water

Review
The Current State-Of-Art of Copper Removal from Wastewater:
A Review
Nur Hafizah Ab Hamid 1, * , Muhamad Iqbal Hakim bin Mohd Tahir 1 , Amreen Chowdhury 1 ,
Abu Hassan Nordin 1 , Anas Abdulqader Alshaikh 1 , Muhammad Azwan Suid 1 , Nurul ‘Izzah Nazaruddin 1 ,
Nurul Danisyah Nozaizeli 1 , Shubham Sharma 2,3 and Ahmad Ilyas Rushdan 1,4, *

1 School of Chemical and Energy Engineering, Faculty of Engineering, Universiti Teknologi Malaysia,
Johor Bahru 81310, Johor, Malaysia
2 Mechanical Engineering Department, University Center for Research & Development, Chandigarh University,
Mohali 140413, Punjab, India
3 Department of Mechanical Engineering, IK Gujral Punjab Technical University, Main Campus-Kapurthala,
Kapurthala 144603, India
4 Centre for Advanced Composite Materials (CACM), Universiti Teknologi Malaysia (UTM),
Johor Bahru 81310, Johor, Malaysia
* Correspondence: nurhafizah.abhamid@utm.my (N.H.A.H.); ahmadilyas@utm.my (A.I.R.)

Abstract: Copper is one of the chemical elements that is widely used in various sectors nowadays
together with the development of civilization especially in agricultural and industrial sectors. Copper
is also considered as one of the heavy metals that is commonly present in wastewater. This preliminary
study conducted is mainly focused on the techniques of removal of copper in wastewater. There
are a variety of approaches for treating industrial effluent contaminated with heavy metals such as
copper. Copper separation can be accomplished using a variety of technologies, each of which has
advantages that vary depending on the application. Chemical removal techniques that are commonly
Citation: Ab Hamid, N.H.; bin Mohd used for copper removal are adsorption, cementation, membrane filtration, electrochemical method,
Tahir, M.I.H.; Chowdhury, A.; and photocatalysis. This study compares the fundamentals and performances of the treatment
Nordin, A.H.; Alshaikh, A.A.; Suid, techniques in addition to the future perspective of copper removal in detail. The study highlights the
M.A.; Nazaruddin, N.‘I.; Nozaizeli, present research in terms of its strengths and shortcomings, pointing out deficiencies that need to be
N.D.; Sharma, S.; Rushdan, A.I. The addressed in future studies, pointing to future research prospects.
Current State-Of-Art of Copper
Removal from Wastewater: A Review. Keywords: copper removal; adsorption; cementation; membrane filtration; electrochemical; photocatalysis
Water 2022, 14, 3086. https://
doi.org/10.3390/w14193086

Academic Editor: Chengyun Zhou

1. Introduction
Received: 11 September 2022
Accepted: 28 September 2022
Copper (Cu) is one of the most important elements and is considered as one of the most
Published: 1 October 2022
widely used metals in various industrial and agricultural practices [1,2]. It is also one of the
earliest metals that was collected and utilized and has contributed to an important role in
Publisher’s Note: MDPI stays neutral
society’s survival and improvement since the early days of civilization. Nowadays, copper
with regard to jurisdictional claims in
is currently used in the structure’s construction, electricity generation and transmission,
published maps and institutional affil-
electronic product manufacturing, industrial machinery manufacturing, and transportation
iations.
vehicle manufacturing [3]. However, heavy metals are non-biodegradable, poisonous, and
easy to accumulate in living organisms in general, and in humans, at low quantities. It can
cause significant disorders such as cancer in the body, harm the neurological system and
Copyright: © 2022 by the authors.
cause kidney failures and can be fatal due to the high concentration.
Licensee MDPI, Basel, Switzerland. Cu is frequently discovered in high concentrations in wastewater as it is widely
This article is an open access article utilized in the industrial applications, including metal polishing, electroplating, plastics,
distributed under the terms and and etching. Furthermore, even at low concentrations, copper is a highly hazardous metal,
conditions of the Creative Commons and copper-contaminated wastewater must be treated before being discharged into the
Attribution (CC BY) license (https:// environment. Heavy metal contamination of soil is becoming a global problem due to the
creativecommons.org/licenses/by/ detrimental effects on environmental safety [4]. As Cu becomes more widely used in daily-
4.0/). life purposes, it has a severe influence on environmental degradation and biodiversity in

Water 2022, 14, 3086. https://doi.org/10.3390/w14193086 https://www.mdpi.com/journal/water

Water 2022, 14, 3086 2 of 15

both aquatic and terrestrial ecosystems, which has unconsciously given an impact toward
the human food sources. As a result of global industrialization, soil contamination with
harmful metals has increased dramatically in the recent years [5]. Therefore, it is important
to use as easy and as effective as possible approaches to treat heavy metals in terms
of treatment and removal [6]. Due to their widespread usage in agricultural activities,
Cu-based agrochemical products such as fertilizers, pesticides, insecticides, herbicides,
fungicides, miticides, and nematicides, which are used to improve crop yield and control
plant pests, are usually major sources of Cu deposition in soils [7]. Thus, it is critical
to remove the presence of Cu, particularly in water resources, prior to its discharge to
the environment [8]. Adsorption, cementation, membrane filtration, electrodialysis, and
photocatalysis are the available technologies that have been developed over the years for
the removal of copper ions from industrial wastewater.
The major goal of this review paper is to evaluate the fundamentals and key techniques
of Cu removal of different types of technologies that are currently applied. Although there
are few equivalent review studies on the removal of pollutants, the available literature is
broad in scope and takes into consideration other metal ions or is only focused on a single
treatment approach. In this study, Cu removal strategies are evaluated in terms of removal
efficiency, practicality, environmental friendliness, and process economics.

