
separation process. The general rejection of NF membranes is a mental study on the heavy metal removal using RO and NF ap-
result of a combination of steric hindrance, Donnan, and plications are listed in Tab. 7.
Table 7. Results of experimental studies on the heavy metal removal using RO and NF treatments.
Metal Initial metal concentration [mg L–1] Application Pressure [bar] pH Removal [%] Ref.
Cd 5 NF 20 5 80.57 [205]
Cd 5 NF 20 5 97.26 [205]
Ni 5 NF 20 5 85.27 [205]
Ni 5 NF 20 5 98.90 [205]
Pb 250 NF N.A 5.8 99.1 [182]
Pb 50 NF 25 5.8 > 99 [182]
Pb 5 NF 50 5.8 > 99 [182]
Pb 25 NF 50 5.8 > 99 [182]
Pb 100 NF 50 5.8 > 99 [182]
Pb 250 NF 50 5.8 98.9 [182]
Ar 400 ppb NF 14 7.1 97 [192]
Ar 400 ppb NF 5 7.1 96.4 [192]
Ar 100 ppb NF 5 7.1 84.9 [192]
Cr 400 ppb NF 14 7.1 95 [192]
Cr 400 ppb NF 5 7.1 85 [192]
Cr 100 ppb NF 5 7.1 52.7 [192]
Cd 80 ppb NF 14 7.1 85 [192]
Cd 80 ppb NF 5 7.1 65.8 [192]
Cd 20 ppb NF 5 7.1 100 [192]
Ni 50 RO 100 N.A 97.3 [206]
Cu 50 RO 100 N.A 97.4 [206]
Cr 50 RO 100 N.A 98.3 [206]
Ni 50 RO 500 N.A 99.5 [206]
Cu 50 RO 500 N.A 99.6 [206]
Cr 50 RO 500 N.A 100 [206]
Ni 50 RO 3.5 3 98.88 [206]
Cu 50 RO 3.5 3 98.83 [206]
Cr 50 RO 3.5 3 99.01 [206]
Ni 50 RO 3.5 9 99.9 [206]
Cu 50 RO 3.5 9 > 99.9 [206]
Cr 50 RO 3.5 9 > 99.9 [206]
3.1.3.3 Microfiltration and Ultrafiltration

