124 Interdisciplinary Environmental Review, Vol. 18, No.

2, 2017

Methodologies for removal of heavy metal ions from

wastewater: an overview

Renu*, Madhu Agarwal and Kailash Singh

Department of Chemical Engineering,
Malaviya National Institute of Technology,
Jaipur, JLN Marg, Jaipur-302017, India
Email: [email protected]
Email:[email protected]
Email: ksingh.mnit.ac.in

Abstract: Heavy metal is a serious problem nowadays. These heavy metals are
discharged into water from various chemical industries. They are harmful for
living organisms and it is necessary to eliminate these heavy metals to
minimise risk of uptake by plants, animal and human. In the last few decades,
several methods have been developed and extensively investigated for heavy
metal removal. There are several methods for heavy metal removal:
chemical precipitation, adsorption, ion exchange, membrane filtration,
coagulation-flocculation and floatation. In this paper, an attempt is made to
review various methodologies for heavy metal removal from wastewater with
their advantages and disadvantages. It is evident from the literature survey that
adsorption method is widely used over conventional methods, (i.e., chemical
precipitation, ion exchange, membrane filtration, coagulation-flocculation and
floatation) because of its low cost, availability and eco-friendly nature.

Keywords: adsorption; heavy metal; methodology; wastewater.

Reference to this paper should be made as follows: Renu, Agarwal, M. and

Singh, K. (2017) ‘Methodologies for removal of heavy metal ions from
wastewater: an overview’, Interdisciplinary Environmental Review, Vol. 18,
No. 2, pp.124–142.

Biographical notes: Renu is a Research Schaolar at the Malaviya National

Institute of Technology, Jaipur (302017), Rajasthan. Currently, she is working
on ‘modelling and experimental study of heavy metal removal from
wastewater’. In 2014, she obtained her MTech in Chemical Engineering
(process modelling and simulation) from the Aligarh Muslim University,
Aligarh. In 2012, she obtained her BTech in Chemical Engineering from the
MJP Rohilkhand University, Bareilly. She is also a member of Indian Institute
of Chemical Engineers (IIChE), India.
Madhu Agarwal pursued her BTech and MTech in Chemical Engineering from
the Calcutta University, Kolkata and PhD from the Malviya National Institute
of Technology, Jaipur (302017). Currently, she is working as an Assistant
Professor in the Department of Chemical Engineering of Malaviya National
Institute of Technology, Jaipur (302017), Rajasthan.
Kailash Singh pursued his BE from the University of Roorkee, MTech from the
IIT Kanpur and PhD from the Curtin University of Technology, Australia.
Currently, he is working as an Associate Professor in the Department of
Chemical Engineering of Malaviya National Institute of Technology, Jaipur
(302017), Rajasthan.

Copyright © 2017 Inderscience Enterprises Ltd.

 Methodologies for removal of heavy metal ions from wastewater 125

1 Introduction

Industrialisation of chemical industries leads to discharging of huge amount of heavy

metals such as zinc (Zn), lead (Pb), iron (Fe), copper (Cu), cadmium (Cd), nickel (Ni),
chromium (Cr) and mercury (Hg) alongwith the wastewater (Liu and Huang, 2011).
These heavy metal ions have toxicity and can cause cancer (Alvarez et al., 2007; Gupta et
al., 2011; Mehdipour et al., 2015; Priya and Selvan, 2014; Grimshaw et al., 2011; Veeken
and Hamelers, 2003).These heavy metals affect soil fertility, water resource and aquatic
ecosystem (Majumdar et al., 2008). Heavy metals in wastewater comes from metal
complex dyes, pesticides, fertiliser, refining, fixing agents, mordant and bleaching agents
(Ullah et al., 2013). The main source of wastewater is electroplating industry, pigment,
printing and textile industry (Gherasim and Mikulášek, 2014). Lead has toxicity which
causes anaemia, gastrointestinal disease and elevates body blood pressure (Gherasim and
Mikulášek, 2014) even at small concentration. Similarly, higher concentration of zinc
causes irritation, stomach cramps, lung disorder and concentration should not increase
more than 2 mg/L in the wastewater. Further, copper is present in two forms monovalent
and divalent. Divalent copper is harmful when it is inhaled in a large amount and causes
headache, vomiting, nausea, liver and kidney failure, respiratory problems and abdominal
pain (Bilal et al., 2013; Chaturvedi, 2013).
Similarly, the major source of cadmium are corrosion of galvanised pipe, erosion of
natural deposits, mining, refining of non-ferrous metal, pigment, printing and
photographic industry (Friberg et al., 1992). Cadmium is toxic and has negative effects
on kidney and in oral route (Friberg et al., 1992). However, source of chromium are
leather tanning, nuclear power plant, electroplating and textile industries (Al-Othman
et al., 2012; Barnhart, 1997; Marín et al., 2010; Mohan et al., 2006; Mohanty et al.,
2005). Source of nickel are electroplating batteries, silver refineries, zinc base casting,
landfill leachates (Kadirvelu and Namasivayam, 2003). Mercury comes out mainly from
chlor alkali industry and battery industries (Liu and Huang, 2011). A number of methods
have been developed for the removal of heavy metals from wastewater. In this review
article, various methods such as chemical precipitation, ion-exchange, adsorption,
membrane filtration, electrochemical treatment technologies, etc. has been discussed.
Moreover advantages, disadvantages, limitations are also discussed in order to find out
the best suitable method for heavy metal removal.