2. Copper (Cu) as a Pollutant in Wastewater

Cu is a heavy metal that can be found abundantly in the earth’s crust. Pure copper is
very malleable, has a relatively high melting point, and is a good heat conductor [9]. It reacts
with oxygen to generate a mild green color when exposed to the environment. Copper
alloyed with tin and zinc are also used to make bronze and brass. Since 9000 before century,
copper and its alloys have been employed by a variety of civilizations [10]. Copper artifacts
have been discovered all over the world. Electrical wiring, plumbing materials, roofing,
cookware, vehicle brake pads, and agricultural items are all examples of modern uses for
copper. Copper is found in the environment as a result of both natural and human activities.
Copper mining, metal and electrical production, agricultural and domestic pesticide and
fungicide use, leather processing, and car brake pads are all anthropogenic sources of
copper in the environment while forest fires, volcanic eruptions, and windblown dust are
the examples of natural sources of copper contamination. Copper is a vital nutrient, but
excessive amounts have been linked to stomach and intestinal irritation, liver and kidney
damage, and anemia [11]. Wilson’s disease patients may be at a higher risk of copper
poisoning than the general public [12]. As Cu(II) is a common heavy metal pollutant in
water supplies, it may cause hemolysis, cirrhosis, chronic anemia, as well as hepatotoxic and
nephrotoxic consequences such as vomiting, cramps, convulsions, and even death. Apart
from that, copper has acute effects on aquatic species in marine waters at 4.8 g/L [13]. Cu is
particularly toxic to salmon, with deleterious effects occurring at the concentrations of 0.18
to 2.1 g/L in freshwater. It has been reported that the changes in salmonid smoltification
processes, interference with fish sensory systems, predator avoidance, juvenile growth, and
migratory success behaviors have all been linked to copper [14].
As Cu is non-biodegradable, poisonous, and easy to accumulate in living organisms
in general and especially in the human body at low concentrations; they can cause major
illnesses such as cancer, nervous system damage, and kidney failure, and can be fatal at high
doses [1]. If ingested, heavy metal-polluted water is harmful to one’s health and can even
be fatal. Cu concentration in drinking water is influenced by pH, hardness, and distribution
system availability. Cu contamination of water networks has been reported from both
natural and artificial causes. Natural sources of copper in water bodies include weathering
of copper-bearing rocks, whereas anthropogenic sources include discharge from urban and
industrial wastes, as well as corrosion of pipelines and agricultural application [6]. Cu is a
necessary element for living beings, but its presence above the guidelines in drinking water
supplies possesses negative health consequences. As a result, to ensure the presence of Cu
in water is within the guidelines, Cu removal from water has been accomplished using a
 both natural and artificial causes. Natural sources of copper in water bodies include
weathering of copper-bearing rocks, whereas anthropogenic sources include discharge
from urban and industrial wastes, as well as corrosion of pipelines and agricultural appli-
cation [6]. Cu is a necessary element for living beings, but its presence above the guide-
lines in drinking water supplies possesses negative health consequences. As a result, to
Water 2022, 14, 3086 ensure the presence of Cu in water is within the guidelines, Cu removal from water 3 ofhas
15
been accomplished using a variety of techniques, including ion exchange, precipitation,
membrane separation, and adsorption [15–18].
variety of techniques, including ion exchange, precipitation, membrane separation, and
3. Copper [15–18].
adsorption Removal Techniques
Copper can be removed from wastewater by various techniques, namely, adsorption
3.using
Copper Removal
natural Techniques
and modified adsorbents, cementation, membrane filtration, electrochemi-
Copper can be removed from
cal methods, and photocatalysis. These wastewater by various
techniques work intechniques, namely,
different ways, but adsorption
all methods
using natural and modified adsorbents, cementation, membrane filtration, electrochemical
serve the same purpose which is to remove copper from the wastewater. However, differ-
methods, and photocatalysis.
ent techniques give different These
resultstechniques
due to many work in different
reasons includingways,
thebut all methods
efficiency of the
serve
methodthe same purpose
and the which that
parameters is to need
remove copper
to be from thewhen
considered wastewater.
using it.However,
Currently, different
there is
techniques give different
no single technique thatresults due tocompletely
can provide many reasons includingtreatment,
appropriate the efficiency of the
owing method
to the com-
and the parameters that need to be considered when using it. Currently, there is no
plicated character of the effluents [19]. Thus, a mix of techniques is frequently utilized to single
technique
obtain thethat can provide
desired completely
water quality in the appropriate treatment,
most cost-effective owing to the complicated
manner.
character of the effluents [19]. Thus, a mix of techniques is frequently utilized to obtain the
desired water quality in the most cost-effective manner.
3.1. Adsorption
Adsorption technique is the process of mass transfer, where adsorbate, the ions from
3.1. Adsorption
the gaseous or liquid stream is transferred to the surface of a porous solid, adsorbent as
Adsorption technique is the process of mass transfer, where adsorbate, the ions from
shown in Figure 1. This process creates a film of the adsorbate on the surface of the adsor-
the gaseous or liquid stream is transferred to the surface of a porous solid, adsorbent
bent and is bounded by chemical and physical interactions. According to Velasco-Gar-
as shown in Figure 1. This process creates a film of the adsorbate on the surface of the
duño et al., adsorption is currently the most simple and viable method of removing copper
adsorbent and is bounded by chemical and physical interactions. According to Velasco-
from wastewaters [20]. The key reason why adsorption is seen as an adaptable approach
Garduño et al., adsorption is currently the most simple and viable method of removing
for removing copper is due to being easily used on a large scale and has high efficiency.
copper from wastewaters [20]. The key reason why adsorption is seen as an adaptable
There are also several parameters that influence the adsorption process including surface
approach for removing copper is due to being easily used on a large scale and has high
area, adsorbate initial concentration, solution pH, temperature and interfering chemicals
efficiency. There are also several parameters that influence the adsorption process including
[21]. area, adsorbate initial concentration, solution pH, temperature and interfering
surface
chemicals [21].