MF and UF are discussed together because they have a lot in effluent [207], while UF is useful in rejecting species like dis-
common. Both are pressure-driven processes with a shared solved macromolecules, colloidal materials, and sometimes
area of usage and almost the same separation procedure. The suspended species [202]. Both have many applications in
main difference between these processes is that solutes that many different industries such as purification of water for
are removed by MF are larger than those rejected by UF the production of potable water, clarification of different so-
[207]. MF is operated to separate suspended particles of lutions, and removing disturbing particles. The most impor-
tant usage is the treatment of waste-
waters to reach discharge standards a) b)
[208, 209].
Basically, the most difficult part in
MF and UF processes is choosing an
appropriate membrane since that can
affect the removal efficiency [207]. The
membranes differ in porosity, structure,
and material. Both UF and MF mem-
branes are porous in nature [195].
Here just two kinds of membranes
structure are mentioned. MF and UF
membranes can be symmetric or asym-
metric [207]. Symmetric membranes
are those whose structural characteris-
tics do not vary over the membrane
cross-section [207]. It is said that MF c) d)
membranes are usually symmetric
unlike UF membranes [195].
Among the materials that are used in
MF and UF membranes, hydrophilic
and hydrophobic membranes as well as
crystalline polymers have been widely
used [207]. Each of the materials has
advantages and disadvantages. In gen-
eral cases, hydrophilic membranes are
not used for MF and UF, because the
water molecules affect mechanical and
thermal resistance. Crystalline poly-
mers are the opposite and hydrophobic
membranes are widely used to mini-
Figure 7. SEM images of a titania membrane prepared by polymeric sol-gel method; (a, b)
mize the adsorption of solute on the
before use; (c, d) after use [210].
membrane surface which can reduce
the permeate flux [207]. Before describ-
ing the separation mechanism, the different existing filtration process [215]. It is used in the treatment of wastewater from
methods are discussed. There are two kinds of filtration meth- different industries [216, 217], water splitting producing acid
ods: dead-end and cross-flow. The dead-end mode is used and base from salts [213, 214] as well as fractionation that
when feed flows perpendicularly to the membrane surface, includes wine stabilization, whey demineralization, etc.
while the feed goes tangentially across the membrane [214, 218]. ED has ion-selective exchange membranes (IEMs).
[195, 207]. There is no reject stream in the dead-end mode, just IEMs do not transport cations and anions simultaneously.
a feed stream, and a permeate one [195]. Cross-flow mode There are two kinds of these membranes: cation (CEM) and
needs more complex utilities, but it has higher flux rates and anion (AEM) exchange membranes [216, 219]. Ion transporta-
membrane lifetime than dead-end [207]. MF and UF processes tion through these membranes happens due to electrical poten-
can be handled in both types [207]. Fig. 7 shows the SEM tial or concentration gradient [213].
images of titania membrane prepared by the polymeric sol-gel When the polarity of ED electrodes is reversed, the process
method used for removing Cr(VI) by surfactant enhanced is called electrodialysis reversal (EDR) which sometimes is bet-
microfiltration [210]. ter than ED. EDR lowers the scaling and fouling and has higher
The separation mechanism in MF and UF processes is typi- recovery rates [216, 220]. But on the other hand, EDR needs
cally based on molecular sieving using porous membranes more plumbing and electrical controls [216].
[207]. Particles larger than the pore size are rejected due to the
pore size constraints [195, 209]. Since the particles are absorbed
3.2 Photocatalysis Process
onto the membrane surface, a pore size reduction occurred so
the separated particles are much smaller than the pore size
Advanced oxidation processes (AOPs) are a new technology in
[195].
air and water purification industries [221–225]. Photocatalysis
is a famous AOP that many researchers have worked on
3.1.3.4 Electrodialysis
[225, 226]. This method uses non-toxic semiconductors that
Electrodialysis (ED) was developed in the 1950s by studies on harness light with appropriate wavelength instead of chemical
desalination [213, 214]. ED is a novel liquid hybrid membrane compounds [227, 228]. In addition, it is preferred over chemi-
Table 8. Results of experimental studies on the heavy metal removal using UF.
Metal Initial metal Concentration [mg L–1] Initial pH Type of membrane Removal [%] Ref.
Ni(II) 320 9 Sorbent-assisted UF* 99.6 [211]
Cu(II) 320 9 Sorbent-assisted UF 99.8 [211]
Pb(II) 320 9 Sorbent-assisted UF 99.9 [211]
Zn(II) 320 9 Sorbent-assisted UF 99.7 [211]
Ni(II) 320 6 Sorbent-assisted UF 25 [211]
Cu(II) 320 6 Sorbent-assisted UF 31.25 [211]
Pb(II) 320 6 Sorbent-assisted UF 95.9 [211]
Zn(II) 320 6 Sorbent-assisted UF 99.1 [211]
Zn(II) N.A 7 PES-20 with PEI-70 88.7 [212]
Zn(II) N.A 7 PES-20 with PEI-25 78.1 [212]
Ni(II) N.A 7 PES-20 with PEI-70 97 [212]
Ni(II) N.A 7 PES-20 with PEI-25 98.1 [212]