2 Methodologies for heavy metal removal from wastewater

In the present ongoing section several methods have been discussed for heavy metal
elimination.

2.1 Chemical precipitation

It is an effective technique for remove of heavy metals from wastewater. In this process,
chemicals react with the heavy metals present in wastewater and there is formation of
insoluble precipitates. Further these precipitates are removed using sedimentation
technique and the cleared water is decanted (Djedidi et al., 2009; Fu and Wang, 2011).
126 Renu et al.

Chemical precipitation are categorised as hydroxide precipitation and sulphide

precipitation.
• Hydroxide precipitation: In hydroxide precipitation process metal hydroxides are
formed because of hydroxides reaction with heavy metals (Dupont, 1990).
Mirbagheri and Hosseini (2005) has utilised Ca(OH)2 and NaOH as a precipitant for
removal of Cu(II) and Cr(VI) ions by converting Cr (VI) into Cr(III) using ferrous
sulphate and sulphuric acid. Maximum conversion was obtained in the pH range of
2.0–2.3 and maximum precipitation of Cr(III) was obtained at pH 8.7 using
Ca(OH)2. The concentration was reduced from 30 mg/L to 0.01 mg/L for chromium
and 48.51 mg/L to 0.694 mg/L for copper and removal efficiency of 98.56%–99.9%
was obtained. However, Chen et al. (2009) has used lime as a precipitant for removal
of copper, zinc, chromium and lead from wastewater. Lime was used because of its
low cost and then fly ash was also added with it as a seed material. Using CaO as a
precipitant has several limitations of comparatively high dose of lime (Tadesse et al.,
2006). Author has reported removal efficiency of 99.37%–99.69% between pH of 7
and 11. Hydroxide precipitation has certain disadvantages such as requirement of
costly disposal because they produce secondary waste such as metal hydroxide
sludge and gypsum, some metal hydroxide are amphoteric in nature (Matlock et al.,
2002).
• Sulfide precipitation: In sulphide precipitation sulphide compounds form insoluble
precipitates when reacts with heavy metals. Sulfide precipitation has several
advantages such as, it removes heavy metals selectively, fast reaction rate, better
settling properties, sulphide precipitates can be used again by smelting (Azabou
et al., 2007; Foucher et al., 2001; Odom, 1993). Matlock et al. (2001) has used
pyridine based thiol ligand for removal of copper, cadmium and it has many
advantages such as availability of multiple sites for heavy metal removal and
formation of stable metal-ligand precipitates. It is a sulphur containing ligand and it
binds heavy metals and forms stable precipitates. This ligand has sufficient length for
interactions between heavy metal and each terminal sulphur group. Thus 99.99%
removal for copper and 99.88% removal for cadmium were obtained at an optimum
pH of 4.5 and 6 respectively.
• Chelating precipitation: Excessive use of strong complexing agent such as EDTA in
wastewater has become environmental problem (Fu et al., 2012). There is a
requirement for removal of not only toxic heavy metals but also chelating agent
EDTA. For this purpose Fenton-chemical precipitation process was used.
In Fenton-chemical precipitation process soluble iron cation interacts with the H2O2
(Fu et al., 2012). Because it is difficult to remove Ni (II) by conventional methods.
Fu et al. (2009) has used Fenton reactions followed by hydroxide precipitation for
removal of Ni (II) from Ni EDTA wastewater. Thus in their work, the concentration
of nickel was reduced from 50 mg/l to 3.6 mg/l and 92.8% of Ni (II) was removed
from wastewater. However, Fu et al. (2012) has used advanced Fenton-chemical
precipitation process for wastewater containing chelated heavy metal. In this
advanced process author has used zero valent ion for treatment of contaminants due
to its low toxicity, cost and easy operation. The concentration reduced from 50 mg/L
to less than 1 mg/L. At optimum condition, 98.4% removal efficiency was obtained
for Ni (II). Comparison of this work with their previous work concludes that
 Methodologies for removal of heavy metal ions from wastewater 127

advanced Fenton process has higher efficiency than the process which was adopted
earlier. Table 1 summarises work done related to removal of heavy metal by
chemical precipitation.
Table 1 Removal of heavy metal by chemical precipitation