Figure1.1.Illustration
Figure Illustrationofofadsorption
adsorptionofofadsorbate
adsorbateonto
ontoadsorbent.
adsorbent.

However, the development of an effective adsorbent is critical for the technique’s

effectiveness. Various adsorbents have been obtained from natural materials, modified
biopolymers, bio sorbents and nanomaterials [1,22]. Adsorbent materials must have a
large internal volume that is accessible to the fluid components being extracted. Next,
the adsorbent must have strength and resistance to attrition, as well as excellent kinetic
effects, which means it must be capable of swiftly transporting adsorbing molecules to the
adsorption sites. The sorption capacity of a material is also determined by its chemical
structure, porosity, specific surface area and diffusion characteristics. Furthermore, the
adsorption process is regulated not only by adsorbent properties, but also by its shape,
chemical composition, water solubility, and pollutant polarity. Last but not least, adsorbents
Water 2022, 14, 3086 4 of 15

also need to have numerous functional groups which can bind heavy metal ions from
wastewater during removal processes [19,23].

3.1.1. Natural Materials as Adsorbents

Natural zeolites with exceptional efficient ion exchange capability are considered
the most natural materials for the adsorption of copper [1]. Natural zeolites are porous
hydrated aluminosilicate minerals having useful physicochemical features including cation
exchange, molecular sieving, catalysis, and sorption [24]. There are over 40 different sorts of
natural zeolite found in nature, with clinoptilolite being one of the most common. Natural
zeolites with high clinoptilolite content are often used in technological application as it has
a high removal capacity of Cu ions. At pH 5, the clinoptilolite performed the best in terms
of Cu2+ ions removal [25]. However, different types of zeolites have selective adsorption of
various copper ions according to Al-Saydeh et al., For example, NaA zeolite removes Cu
(III) at natural pH while A4 zeolite is used to adsorb Cu (II) at natural and alkaline pH and
the adsorption of Cu (VI) is achieved at acidic pH using the same zeolite. Al-Saydeh et al.,
also mentioned that clinoptilolite has features of high selectivity for copper ions [1].
Other than that, clay–polymer composites that are made of natural clay minerals
can also be used to take out copper ions. Clay minerals are widely used as adsorbent
materials deu to their large specific surface area, chemical and mechanical stability, and
a wide range of surface and structural features, high cation exchange capacity and low
cost [26]. They may be reinforced with a polymeric material to increase their capacity to
separate Cu ions from aqueous solutions. Abd Hamid et al. also mentioned that due to
the negatively charged membrane surface, the presence of clay particles in the membrane
played an important role during adsorption as it can attract positive charge ions, which
improved metal adsorption [27]. Natural clay minerals are a good option as the adsorbents
for water purification since they are readily available, low-cost, natural resources that are
not toxic to the ecosystem. Thus, they will not negatively affect the wastewater when being
used for the treatment process.

3.1.2. Modified Biopolymers as Adsorbents

Modified biopolymers adsorbents are appealing to industries because they offer sev-
eral advantages over synthetic polymers, such as great abundance, biodegradability and
low cost. In addition, biopolymer-based adsorbents could be regenerated and reused
for metal removal after a number of adsorption-desorption cycles [28]. The main advan-
tage of using biopolymers is that its structure contains a variety of functional groups,
including amines and hydroxyls, which can improve the effectiveness of heavy metal ion
separation [1]. Examples of modified biopolymers that can be employed as adsorbents are
cellulose, chitin, chitosan, starch, and lignin.
Cellulose is the primary component of woody plant cell walls. It is the most abundant
and widely accessible carbohydrate on the planet. Cellulose has a limited chelating ability
to bind heavy metals. However, its modified forms, have extraordinary metal-binding
capacities. From the study, they also stated that modification of cellulose can be accom-
plished either by a direct chemical modification process or by grafting monomer to cellulose
backbone. On the other hand, chitin and chitosan are natural amino polysaccharides by
which could bind the heavy metals. Physical or chemical modification could be done on
chitin and chitosan to enhance the adsorption capacity for heavy metals and their resilience
towards the extreme pH conditions [28]. In addition, the modifications could also enhance
the mechanical robustness and chemical barrier.