*Made by polyvinylidene fluoride with a nominal pore size of 0.04 mm
cal processes because of not using toxic materials as catalysts exchanging photo-holes and photoelectrons according to
[227, 229]. The photocatalysis process became popular as an Eqs. (14) and (15). According to the redox potential of each
efficient process because of its simple design, low-cost opera- pollutant, electron-holes proceed to the acceptor molecules and
tion, high stability, and high removal efficiency [230, 231]. This photo-holes transfer to the donor. After formation of ions in
process is applied in many areas of interest including photo- this phase, they react to form the intermediates and final prod-
splitting and decomposition of water to produce hydrogen gas ucts.
[221, 232], disinfection of microorganisms [233–235], degrada-
tion of organic compounds [236], selective oxidation [237], Reduction: A þ e fi A (14)
manufacturing liquid chemical fuels [238, 239]. Besides that, it
is powerful in eliminating pollutants such as heavy metals to Oxidation: D þ hþ fi Dþ (15)
protect the environment from contamination [240–242].
When a solution containing pollutants is introduced into a where A and D stand for pollutant species. Along these reac-
photocatalytic system, a five step process is conducted. First, tions, sometimes electron-hole recombination occurs according
the pollutants transfer to the surface from the aqueous phase. to Eq. (16). The process efficiency can be reduced by this reac-
They are then absorbed by the semiconductor surface. The tion that degrades the photo-electric energy into heat [243]:
third step are photocatalytic reactions occurring in the
absorbed phase. Finally, the products are decomposed and Recombination: e þ h fi heat (16)
removed from the interface region [225, 230]. The major step
of the treatment system is the third one, where the photocataly- Heavy metals can be eliminated by being deposited on the
sis processes occur. The whole process uses light as an activator. photocatalyst surface through the following reaction [244, 245]:
Therefore, the thermal activation of old processes is omitted
[225]. Mnþ þ e fi M (17)
The photon excitation of the semiconductors is the initial
step. When a light, especially visible light, with energy equal to The deposition happens by the formation of small crystalli-
or larger than the band gap energy of the semiconductor (not tes, whose size depends on the nature of the metal. This reac-
the pollutants) is illuminated, electrons from the valence band tion transforms the ionic species into less toxic forms. When
(VB) promote to the conduction band (CB). By this promotion, the transformation is done, the recovery of the heavy metals by
an electron-hole pair is created that leaves a photo-hole (h–) in mechanical and thermal procedures is possible [222]. The fol-
the VB and a photo-electron (e–) in the CB, so in the light lowing reactivity pattern was found under specific conditions
absorption process the following Eq. (13) takes place. Ag > Pd > Au > Pt >> Rh >> Ir >> Cu = Ni = Fe = 0 [225].
Semiconductors that are used in photocatalysis are mostly of
SC þ hv fi e þ h (13) the chalcogenide type including oxides like TiO2, ZnO, ZnO2,
CeO2, WO2, and sulfides like CdS, ZnS, WS2, etc. [246].
At the same time, when electron-hole pairs are created, the Among these materials, TiO2 is an experimentally popular
reduction and oxidation of the pollutants takes place by photocatalyst due to its environment-friendly features
[247–249] and properties such as being safe to work with, sta- mostly starts by injecting it to the wastewater solution. It in-
ble against photo-corrosion, chemically inert, potentially active creases the ambient pH and decreases the redox potential of
in oxidizing every organic and inorganic particles, and inex- the solution. In addition to the changes applied to the waste-
pensive [227, 250]. water after injecting the nZVI, the nZVI particles themselves
Despite the development of photocatalysis processes, they undergo a chemical transformation by coating with natural or-
still face some limitations like recombination of electron or ganic matters in the waste solution [269].
hole, producing unwanted byproducts, and the fault in absorb- The last kind of nanoparticles are hybrid magnetic nanopar-
ing visible lights [251, 252]. ticles (MNPs). They are called hybrid because they contain two
or more nanometer-scaled components and magnetic because
at least one component is magnetic [270]. They are widely used
3.3 Nanotechnology in a variety of applications not only because of their convenient
magnetic properties, low-toxicity, and low price, but also be-
Objects when are at nanoscale displays considerable properties cause they possess a high surface-to-volume ratio which leads
compared to their bulk counterparts [189, 253]. Some of these to a high adsorption capacity and high removal rates of con-
properties are extremely high specific area and chemical reac- taminants [271, 272]. At diameters less than 20 nm, these par-
tivity, super magnetism behaviors, short intraparticle diffusion ticles have the maximum surface area and are in the super-
distance and easier penetration into cells [254, 255]. NMs are magnetic state at room temperature [273]. Among the mag-