Initial metal Optimum Removal

Heavy metal Precipitant References
cocn. pH efficiency
Ni 50 mg/L Alkali 2.5 98.4% Fu et al. (2012)
Ni 50 mg/L Alkali 11 92.8% Fu et al. (2009)
Ni 100 mM FeSO4 3 99.9% Shih et al. (2013)
Cu, Zn, Cr, 100 mg/L Lime 7–11 99.37- Chen et al. (2009)
Pb 99.6%
Cu, Cr 48.51 mg/L Ca(OH2) and 8.7 and 98.56% Mirbagheri and
NaOH 12 Hosseini (2005)
Cu, Cd 50 mg/L Pyridine based 4.5 99.99% Matlock et al.
thiol legand 99.88% (2001)
Zn 200 mg/L Sulfate reducing 6.8 – Azabou et al.
bacteria (2007)
Cd, Cu, Pb, – Sodium decanoate 4–8 > 90% Mauchauffée and
Ni, Zn Meux (2007)
Cu 100 mg/L 1, 3, 5 3–9 99.6% Fu et al. (2007)
Hexahudrotriazine
Dithio-carbamate
(HTDC)
Fe 194 mg/L 1, 3- 4.5 > 90% Matlock et al.
Benzenediamidoet (2002)
Hanethiol dianion
Cu 25 mg/L Ca(OH)2 12–13 > 99% Jiang et al. (2008)

2.2 Flotation
Flotation process is a well known method for the removal of heavy metals (Fu and Wang,
2011). Floatation process has many advantages such as selective metal ion recovery, low
sludge generation and it provides high separation efficiency (Rubio et al., 2002).
Scorzelli et al. (1999) has used sodium dodecylsulfate (SOS) as a collector and
isopropanol and methyl isobutyl carbinol (MIBC) as a frother for cadmium removal from
wastewater. Best removal of 89.2% was reported. Further addition of frother at
concentration 0.1% v/v has increases cadmium removal up to 98.8% and 97.7% for
isopropanol and methyl isobutyl cabinol. However, Polat and Erdogan (2007) have
removed copper, zinc and chromium from wastewater using ion floatation method.
Sodium dodecyl sulfate and hexadecyltrimethyl ammonium bromide were used as a
collector, ethanol and methyl isobutyl carbinol (MIBC) were used as frothers. The
removal obtained was 74% and it has increased up to 90% on increasing pH. Ion
floatation has several advantages of less energy requirements, rapid operation, low
concentration of metals, small space requirements, less operating cost (Scorzelli et al.,
128 Renu et al.

1999). Blöcher et al. (2003) has combined hybrid floatation and membrane filtration for
copper, nickel and zinc removal and for this purpose a system by integrating specially
designed submerged microfiltration module directly into floatation reactor has been
designed. System has many advantages such as it provides high membrane flux instead of
low turbulence created by air, low operating cost and high concentration. Regeneration
and disposal become easier due to presence of bonding agents in the froth. It has
combined advantages of both processes and overcome their limitations. Author has done
bonding of metals using zeolite because of its efficiency for heavy metal removal. Then
loaded bonding agent was separated from wastewater and hexadecyl trimethyl
ammonium bromide was used as a collector. Concentration of Cu, Ni and Zn
concentration has been reduced from 474, 3.3, 167 mg/L to below 0.05 mg/L. Yuan et al.
(2008) has removed cadmium, lead and copper using ion floatation with plant derived
bio-surfactant tea saponin. Biosurfactants have high specificity, biodegradability and
biocompatibility. In their work, surfactants as the collector and frother by enabling the
adsorption of the colligend classes onto the exterior of an air bubble. Removal of 89.95%,
81.13% and 71.17% was obtained for lead, copper and cadmium respectively when ratio
of collector to metal was 3:1. Table 2 summarises work done related to heavy metal
removal using chemical floatation.
Table 2 Removal of heavy metals by floatation method

Heavy Initial metal Optimum Removal

Frother References
metal conc. pH efficiency
Cd 20 mg/L Isopropanol methyl 4–5 99.1% Scorzelli et al.
isobutyl (1999)
Cu, Zn, 50 mg/L Ethanol and methyl 4–10 90% Polat and
Cr Isobutyl carbinol Erdogan (2007)
Pb 2–10mg/L Octadecylamine 10 Pb-100% Aldrich and
Chloride and cetyl- Ni-80% Feng (2000)