3.1.3. Low-Cost Bio Sorbents as Adsorbents

In the recent years, progressive research has been conducted for the removal of heavy
metals from industrial wastewater by utilizing the adsorbents produced from agricultural
wastes, commonly referred to as bio-sorbents [1]. According to Lu and Gibb, spent grain is
one of the low-cost bio sorbents that can be utilized for the adsorption technique [29]. It
Water 2022, 14, 3086 5 of 15

is proven to be a safe and biodegradable bio-sorbent for application in the restoration of

copper-contaminated wastewater. From the study, they also stated that to avoid competitive
inhibition by protons or desorption of Cu2+ ions via ion exchange, the pH of the starting
solution must be kept above pH 3.6. The total quantity of Cu2+ ions adsorbed by wasted
grain was generally unaffected by flow rate but increased with Cu2+ ion concentration.
Aside from that, sawdust could be used as a functional adsorbent for the separation of
copper from wastewater as it has a high retention capacity after chemical activation [30].
Apart from that, coconut waste can also be used as a low-cost bio-sorbent. Because
of its high tannin content, coconut has a high sorption capability. Next, orange peel can
also be utilized to adsorb copper from wastewater. Orange peel is mostly made up of
components such as cellulose, pectin and lignin that can help to bind the copper ion and
separated them from the wastewater. Adedamola et al., also stated that these components
have numerous functional groups, such as carboxyl and hydroxyl, which make them a
promising adsorbent material for extracting metal ions from wastewater [31].
On the other hand, biodegradable composite can be one of the alternatives to low-
cost bio-sorbents. Velasco-Garduño et al., reported that the Ch-based biodegradable bio-
composite can efficiently remove Cu2+ in contaminated wastewater allowing for re-use
cycles besides having high robustness [20]. The study also shows that Ch-based bio-
composites are superior to other commercial absorbents, which are costly, have limited
biodegradability, and pose toxicity problems. The use of low-cost adsorbents may aid in
the preservation of the surrounding environment.

3.1.4. Nanomaterials as Adsorbents

Materials such as carbonaceous nanofibers (CNFs) and graphene oxide (GO) have
been applied for the removal of heavy metals from wastewater. Their distinct features,
which include strong resistance, good electrical conductivity, and thermal stability, as well
as their huge specific surface areas, make them viable adsorbents. The results reported by
García-Díaz et al., prove to demonstrate that helical carbon nanofibers are a viable copper
adsorbent in wastewaters. The pH value has the biggest impact on copper adsorption
capacity among the factors which were tested at a pH of 10. For GO, Al-Saydeh et al.
stated that the maximum copper ion sorption capacity was found to be 45.2 mg/g on pure
GO [1,32].
Moving on, nanocomposites made from clay minerals and polymers have developed
as a revolutionary method for cleaning polluted water and are employed as a coagulant,
catalytic agent, membrane, or filter. The addition of clay in appropriate amounts with
numerous inorganic polymers and biopolymers in the nanoscale range, or nano clay, for
the development of nanocomposites boosted its efficacy for pollutant removal in aqueous
systems [32]. However, to improve the environmental sustainability and safety of created
nanocomposites, the use of cost-effective and environmentally friendly resources such as
agro-waste, green extract, and industrial by-products should be encouraged.

3.2. Cementation
Cementation is a simple method for removing and recovering dangerous or valuable
metals in their metallic and reusable condition. Cementation involves the electrochemical
precipitation of one metal by another metal that is more electropositive. In the case of
copper removal, cementation is the process in which the copper ions are reduced to zero
valances at the interface of iron by spontaneous electrochemical reduction to reach the
copper metallic state [1]. The cementation is a cost-effective process as it is simple to operate.
However, an excessive sacrificial metal consumption is the drawback of this cementation
approach [33]. Furthermore, the sacrificial metal dissolution, which is more critical at
low pH levels is also the disadvantage of this technique. Thus, one critical feature of this
technique is the use of a non-toxic metal or a metal that is already present in the solution,
in order to avoid contamination with another ion [34].
Water 2022, 14, 3086 6 of 15

This technique’s efficiency is influenced by many factors including the pH value,

amount of sacrificial metal, copper concentration, temperature, stirring speed, the presence
of other ions, size of zinc particles and type of atmosphere. Based on Panão et al., the
cementation with zinc is favorable to be used to remove copper from solutions containing
zinc and iron compared to the use of iron and aluminium. This is because zinc is a superior
precipitant as it has a larger oxidation potential than iron. Despite having a larger oxidation
potential than zinc, the protective oxidation layer generated on the surface of aluminium
resulted in worse outcomes [34].

3.3. Membrane Filtration

Membrane filtration has gained lots of attention in the recent years for its ability to
remove suspended particles, organic molecules, and inorganic substances such as heavy
metals from copper-contaminated industrial waste water [8]. Furthermore, the key benefits
of using a membrane technique are no phase change, economic productivity, simplicity
of scaling up, high separation efficiency, and environmental safety. Ultrafiltration (UF),
nanofiltration (NF), and reverse osmosis (RO) are the commonly used membrane filtration
technique to remove copper from the wastewater.

3.3.1. Ultrafiltration (UF)

At low transmembrane pressures, ultrafiltration (UF) is a viable membrane technology
for removing copper ions from sewage. The pore size of UF is 5–20 nm, and the molecular
weight (MW) of isolated particles should be in the 1000–100,000 Da range. Based on the
membrane’s properties, UF membranes may achieve a good removal rate of over 90% for
initial copper concentrations ranging from 10 to 160 mg/L, with the optimal pH range
being 5.5 to 6, and an operating pressure of 2 to 5 bars [35]. The high packing density of UF
is a significant benefit, as it reduces the amount of space required.
Polymer enhanced ultrafiltration (PEUF) has also been studied in the recent years [35].
PEUF has been suggested as a method for removing copper ions from industrial effluent,
as shown in Table 1. The incorporated polymers are responsible for binding metal ions
and forming macromolecular metallic complexes that the UF can reject. These polymers
are normally polyelectrolytes containing functional groups, such as polyethyleneimine
(PEI), carboxyl methyl cellulose (CMC), and poly (acylic acid) sodium, which may interact
with ions by electrostatic attraction or establish stable bonds with them. The metal to
polymer ratio, polymer type, and pH levels are just a few of the many variables that
influence the PEUF process. Progressive research has been conducted to find the best
polymer to be used in the PEUF approach. PEI, humic acid, polyacrylic acid (PAA),
and diethylaminoethyl cellulose were among the polymers examined by Fu et al., that
exhibited selective separation of copper ions with higher energy efficiency. Molinari et al.,
demonstrated that polyethyleneimine (PEI) is successful in removing Cu (II) from polluted
wastewater, with the greatest results achieved when the pH was greater than 6 and the
metal to polymer mass ratio was about 3. PEUF has a plethora of benefit, including strong
affinity selectivity and efficacy in the elimination process. PEUF has yet to find widespread
industrial use, despite a substantial amount of research and several articles in this sector.