great adsorbents owing to their large surface area; therefore netic nano-sized materials, iron oxides like magnetite (Fe3O4)
they are used widely in treating wastewaters containing heavy and maghemite (g-Fe2O3) are the main representatives of
metals [254]. It should be noticed that increasing use of nano- MNPs [271, 274, 275]. Surface modification of MNPs to obtain
products and nano-adsorbents increase the risk of nano-pollu- more stabilized particles is essential [271, 276]. There are vari-
tants in the environment [256]. ous kinds of materials that can be used to coate MNPs, like pol-
In the last two decades, nanotechnology is becoming a sci- ymer coating materials of lipids, poly(vinylpyrolidone)(PVP),
ence of nanomaterials [189, 257]. This technology is getting a poly(vinylalcohol) (PVA), etc. [273]. The MNPs can be recov-
lot of attention not only in the academic communities but also ered and regenerated through a desorption process in a mag-
among investors and industries [258]. It is used extensively in netic field [256, 272]. Fig. 8 shows the TEM images of maghe-
chemistry, biology, engineering, health and medicine, consumer mite nanoparticles before and after Cu and Ni adsorption
products, and water information technology [259, 260]. Nu- [277].
merous studies [261–264] have highlighted nanotechnology as Hu et al. [278] have synthesized various types of MNPs that
a practical developing wastewater treatment system. The treat- were prepared by chemical co-precipitation and used for the
ment systems of this technology overcome old major deficien- removal of Cr(VI) from synthetic electroplating wastewater.
cies and provide systems with higher removal efficiency, low The Cr(VI) removal performances were compared and the ad-
waste generation, and specific uptake [261, 265]. sorption capacities followed the order: MnFe2O4 > MgFe2O4 >
Generally, two major developing technologies are applied in ZnFe2O4 > CuFe2O4 > NiFe2O4 > CoFe2O4.
treating wastewater solutions by nanomaterials that they are Song et al. [279] prepared polyrhodanine-encapsulated
called in situ and ex situ. In situ technologies are used when MNPs via one-step chemical oxidation polymerization and in-
the wastewaters are treated in the place of contamination by investigated their potential for adsorptive removal of heavy metal
jecting nano-sized particles whereas ex situ refer to treatments ions from aqueous solutions. Typically, 5.0 mg of the PR-MNPs
done after transferring the waste solution to a more convenient were added into 10 mL of Hg(II) ion solution (80 mg L–1) at a
area. Whenever in situ technologies are feasible, they are pre- pH of 4.0. Then, the prepared samples were shaken at 350 rpm
ferred to ex situ, due to the cost effective features and higher re- using a mechanical shaker at 25 C in a batch mode. It was
moval [265]. found that the adsorption capacity increases sharply with an
There are three kinds of nanoparticles: adsorptive, reactive, increase in pH from 2.0 to 4.0, but decreases slightly with a pH
and hybrid magnetic. Nano magnetic oxides (NMOs) are ad- rise from 4.0 to 8.0. This means that the concentration of
sorptive nanomaterials. They are widely used in wastewater H+ ion significantly affects the adsorption behavior of
treatment systems due to their high surface area, stability, and PR-MNPs. Other case studies are mentioned in Tab. 9.
the mesoporous structure [265, 266]. NMOs use the adsorption
mechanism which was comprehensively discussed in the
Sect. 2.2.3. The adsorption mechanism is based on the seques- 4 Summary and Perspective
tration of heavy metal ions which leads to deep removal of
heavy metals to reach the maximum contaminant limits Widely distributed toxic substances such as heavy metals, phe-
(MCL) [265]. Adsorption efficiency obviously relies on physi- nolic compounds, and other non-biodegradable pollutants
cochemical conditions of the system and the chemical nature from industrial wastewaters are considered to be harmful to
of the used absorbent [267]. humans and the environment. In this paper, some of the most
Nano zero-valent iron (nZVI) is another noticeable nanopar- used methods for wastewater treatment are reviewed. These are
ticle used for wastewater treatment and heavy metal removal. It electrochemical and physicochemical methods, membrane fil-
removes heavy metal ions by using reactive technologies, which tration, photocatalytic processes, and nanotechnology treat-
make degradation and transformation of contaminants into ments. Each method has its own heavy metal removal efficien-
harmless products possible [265, 268, 269]. In situ use of nZVI cies and the specific parameters that affect the removing
a) b) c)
Figure 8. TEM images of: (a) pure maghemite nanoparticles; (b) Cu-adsorbed maghemite nanoparticles at pH 6.5; (c) Ni-adsorbed mag-
hemite nanoparticles at pH 8.5 [277].
Table 9. Removing heavy metal ions by MNPs.
Synthesis Method Ting agents Surface-functionalized group Metal removed Ref.
Thermolysis of precursors Dimercaptosuccinic acid Thiol group Hg(II), Ag(I), Pb(II), Cd(II), Tl+ [280]
Co-precipitation Succinic acid Carboxylic group Cr(III), Co(II), Ni(II), Cu(II), [272]
Cd(II), Pb(II), As(III)
Thermolysis of precursors Ethylenediamine Amine group Cr(III), Co(II), Ni(II),Cu(II), [272]