Trimethyl- Cu-60%
ammonium
Chloride Cd-50%
Cu, Ni, 474, 3.3, 167 Zeolite 8–10 - Blöcher et al.
Zn (2003)
Cd, Pb, 10–5 mol/L Tea saponin 6 Cd-89.95% Yuan et al.
Cu (2008)
2 × 10–5 mol/L Cu-81.13%
8 × 10–5 mol/L Cu-
71.17%
Cd – Ethanol 4 92.1% Salmani et al.
(2013)

2.3 Ion exchange

Ion exchange produces lesser sludge volume and having other advantages such as
recovery of selective and the meeting of strict release specifications (Lee et al., 2007;
Zewail and Yousef, 2015). Thus, for ion exchange process different types of resins were
used (Dorfner, 1991). Further, resins can also be categorised as natural resin and
 Methodologies for removal of heavy metal ions from wastewater 129

synthetic resin. Different resins were used by different authors for removal of heavy
metal in ion exchange process. Badawy et al. (2009) has demonstrated feasibility of
Purolite C100 resin for separation of lead ions from binary mixtures and solid phase
extraction was preferred because of fastness, simplicity and cost saving (Liang et al.,
2006) and 99.71% recovery of lead was reported. However, Thakare and Jana (2015)
have removed copper from wastewater using high density ion exchange resin INDION
225H. This high density ion exchange resin has advantage that they offer hydrodynamic
advantage while it is used in expanded bed adsorption. Shaidan et al. (2012) has used
strong acidic cation exchange resin in a fixed bed for nickel removal from wastewater. It
has several advantages such as it can treat large volume of effluents at one time and it is
more efficient heavy metal removal from wastewater. Author has obtained 97% removal
of nickel from wastewater. However, Zewail and Yousef (2015) has used spouted bed
with AMBERJET 1200 Na resin for nickel and lead removal from wastewater because it
has many advantages such as they provide mixing of solid phase and their intensive heat
and mass characteristic between fluid and solid phase yields isothermal conditions.
Author has reported 99% and 98% removal for lead and nickel respectively. Table 3
summarises work done related to heavy metal removal using chemical floatation.
Table 3 Heavy metal removal using ion exchange method

Heavy Initial metal Optimum Removal

Resin References
metal cocn. pH efficiency
Cu, Zn, Cd – Amberlite IR- – – Lee et al. (2007)
Pb – Purolite C100 – 99.17% Badawy et al.
(2009)
Cu 50–150 mg/L Indion 225H 6.3–6.5 – Thakare and Jana
(2015)
Ni, Pb 800, 1,000, Amberjet 1,200 – 98%, Zewail and Yousef
1,250 mg/L Na 99% (2015)

Hg, As – – – 98.56% Oehmen et al.

(2006)
Ni 1,800, 2,800, Acidic cation 3–7 97% Shaidan et al. (2012)
3,800 mg/L exchange resin

Cd, Pb 0.1 to 6 Sargassum 5 – Carro et al. (2015)

mmol/L muticum loaded
with calcium

2.4 Coagulation and flocculation

Coagulation is a process which uses coagulants and these coagulants are formed by
combination of insoluble particle and/or dissolved organic matter into large aggregates.
These coagulants are aluminium sulphate (alum), magnesium chloride (MgCl2),
polyaluminium chloride (PACL), aluminium hydroxide oxides (Renault et al., 2009; Lin
and Reed, 1996). Pang et al. (2011) has removed lead from wastewater in the existence of
other heavy metals such as iron and zinc with aluminium sulphate (alum), polyaluminium
chloride, magnesium chloride as a coagulant and korat PA3230 as the polyelectrolyte.
The presence of other heavy metals affects removal of lead and it may hinder their
130 Renu et al.