Table 1. Cu (II) removal by PEUF membrane.

Removal
UF Type Membrane Type Surfactant Agent Initial Conc. Ideal pH Reference
Efficiency
PEUF Polyethersulfone PEI 50 mg/L pH > 6 94% [36]
PEUF Polyethersulfone Carboxy methyl cellulose 10 mg/L pH = 7 97.6% [37]
PEUF Ceramic Poly (acylic acid) sodium 160 mg/L pH = 5.5 98–99.5% [38]
Water 2022, 14, 3086 7 of 15

3.3.2. Nanofiltration
The use of nanofiltration (NF) for the removal of heavy metals has grown quickly in
recent years, owing to the fact that it solves some of the issues associated with traditional
removal methods [39]. Al-Rashdi et al., proved the effectiveness of the NF membrane
in the removal of heavy metal ions. The NF is a pressure-driven process with particle
diameters ranging from ultrafiltration (UF) to reverse osmosis (RO). Donnan exclusion
(charge repulsion) and size exclusion are two distinct separation processes found in the NF
membrane [40]. The NF membrane has a number of advantages over other membrane types,
including a better rejection of multivalent copper ions than the UF membrane [24]. NF
membranes also have a greater water permeability, a higher refusal, and a reduced pressure
than RO membranes. As a result, the NF membrane approach is widely regarded as a
low-energy way of eliminating heavy metal ions. NF membranes generally have a particle
size of 1 nm, which corresponds to a MW cut-off (MWCO) of 300–500 Da, according to
Mohammad et al., Many different membrane separation technologies have been developed
to minimize the upfront cost and solving the issues of toxic elements in the industrial
water [41]. According to Kotrappanavar et al., most NF membranes are made up of thin
layer fiber composites of several manufactured materials with electrostatic interactions.
These groups have the potential to improve the polymer’s ability to remove charged
heavy metal ions from effluent. Electro migration, as well as sieving, the Donnan effect,
solution diffusion, and dielectric exclusion, are employed in NF membranes to separate
electrically neutral and charged particles, making them ideal for removal. According to
Al-Rashdi et al., under pressures ranging from 3 to 5 bar and pH values ranging from 1.50
to 5, the NF membrane completely recovered copper ions in a 1000 mg/L copper solution,
suggesting the feasibility of NF membranes for copper ions refusal. When the concentration
of copper rises to 2000 mg/L, however, the capacity of NF membranes to reject copper ions
decreases. Table 2 compares the removal of Cu (II) utilizing various NF technologies under
various operating circumstances. It can be observed that the integrated NF/RO membranes
have the capability to remove high concentrations of Cu (II) under low pressure. These
combination membranes can be used to treat wastewater with high rejection and pure
water recovery.

Table 2. Cu (II) removal techniques.

Membrane Types Initial Concentration Removal Efficiency Operation Circumstance References

NF 0.01 M 47–66% Transmembrane pressure 1–3 bar [42]
NF 0.47 M 96–98% Pressure = 20 bars [43]
RO 7.86 × 10−3 M 98–99.5% Pressure = 5 bars [44]
RO Between 4.7 × 10−4 and 1.57 × 10−3 M 70–90% Low pressure RO [45]
RO+NF 2M More than 95% Pressure = 35 bars [46]
RO+NF 0.015 M 95–99% Pressure = 3.8 bars [47]

3.3.3. Reverse Osmosis

Reverse osmosis (RO) is a method of separating polluted wastewater by pushing it
through a membrane that rejects the impurities solely on a single side while allowing the
clean solution to flow through on the other (Figure 2) [35]. Over the last decade, reverse
osmosis (RO) has emerged as one of the most effective separation technologies for industrial
effluent treatment and groundwater recharge [44]. The majority of the separation occurs in
the polymer matrix of RO membranes, which has a substantial protective film. On a broad
scale, the RO process may be used to eliminate a range of compounds from dirty water,
especially in industrial settings. However, Gunatilake shows that the RO process is mostly
composed of diffusive processes, and that the separation efficiency is highly dependent
on water flow rate, pressure, and solute concentration. RO brine is typically rich in heavy
metals (such as Mo, Cu, and Ni) as well as other less harmful toxic metals (i.e., Zn and
Fe) [44]. Hybrid systems combining electrodialysis and a particulate reactor are the best
alternative for increasing RO recovery by treating its core since the pellet reactor reduces
scalability capability while the electrodialysis treats the dirty wastewater [44]. Research has
 water, especially in industrial settings. However, Gunatilake shows that the RO process
is mostly composed of diffusive processes, and that the separation efficiency is highly de-
pendent on water flow rate, pressure, and solute concentration. RO brine is typically rich
in heavy metals (such as Mo, Cu, and Ni) as well as other less harmful toxic metals (i.e.,
Water 2022, 14, 3086 Zn and Fe) [44]. Hybrid systems combining electrodialysis and a particulate reactor 8 ofare
15
the best alternative for increasing RO recovery by treating its core since the pellet reactor
reduces scalability capability while the electrodialysis treats the dirty wastewater [44]. Re-
search
been has beenon
conducted conducted on of
the efficacy thethe
efficacy of thefor
RO method ROcopper
method for copper
removal removal andthat
and determined de-
termined that extraction efficiencies of 70–99.9% may be achieved. In a lab-scale
extraction efficiencies of 70–99.9% may be achieved. In a lab-scale experiment which inte- experi-
mentthe
grate which integrate
bioreactor the bioreactor
system system with RO
with RO membranes, membranes,
Dialynas Dialynas and Diamado-
and Diamadopoulos observed
poulos
that the observed
eliminationthat
of the elimination
copper ions wasofsuccessfully
copper ionsremoved.
was successfully removed.