Cd(II), Pb(II), As(III)
Thermolysis of precursors Ercaptosuccinic acid Thiol group Cr(III), Co(II), Ni(II), Cu(II), [272]
followed by ligand exchange Cd(II), Pb(II), As(III)
process
Co-precipitation Humic acid Carboxylic and phenolic group Hg(II), Pb(II), Cd(II), Cu(II) [281]
Co-precipitation Carboxymethyl-b-cyclodextrin Carboxylic group Cu(II) [282]
Crystallization from ferrous Polyethylenimine Amine group Cu(II) [283]

hydroxide gels
Co-precipitation Dendrimers Amine group Zn(II) [284]
Co-precipitation followed (3-Aminopropyl) trimethoxysilane Amine group Pb(II), Cd(II), Cu(II) [285]
by a sol-gel process using
sodium silicate (Fe3O4@SiO2)
Co-precipitation followed by Salicylic acid-functionalized silica Carboxylic group Cu(II), Cd(II), Ni(II), Cr(III) [286]
hydrolysis of TEOS,
(Fe3O4@SiO2)
Modification of co-precipitation Starch Hydroxyl group As(V) [287]

method
Modification of co-precipitation Starch Hydroxyl group As(V) [288]

Method
process. The results are different for each method and their troflotation, and electrocoagulation, can completely remove
experimental condition. Depending on the variable parameters; (>99%) the heavy metals or reduce their dosage to standard
removal efficiencies vary from 12 % to 100 %. However, for limits under optimum condition. However, the results for elec-
most of them, adequate removing was observed. Some meth- trodeposition showed a varying removal efficiency for metals
ods, such as RO, NF, adsorption, chemical precipitation, elec- from 12 to 92.1 %.
Arezoo Azimi obtained her Meisam Ansarpour obtained
B.Sc. in Chemical Engineering his B.Sc. in Chemical Engi-
in 2016 from the Persian Gulf neering from Persian Gulf
University and is currently University. He currently works
pursuing M.Sc. in Chemical on heat and mass transfer of
Processes Designing at Shiraz nanofluids. His expertise lies in
University of Technology. Her nanofluids heat and mass
research interests include envi- transfer, adsorption processes,
ronmental biotechnology, re- biotechnology and renewable
newable energy, and industrial energies.
wastewater treatment for re-
use.
Ahmad Azari obtained his

B.Sc. in Chemical Engineering
from Shiraz University in Abbreviations
2006, and his M.Sc. in Chemi-
cal Engineering from Tehran AC activated carbon
University in 2008. After re- AC-K9 activated carbon prepared at 900 C
ceiving his Ph.D. in Chemical AEM anion exchange membrane
Engineering from AmirKabir AOP advanced oxidation processes
University of Technology CB conduction band
(Tehran Polytechnic) in 2012, CEM cation exchange membrane
he has been Assistant Profes- CNT carbon nanotube
sor at the faculty of Oil, Gas, CTABr hexadecyl-trimethyl-ammonium bromide
and Petrochemical Engineer- EC electrocoagulation
ing at the Persian Gulf Univer- ECF electrocoagulation-flotation
sity. His research interests focus on CFD simulation and ED electrodialysis
process optimization, nanofluids and industrial wastewater EDR electrodialysis reversal
treatment for resource recovery and reuse in the Energy and EF electroflotation
Environment research center. EP electrodeposition
IP interfacial polymerization
Mashallah Rezakazemi re- MCL maximum contaminant level
ceived both his B.Sc. and M.Sc. MF microfiltration
in Chemical Engineering in MNP magnetic nanoparticle
2009 and 2011, respectively, MWCNT multi-walled carbon nanotube
from the Iran University of MWCO molecular weight cut-off
Science and Technology. After N.A not available
completion of his Ph.D. at the NF nanofiltration
University of Tehran in 2015, NMO nano metal oxides
he became assistant professor nZVI nano zero-valent iron
of the Department of Chemical PAN polyacrylonitrile
Engineering at the Shahrood PES polyethersulfone
University of Technology in PP polypropylene
2016. His research focuses on PSU polysulfone
the general area of the water-energy nexus in engineered PVDF polyvinylidene fluoride
and natural environmental systems, specifically, membrane- RO reverse osmosis
based processes for energy-efficient desalination and waste- S steel
water reuse, environmental applications and implications of SDS sodium dodecyl-sulphate
nanomaterials, and water and sanitation in developing SIS synthetic iron sulfide
countries. SS-C carbon without activation treatment
SS-P H3PO4-activated carbon
SS-S H2SO4-activated carbon
SSS stainless steel
SS-Z ZnCl2-activated carbon
TT treatment technique
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21969744, 2017, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cben.201600010 by Indian Institute Of Tech - Roorkee, Wiley Online Library on [13/01/2023].