removal efficiency. It was observed that the addition of coagulants decreases settling time
of flocs. Also, flocs settling time was reported in the decreasing order as MgCl2 >
polyaluminuim chloride alum. It was reported that maximum removal of lead was 99% at
an optimum pH of 6.2–7.8 for alum, 8–9.3 for PACL and 8.7–10.9 for MgCl2. Use of
coagulants for removal of heavy metals causes so many problems such as it increases
heavy metal concentration in wastewater, large volume of sludge is produce and health
problems. To eliminate these problems alternative of Coagulants have been considered.
Chitosan can be used as an alternative. Chitosan is a polymer which is natural and
biodegradable and works as a coagulating and flocculating agent (Yang and Zall, 1984).
Biopolymers are being used as chitosan (Renault et al., 2009). Assaad et al. (2007) has
used chitosan-montmorillonite system for removal of cobalt, nickel and copper from
wastewater. Maximum adsorption capacity of 76.3 mg/g for cobalt, 89.3 mg/g for nickel
and 112.4 mg/g for copper has been reported. Flocculation is one of the widely applied
techniques to remove heavy metals from wastewater (Staicu et al., 2015). In the process
flocs bind the particles forms the bridges in between which convert into large
agglomerates or clumps (Fu and Wang, 2011). PAC, sodium dodecyl sulphate, polyferric
sulfate and polyacrylamideare being used as flocculants in the treatment of wastewater
(Fu and Wang, 2011). Shen et al. (2015) has used polymer surfactant complexation and
flocculation for removal of chromium, zinc and copper. Poly diallyldimethylammonium
chloride (PolyDADMAC) or polyethylenimine (PEI) was used as a cationic polymer and
sodium dodecyl sulphate (SDS) as an anionic surfactant. Maximum removal of 99% was
reported at an optimium pH of 6–9. Table 4 summarises work done related to
coagulation/flocculation for the removal of heavy metals.
Table 4 Removal of heavy metalby coagulation/flocculation

Heavy Initial
Coagulant/flocculant Optimum pH Removal References
metal metal cocn.
Aluminium sulphate Alum-6.2–7.8
Fe, Zn Polyaluminium 25–45 PACL-8–9.3 99% Pang et al.
chloride mg/L (2011)
Magnesium chloride MgCl2-8.7–10.9
Co, Ni, Chitosan 20–100 6.8 – Assaad et al.
Cu montmorillonite mg/L (2007)
system
Cr, Zn, Sodium dodecyl 11.2 mg/L 6–9 99% Shen et al.
Cu sulphate (2015)
Cr, Ni, Tanfloc 20 mg/L Cu-6 75% Heredia and
Zn Martin (2009)
Zn-7

2.5 Membrane filtration

There are different types of membrane filtration techniques based on different kind of
membranes. Membrane filtration has several advantages compared to other conventional
technique such as it provides high separation efficiency, it involves no phase change,
saves energy, can be scaled up easily and environmental friendly (Zhu et al., 2014). The
 Methodologies for removal of heavy metal ions from wastewater 131

technique used for removal of heavy metals is ultrafiltration (UF), reverse osmosis (RO)
and nanofiltration.

• Reverse osmosis: RO is a process driven by pressure (Ujang and Anderson, 1996).

Mohsen-Nia et al. (2007) has removed Cu and Ni from wastewater using disodium
salt ethylenediaminetetraacetic acid (Na2EDTA). It was reported that addition of
Na2EDTA has increased the chelated ion size of copper and nickel and there
rejection efficiency has been increased up to 99.5%. However, Ozaki et al. (2002)
has used aromatic polyamide (ES20) ultralow membrane for removing copper, nickel
and chromium from wastewater. Thus the removal of heavy metals was found
greater than 95%. Ipek (2005) has removed nickel and zinc from wastewater by
pre-treatment before RO process. However, removal percent obtained from both
pre-treatment unit and RO is 99.2% and 98.8% for nickel and zinc respectively.

Table 5 Heavy metal removal using RO method

Membrane Heavy metal Initial metal cocn. Removal efficiency References

RO Cu, Ni – 99.5% Mohsen-Nia et al.
(2007)
RO Ni, Zn 44–169 mg/L 99.2%, 98.8% Ipek (2005)
RO Cu – 95% Ozaki et al. (2002)
Ni
Cr
RO Pb – 100% Dialynas and
Diamadopoulos (2009)
Ni 100%
Cr 89%
Cu 49%

• Ultrafiltration: UF is a method which works at low pressures and removes dissolved

and colloidal material. There are two types of UF technique. Micellar enhanced
ultrafiltration (MEUF) and polymer enhanced ultrafiltration (PEUF). MEUF is a
physicochemical membrane separation technique in which there is addition of
anionic surfactant in the wastewater. So that the monomers of anionic surfactant
aggregate and they form micelles. Heavy metals are trapped in outer part of micelle
because of electrostatic force. The heavy metals which are not trapped in micelle
outer part and the remaining surfactant passes through the UF membrane.
MEUF has several advantages such as it gives high flux, high removal and low
energy cost however, it has disadvantage that it increases operating cost as well
(Landaburu-Aguirre et al., 2010). Second one is polymer enhanced UF, it uses water
soluble polymer in the wastewater. These polymers are retained in the membrane if
the size of these polymers is larger than molecular weight cut off of the membrane.
PEUF helps for removal of small solute molecules which can nor remove by
conventional UF (Huang et al., 2010).
132 Renu et al.