Figure2.2.Reverse
Figure Reverseosmosis
osmosismechanism
mechanism[35].
[35].

3.4.
3.4.Electrochemical
ElectrochemicalMethods
Methods
In
In metallurgicaland
metallurgical andmetal
metalprocessing,
processing,electrochemical
electrochemical removal
removal techniques
techniquesforfor
separat-
sepa-
ing metal ions have been commonly adopted [48]. Electrocoagulation and
rating metal ions have been commonly adopted [48]. Electrocoagulation and electrodial- electrodialysis
are
ysisthe
aretwo mostmost
the two common
common electrochemical
electrochemical procedures
procedures forfor
removing
removingheavyheavymetal
metalions.
ions.
Electrodialysis
Electrodialysis is an electrochemical process to separate copper ions from industrial efflu-
is an electrochemical process to separate copper ions from industrial efflu-
ent,
ent,bybywhich
whichthe
thecopper
copper ions
ions exchange
exchange isis done
done via
via surfaces
surfaces under
under an an electric
electric field
field [49].
[49].
Furthermore,
Furthermore, the electric field starts when surface activities generate hydroxyl ions atthe
the electric field starts when surface activities generate hydroxyl ions at the
cathode
cathode andand protons
protons at the anode,
at the anode, respectively.
respectively. Metal
Metalions
ionshave
havea asignificant
significantattraction
attraction to
to
bebe desorbed
desorbed andand moved
moved moremore towards
towards the the cathode
cathode by electromigration
by electromigration because
because the
the ionic
ionic transformation
transformation of protons
of protons is much
is much bigger
bigger thanthan
thatthat of hydroxyl
of hydroxyl ionsions [50].
[50]. UrUr Rahmanet
Rahman
et al., invented a cost-effective and efficient electrolytic–electrodialytic equipment and
al., invented a cost-effective and efficient electrolytic–electrodialytic equipment and pro-
procedure for recovering metal ions from municipal wastewater. According to Nasef et al.,
cedure for recovering metal ions from municipal wastewater. According to Nasef et al.,
the features of the membrane used in the electrodialysis mechanism must be examined
the features of the membrane used in the electrodialysis mechanism must be examined
since all these factors impact the extent of copper ions segregation. Caprarescu et al., also
since all these factors impact the extent of copper ions segregation. Caprarescu et al., also
looked at the requirements for the membrane utilized in the electrodialysis process, which
looked at the requirements for the membrane utilized in the electrodialysis process, which
included chemical and thermal stability, as well as the capability to perform the separation
included chemical and thermal stability, as well as the capability to perform the separation
process at high temperatures and in solutions with extremely high or low pH values. A
process at high temperatures and in solutions with extremely high or low pH values. A
constant speed of metal-contaminated effluent may be recovered in a single unified cell flow
constant speed of metal-contaminated effluent may be recovered in a single unified cell
battery, as shown in Figure 3. There are three major portions in each individual cell: the
flow battery, as shown in Figure 3. There are three major portions in each individual cell:
catholyte section (101), the metal-contaminated wastewater section (102), and the anolyte
the catholyte section (101), the metal-contaminated wastewater section (102), and the
section (103). In order to access all cells from (108) and exit from the metal-contaminated
wastewater stream (100) will be split into many streams (109). The anolyte portion will
receive the metal ions via (110), while the oxygen generated by the anode and the hydrogen
produced by the cathode both exit from (112). (113). The stream will contain all effluent
wastewater (114).
Electrocoagulation, according to Lakhsamanan et al., is a great method for heavy
metals removal, particularly Cu, from industrial effluent. One of the electrochemical
methods for removing copper ions from industrial effluent is electrocoagulation [40]. This
is depending on dissolved metal anode from Al, Fe, or hybrid Al/Fe electrode materials in
situ to produce coagulant [51]. Metal ions are generated at the anode, while hydrogen gas
is formed at the cathode, which can assist in floating the agglomerates particles out of the
water. Electrocoagulation provides a number of advantages over alternative treatments,
including the fact that it is quick, efficient, economical, and ecologically friendly [52]. The
available density is the main factor in the electrocoagulation process since it impacts several
variables such as bubble generation rate, coagulant dosing rate, and floc size or growth,
in which these factors might affect electrocoagulation effectiveness. When the present
density rises, the anode dissociation rate rises as well, resulting in a rise in the quantity of
 Water 2022, 14, x FOR PEER REVIEW 9 of 15

Water 2022, 14, 3086 9 of 15

anolyte section (103). In order to access all cells from (108) and exit from the metal-con-
taminated
copper wastewater
hydroxide stream
flocs and (100)
a rise will be percentage
in copper split into many streams
removal [53].(109).
TableThe anolyte por-
3 demonstrates
tion will receive the metal ions via (110), while the oxygen generated by the
the impact of the electrocoagulation process operating conditions, electrode composition,anode and
the hydrogen produced by the cathode both exit from (112). (113). The stream
current or existing density, ideal pH, solution conductivity, and energy usage on copperwill contain
all effluent
removal rate. wastewater (114).