Cd 0.005 Kidney damage

Cr(total) 0.1 Allergic dermatitis

Ni 0.20 Dermatitis, nausea, chronic asthma, coughing, human carcinogen

Zn 0.80 Depression, lethargy, neurological signs, and increased thirst

Many researchers have worked on developing efficient treat- 2 Conventional Methods

Electrocoagulation (EC) is a simple and productive technology

Anode: Al Ð Al3 þ þ 3e (1)

2H2 O2 ﬁ O2 þ 2H2 (4)

Cr 17.1 Fe-S 304 N.A 6.9 30 97 50 A m–2 (DC) [40]

Cr, Cu 50 Al-Al-Al Parallel 4 15 99.9 0.8 A [41]

Zn 50 Al-Al-Al Parallel 4 15 83 0.8 A [41]

Cr 50 Al-Al-Al N.A 8 15 58 0.8 A [41]

Cr 100 Al-Al N.A 5 24 90.4 [45]

Fe 25 Al-Al N.A 7.5 35 99.2 0.4 A m–2 (DC) [47]

Cr 8000 Mild S Parallel 5.91 50–60 99 1000 mA [48]

Cr N.A Fe-Fe N.A 8 5 100 7.94 mA cm–2 [49]

Cu, Zn 1000 Al-Al Vertical >7 5 100 N.A [33]

Ni 1731 Al-Fe N.A N.A 180 52 N.A [50]

Cu 1530 Al-Fe N.A N.A 180 90 N.A [50]

Cr 400 Al-Fe N.A 4 180 99 N.A [50]

N N.A Fe Parallel 3 15 97.8 60 A m2 (DC) [37]

Zn N.A Al Parallel 5 25 96.7 60 A m2 (DC) [37]

Cr 14.70 SSS N.A 1.84 70 100 7.4 A (DC) [52]

Table 3. Removal of heavy metals by EF.

Cu 50 5 60 99 Without electrolyte [85]

Cu 500 5 60 71 Without electrolyte [85]

Cu 100 5 15 57 Without electrolyte [85]

Ni 100 6 300 37 Without electrolyte [85]

Cu 3.5 5.5 N.A 98.26 Chabazite [86]

Ni 2 5.5 N.A 98.6 Chabazite [87]

Zn 2 5.5 N.A 98.6 Chabazite [87]

Cu 474 8–10 N.A 99.99 CTABr [87]

Ni 3.3 8–10 N.A 98.50 CTABr [87]

Zn 167 8–10 N.A 99.97 CTABr [87]

Cu 12.7 6.7 N.A 85 Trien [88]

Ni 5.87 7 N.A 70 Trien [88]

Cr 58.8 N.A. N.A 95 Hydrotalcite [89]

Cu 60 8–10 N.A 97 Zeolite [90]

Zn 50 6 N.A 99 Zeolite [91]

Zn 50 9 N.A 96 Zeolite [91]

Cu 500 5 N.A 97 Zeolite [91]

Cr 50 4 N.A 98 Surfactin-105 [92]

Zn 50 4 N.A 100 Lycheny-sin-A [92]

Zn 50 7-9 N.A 100 SDS [93]

Fe 50 7.8 15 98 Sulfates [54]

Pb 50 7.8 15 >98 Sulfates [54]

Ni 50 7.8 5 98 Sulfates [54]

Cu 50 7.8 15 98 Sulfates [54]

Zn 600 7.8 10 93 Sulfates [54]

Zn 50 7.8 10 > 99 Sulfates [54]

Cd 50 15 99.5 Sulfates [54]

Ni 100 7.8 10 99.7 Polymetallic solution [54]

Cu 100 7.8 10 98.8 Polymetallic solution [54]

Zn 100 7.8 10 99 Polymetallic solution [54]

Cd 100 7.8 5 98.8 Polymetallic solution [54]

Pb 100 7.8 ~2 100 Polymetallic solution [54]

Pb 100 7.8 15 > 81 Acetates [54]

Zn 100 7.8 15 99.5 Acetates [54]

Cr Single cell 100 2.16 23 240 N.A [103]

Cu Single cell 1554 2.16 46.7 240 0.5 [103]

Ni Single cell 156 2.16 44.9 240 N.A [103]