Table 6 Removal of heavy metal using UF method

Heavy Removal
UF type Complexing agent pH References
metal efficiency
MEUF SDS, TX114, TX100 Cu, Ni 11 – Tanhaei et al. (2014)
Brij35, TX405
MEUF SDS Cd, Zn 99% Aguirre et al. (2010)
PEUF Polyvinylamine Hg – 99% Huang et al. (2015)
PEUF PVA and sulfonated Co 5.93 31.81% Uzal et al. (2011)
PVA 6.5 99.98%

Landaburu-Aguirre et al. (2010) has removed cadmium and zinc from wastewater
using MEUF process and sodium dodecyl sulphate as a surfactant. Removal of 98%
for zinc and 99% for cadmium has been found. However, Camarillo et al. (2012) has
used polyethyleneimine for removal of copper from wastewater at an optimum pH of
4–5 and 92% rejection coefficient was obtained and Uzal et al. (2011) has used
sulfonated PVA (SPVA) and non-sulfonted PVA. Thus, 31.81% removal was
obtained by using non-sulfonated PVA and 99.98% removal was obtained by using
sulfonated PVA. Thus, it was observed that after sulfonation of PVA removal of
copper has been increased. However, use of this synthetic surfactant in PEUF causes
secondary pollution because of leakage problem. So, that use of bio-surfactants can
eliminate this problem. In bio-surfactant based UF technique, leakage into permeates
of bio-surfactants is not considered as a pollution, because of biodegradability,
compatibility and non-toxic nature of bio surfactants (Huang et al., 2015).
• Nanofiltration: Nanofiltration is one of the membrane filtration process ranging the
pore size in between UF and RO (Mehdipour et al., 2015). Commercial
nanofiltration membranes are composed of synthetic polymers containing charged
groups (Al-Rashdi et al., 2013; Zhu et al., 2014). Positively charged polyethylimine
crosslinked polyimide nanofiltration membrane (PEI) has good thermal, chemical
and mechanical property. But it has one limitation that it gives higher rejection
efficiency only for the multivalent cations. Thus we can modify this membrane for
removal of anions also. Gao et al. (2014) has performed adsorption of negatively
charged functional group containing chelating polymer over the charged PEI cross
linked P84 hollow fibre substrates. Adsorption of these chelating polymers improves
membrane performance, change in membrane surface charge, pore size and they
become capable of removing multivalent anions. This membrane gives rejection
efficiency greater than 98%. However, Zhu et al. (2014) has fabricated membrane by
simultaneous co-extrusion of polybenzimidazole (PBI) and polyethersulfone
(PES)/polyvinylpyrolidone (PVP) dopes through a triple orifice spinneret with the
help of dry jet wet phase inversion process. Using PBI has advantage that it has
superior chemical resistance and unique charge characteristic while a PES/PVP has
reasonable cost, superior spinnerablity, hydrophilic nature, good mechanical property
and easy formation of porous membrane. This membrane has given 95% rejection
for cadmium, 98% for Cr2O–7 and 93% for lead respectively. Gholami et al. (2014)
has fabricated membrane by combining it with the nanosized ferric oxides in
membrane matrix to improve lead removal from wastewater. Mehdipour et al. (2015)
 Methodologies for removal of heavy metal ions from wastewater 133

has used polyamide NF membrane for lead removal. It was also observed that
increase in pressure and initial feed concentration increases removal of lead 97.5%.
Table 7 Heavy metal removal using nano-filtration method

Membrane Heavy metal Removal efficiency References

NF Cd, Cr and Pb 95%, 98%, 93% Zhu et al. (2014)
NF Pb, Cu, Ni, Zn, Cd > 98% Gao et al. (2014)
and Cr
NF Cd 99% Rashdi et al. (2013)
Mn 89%
Pb 74%
Membrane with metal – – Nędzarek et al. (2015)
complexing polymer
NF Cu, Zn, Cd, Pb 97.5% Mehdipour et al. (2015)