Figure3.3.The
Figure Theprinciple
principleofofelectrodialysis
electrodialysiscell
cellused
usedinincontinuous
continuousprocess
process[1].
[1].

Table 3. Different electrocoagulation

Electrocoagulation, techniques
according for removingetCu(II).
to Lakhsamanan al., is a great method for heavy
metals removal, particularly Cu, from industrial effluent. One of the electrochemical
Reactor Current Density Conductivity Expenditure of Ideal industrial
pH Electrode Removal Rate References
methods
(mS/cm)for removing Energy
copper ions from effluent is electrocoagulation
Component [40]. This
4.8 A/dm3 is depending
- on dissolved - metal anode4 from Al, Fe, or hybrid Al/Fe
Al-Al 99%electrode materials
[54]
Continuous 5A in situ to- produce coagulant
10.99 kWh/kg 0.64ions are generated
[51]. Metal Ss-Ti 98.8% while hydrogen
at the anode, [55]
5A 1600 35.63 kWh/g 7 Fe-Fe 99.99% [56]
5A gas is formed
1600 at the cathode, which
35.06 kWh can 7assist in floating
Al-Al the agglomerates
99.9% particles
[56]out of
Batch 0.3 A 0.634 - 5 RO-Ti-Ss 99% [57]
the water. Electrocoagulation 3provides3 a numberFe-Al of advantages 100%over alternative treat-
100 A/m2 2 10.07 kWh/m [28]
33 A/m2 ments, 20 including the fact- that it is quick,
9 efficient,Al-Al
economical, and ecologically [58]
>50% friendly
[52]. The available density is the main factor in the electrocoagulation process since it im-
pacts several variables such as bubble generation rate, coagulant dosing rate, and floc size
Despite the significant numbers of study and method advances in electrocoagulation
or growth, in which these factors might affect electrocoagulation effectiveness. When the
technology over the last decade, more research is required to fathom the implications of cell
present density rises, the anode dissociation rate rises as well, resulting in a rise in the
design and electrode configuration on heavy metal removal efficiency. Moreover, because
quantity of copper hydroxide flocs and a rise in copper percentage removal [53]. Table 3
the majority of recent research has been executed on a laboratory level, extra work has to
demonstrates the impact of the electrocoagulation process operating conditions, electrode
be done into assessing the electrocoagulation mechanism at the production plant scale.
composition, current or existing density, ideal pH, solution conductivity, and energy us-
agePhotocatalysis
3.5. on copper removal rate.
Photocatalysis is a promising treatment technology for a variety of municipal wastew-
Table 3. Different electrocoagulation techniques for removing Cu(II).
aters. Under solar radiation, electron–hole pairs (e/h+) can be continuously created from
Current semiconductors
Conductivityin Expenditure of Ideal
this process. ZnO, Electrode
ZnS, TiO2, and CeO2 are just Removal
a few of the semiconduc-
Reactor References
Density tors that have been used
(mS/cm) [59]. In order pH
Energy to discover the optimum semiconductor
Component Rate for removal
4.8 A/dm3 of copper, - numerous experiments- have 4 been reported
Al-Al in various99% studies. According
[54] to
Continuous Mahdavi, et al. [60], TiO is the most extensively used because of its strong photocatalysis,
5A - 10.99 kWh/kg
2 0.64 Ss-Ti 98.8% [55]
5A durability,
1600low toxicity,35.63and exceptional7 dielectric Fe-Fe
kWh/g characteristics.99.99%
A photocatalytic [56]proce-
dure to remove Cu (II) has been reported utilizing TiO2 as a semiconductor and a 254 nm
5A 1600 35.06 kWh 7 Al-Al 99.9% [56]
UVC light in varied test conditions. The best results for Cu (II) removal were obtained
Batch 0.3 A 0.634 - 5 RO-Ti-Ss 99% [57]
when the pH was between pH 3.5 and pH 4.5 and the TiO2 mass was between 0.5 and
100 A/m2 2 10.07 kWh/m3 3 Fe-Al 100% [28]
0.75 g. TiO2 can be employed in the photocatalysis removal process roughly 80% of Cu (II)
33 A/m according
2 20to the findings [1]. - Furthermore, 9 Barakat Al-Al
et al., performed >50%
a photocatalytic[58]degra-
dation experiment utilizing UV-irradiated TiO2 suspension to remove copper and destroy
complexDespite the significant
cyanide. Copper with numbers ofconcentration
an initial study and method
of 102advances
M was fully in electrocoagulation
eliminated in 3 h,
technology over the last decade, more research is required to fathom
according to the data. Wahyuni et al., investigated the photocatalytic elimination the implications of
of Cu (II)
cell design and electrode configuration on heavy metal removal efficiency.
using an UV light with a spectrum of 290–390 nm and a starting concentration of 10 mg/L. Moreover, be-
cause50
When themgmajority
of TiO2of recent
was usedresearch
at pH 5,hasthe been executed
greatest on a laboratory
photocatalytic efficiencylevel,
wasextra work
achieved,
removing 45.56% of the copper ions.
 catalytic degradation experiment utilizing UV-irradiated TiO2 suspension to remove cop-
per and destroy complex cyanide. Copper with an initial concentration of 102 M was fully
eliminated in 3 h, according to the data. Wahyuni et al., investigated the photocatalytic
elimination of Cu (II) using an UV light with a spectrum of 290–390 nm and a starting
Water 2022, 14, 3086
concentration of 10 mg/L. When 50 mg of TiO2 was used at pH 5, the greatest photocata-
10 of 15
lytic efficiency was achieved, removing 45.56% of the copper ions.