2.6 Adsorption
Adsorption method is relatively low-cost process. Adsorption has certain advantages over
conventional methods such as they minimise chemical and biological sludge, low cost,
high efficiency, regeneration of adsorbents and possibility of metal recovery. Adsorbents
which have been already used for heavy metal removal are activated carbon (Sardella
et al., 2015), zeolite, manganese oxides, agricultural waste product such as water
hyacinth, hazelnuts shells (Kobya et al., 2005), orange peel pith (López-Téllez et al.,
2011), sunflower (Jain et al., 2010), coconut coir pith (Suksabye and Thiravetyan, 2012),
bacterial biosorbent, fungal biosorbent, marine algae, microbial and plant derived
biomass.
Following adsorbents has been used for heavy metal removal using adsorption
process.
• Activated carbon adsorbents: Activated carbon is the widely used adsorbent for
heavy metals removal (Bansal et al., 1988). Activated carbon has well developed
pores and high internal surface area for adsorption (Rao et al., 2006). Activated
carbon can be obtained from any material which has high content of carbon such as
industrial wastes. But they have high cost because of that there use is restricted
(Anirudhan and Sreekumari, 2011). Activated carbon is prepared from various
agricultural wastes such as from coconut button (Anirudhan and Sreekumari, 2011),
moso and ma bamboo (Lo et al., 2012), grape (Sardella et al., 2015), olive stones
(Bohli et al., 2015), lignin (Gonzalez-Serrano et al., 2004) and dust (Bohli et al.,
2015; Karthikeyan et al., 2005; Sardella et al., 2015) are cheap.
Anirudhan and Sreekumari (2011) have prepared activated carbon from waste
coconut button for removal of lead, Mercury and copper from wastewater. Author
has found maximum adsorption capacity for Pb(II) and Cu(II) at pH 6.0 and for
Hg(II) at pH 7.0. The adsorption capacities of the activated carbon decreases as
Pb(II) > Hg(II) > Cu(II). The adsorption capacity was reported to be 94.35 mg/g,
82.09 mg/g and 75.78 mg/g respectively. The percent removal obtained for lead is >
90% and for copper and mercury it is > 95%. On comparing adsorption capacities
134 Renu et al.

obtained in this work with other adsorbents, it was observed that the achieved
adsorption capacity from activated carbon prepared from coconut buttons is higher
than the adsorption capacities for red mud (64.79, 34.72, 12.61 mg/g) (Gupta et al.,
2001), carbon aerogel (Goel et al., 2005) and rice husk ash (Feng and Aldrich, 2004)
for lead removal. However, Lo et al. (2012) has prepared activated carbon by using
moso and ma bamboo activated carbons for removal of lead, copper, chromium and
cadmium. Removal efficiency was found in the decreasing order: Pb > Cu > Cr > Cd
for bamboo activated carbons and the removal efficiency obtained for lead, copper,
chromium and cadmium are 99.9%, 100%, 100% and 96.4%. Sardella et al. (2015)
has prepared activated carbon from grape industry wastes such as Cuyo Region,
Argentina, grape stalk, lex and pomace which is used for removal of lead and
cadmium. The adsorption capacity was found for lead and cadmium are 1.93 mmol/g
and 0.67mmol/g. However, Bohli et al. (2015) has prepared activated carbon using
olive stones for removal of Cu(II), Cd(II), Pb(II). Adsorption capacity observed were
17.667 mg/g and 57.098 mg/g for copper and cadmium respectively.
Table 8 Removal of heavy metal using activated carbon adsorbent

Removal
Adsorbent Heavy metal pH References
efficiency
Activated carbon Hg and Cu Pb(II), Cu(II): pH Pb(II) > 90% Anirudhan and
(waste coconut 6.0 Hg(II) : pH Hg(II) > 95% Sreekumari
button) 7.0. (2011)
Cu(II) > 95%
Moso and ma Cu, Cr and Cd 5.81–7.86 and Pb(II) 99.9% Lo et al. (2012)
bamboo activate 7.10–9.82 Cu(II) 100%
carbons
Cr(III) 100%
Cd(II) 96.4%
Activate carbon Cd(II) 6 and 5.5 98% Sardella et al.
prepared from grape Pb(II) (2015)

• Carbon nano tube adsorbents: In the past decade carbon nanotubes have gained
much attention because they have stability, large specific area, excellent adsorbent
properties and excellent mechanical and electrical properties (Ihsanullah et al., 2015;
Salam et al., 2011). Sankararamakrishnan et al. (2014) has used chemical vapour
deposition technique to grow carbon nanotubes over Fe and Ni doped activated
alumina. It gives nanofloral clusters for removal of chromium and cadmium. The
adsorption capacity observed was 264.5 mg/g for chromium and 229.9 mg/g for
cadmium. Kosa et al. (2012) has modified multi-walled carbon nanotubes using
eight-hydroxyquinoline for removal of cadmium, copper, lead and zinc. The removal
efficiency reported for cadmium was > 80%.
• Agricultural wastes: Biosorption process is an eco-friendly for removal of heavy
metals from wastewater. Biosorption process has a sorbent and solvent; this solvent
consists of species have to be adsorbed on sorbent (Volesky and Holan, 1995). These
sorbents have affinity for metal ions species. Agricultural waste materials mainly
consist of cellulose and lignin and other components are hemicellulose, lipid,
protein, water, starch, ash, etc. and many more compounds. Cellulose is an organic
compound, a polysaccharides consisting of linear chain of several hundred to many
 Methodologies for removal of heavy metal ions from wastewater 135

thousands of β linked D-glucose units (Demirbas, 2008). This compound contains

variety of functional groups such as phenolic, carbonyl, amido, amino, carboxyl
group, alcohols’, ester and sulphydryl (Beveridge and Murray, 1980; Gupta and Ali,
2000). These groups have capability of complex formation with metals. There are a
number of agricultural wastes like hazelnut shells (Kobya, 2004), orange peel pith
(López-Téllez et al., 2011), peanut shell (Al-Othman et al., 2012), sunflower,
coconut coir pith, eucalyptus plant, Rice bran, wheat bran, rice husk, activated rice
husk carbon,neem saw dust, mango saw dust, sugarcane baggase, wheat bran (Singh
et al., 2009), rice husk (Singh and Singh, 2012) walnut shell, almond shell (Pehlivan
and Altun, 2008), pomegranate husk, (El Nemr, 2009), corn cob powder (Sallau
et al., 2012), tea waste (Dave et al., 2012) are used for removal of heavy metal.
Sawdust is obtained by cutting, grinding, drilling, sanding or by pulverising wood
with a saw or other tool producing fine wood particles. Argun et al. (2007) has
modified oak saw dust (Quercus coccifera) using hydrochloric acid for the removal
of chromium. Daraei et al. (2015) has used egg shell for chromium removal and 93%
of removal was found. Namasivayam and Sureshkumar (2008) have modified coir
pith using the surfactant for chromium removal and 90% removal was obtained.
Ahmad et al. (2013) has removed chromium using chromium-resistant reducing
bacteria Acinetobacter haemolyticus inside sugarcane bagasse and this bacteria has
converted Cr(VI) into Cr(III) which is less toxic and less soluble as compared to
Cr(VI) and a removal of more than 90% was obtained. Garg et al. (2009) has used
modified sugarcane bagasse using succinic acid and found 92% removal. Further,
Cronje et al. (2011) has activated sugarcane bagasse for removal of chromium and >
87% chromium was reported at an optimum pH of 8.58.
Table 9 Heavy metal removal using carbon nanotubes adsorbent

Adsorbent Heavy metal pH Removal efficiency References

Composite of carbon Chromium 2 Cr > 95% Sankararamakrishnan
nanotubes and Cadium 7–9 Cd > 80% et al. (2014)
activated alumina
CNT modified Cadmium, 7 Cu > 99% Kosa et al. (2012)
by using eight- copper, lead, Pb > 80%
hydroxyquinoline zinc
Zn > 99.99%
Cd > 80%
CNT modified by Copper, 7–10 > 99% Salam et al. (2011)
using chitosan cadmium,
zinc, nickel

Table 10 Heavy metal removal using agricultural wastes

Adsorbent Heavy metal Removal efficiency References

Black tea waste Cu (II) > 99% Weng et al. (2014)
Rice husk Cr (VI) 93–94% Singh and Singh (2012)
Sugarcane Cr(III) Cr (III): 41.5% Ullah et al. (2013)
Cr(VI) Cr(VI): 80.7%
136 Renu et al.

3 Conclusions

Removal of heavy metals from wastewater by chemical precipitation is simple and

inexpensive. It has disadvantage such as production of sludge. This method is useful for
the case when concentration of heavy metals is high and for low heavy metal
concentration it is not effective. Further, adsorption is also an economical method which
has certain advantages over conventional methods such as they minimise chemical and
biological sludge, high efficiency, low cost, regeneration of adsorbents and possibility of
metal recovery. Adsorption is based on bio-sorption mechanism. The efficiency of
adsorbents depends on type of adsorbents for the removal of heavy metals. Membrane
filtration process produces less solid waste and it consumes less chemical and has high
efficiency, one of the disadvantages is that they have low flow rates. In coagulation-
flocculation method this method has advantage of sludge settling and dewatering and its
disadvantages are it has high cost and large consumption of chemicals. Ion exchange
method has advantages that there is no change in pH wastewater. Other advantages are
excellent process reliability, process stability and chemical safety. It has disadvantages of
high membrane cost, requirement of resin fouling and resin regeneration. The choice of
the method depends on the initial metal concentration, capital investment, operational
cost and environmental impact.

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