3.6. Comparison of Copper Removal Processes

3.6. Comparison of Copper Removal Processes
In general, alternatives for removing copper ions from industrial wastewater have
In general,
undergone alternatives
progressive for
research. removing
Figure copper ions
4 summarizes from industrial
the process of copperwastewater have
removal from
undergone progressive research. Figure 4 summarizes the process of copper removal
wastewater using different techniques that have been discussed previously. Chemical, from
wastewater using different techniques that have been discussed previously. Chemical,
physical, and biological treatments are the most common, and they are chosen for a vari-
physical, and biological treatments are the most common, and they are chosen for a variety
ety of reasons, including high selectivity, ease of control, and reduced space requirements.
of reasons, including high selectivity, ease of control, and reduced space requirements. The
The most acceptable treatment methods for removing copper ions from industrial efflu-
most acceptable treatment methods for removing copper ions from industrial effluents are
ents are physico-chemical treatments. However, due to the high cost of the chemicals re-
physico-chemical treatments. However, due to the high cost of the chemicals required and
quired and the significant energy consumption, they still have a high operational cost.
the significant energy consumption, they still have a high operational cost. Since metal-
Since metal-contaminated effluent can contain both inorganic and organic contaminants,
contaminated effluent can contain both inorganic and organic contaminants, photocatalysis
photocatalysis is a promising technology for eliminating them at the same time. Therefore,
is a promising technology for eliminating them at the same time. Therefore, every method
every method of treatment does have its own benefits and drawbacks. The key benefits
of treatment does have its own benefits and drawbacks. The key benefits and drawbacks
and drawbacks of the various physicochemical procedures considered in this analysis are
of the various physicochemical procedures considered in this analysis are represented in
represented in Table 4, with their Cu(II) removal efficiencies shown in Table 5.
Table 4, with their Cu(II) removal efficiencies shown in Table 5.

Figure 4. The
Figure process
4. The of of
process copper removal
copper from
removal wastewater.
from wastewater.

Table 4. Advantages and disadvantages of different treatment methods.

Removal Technique Benefits Drawbacks

• Minimal start-up costs • Copper ions are restricted to certain
Adsorption using inexpensive adsorbents
• Simple concept concentrations.
• Inexpensive cost procedure
Cementation • Low energy usage • Excessive use of sacrificial metal
• Simple functioning and convenient
• Low operating pressure
Membrane filtration • Small space requirement • Operating costs are high.
• Highly selective separation
• Separation that is
Electrochemical methods • A substantial operating cost
extremely selective
• Extremely high energy usage
• Environmentally safe
• Removal of chemical and metal
Photocatalysis • The time span is rather long.
contaminants in tandem
• It is only beneficial in situations.
• Creates less harmful by-products

Table 5. Cu (II) removal efficiency using different treatment methods.

Removal Technique Type of Material Operating Condition Removal Ref.

Efficiency
Initial concentration of 100 mg/L, adsorbent
• Orange peel 86.3% [61]
Adsorption using dosage of 1 g, reaction time of 120 min, pH 5.
• Activated carbon derived from Initial concentration of 500 mg/L, adsorbent
inexpensive adsorbents 99.0% [62]
Ascophyllum nodosum seaweed dosage of 0.2 mg, reaction time of 6 hr, pH 5.
Water 2022, 14, 3086 11 of 15

Table 5. Cont.

Removal Technique Type of Material Operating Condition Removal Ref.

Efficiency
Initial concentration of 750 mg/L, reaction time
95% [63]
• Iron Powder of 7 min, pH 2.95, linear speed of 24.13 m/s.
Cementation Initial concentration of 3 g/L, reaction time of
• Zinc powder 90% [64]
10 min, pH 1, rotational speed of 500 rpm.
Initial concentration of 25 mg/L, Pressure of
• PEUF+polyvinylamine (PVA) 90% [65]
200 kPa, pH 6
Membrane filtration • NF: Poly (amidoamine) Initial concentration of 1000 mg/L, Pressure of
dendrimer (PAMAM) 99% [66]
1000 kPa, pH 8
Initial concentration of 0.06 M, pH 6.6, energy
70% [67]
• Nickel Sulfate supply 10 V, 20 h
Electrochemical methods • Graphene oxide/polypyrrole Initial concentration of 100 mg/L, pH 7.0,
82.8% [68]
energy supply 0.6 V, 96 h
Initial concentration of 20 mg/L, reaction time
98.9% [69]
of 2 h, pH 7
Photocatalysis • TiO2/ZnO–CaAlg
Initial concentration of 10−4 mol/L, reaction 70% [70]
time of 30 min, pH 5

4. Challenges of Copper Removal

As discussed before, copper (Cu) is removed from wastewater by different methods
for examples chemical, physical, and biological. However, the selection is influenced
by numbers of factors with the consideration of advantages and disadvantages. For the
current methods applied, the challenges are copper concentration limits, high operating
costs, excess consumption of sacrificial metals, high energy consumption, and the long time
required for the process [1]. In addition, in the presence of other metals, the selectivity of
copper could be a problem, by which most copper is bound with other metals in wastewater.
For example, the work done by Larsson and his coworkers—on real acid mine drainage
solutions with copper and other metals in acidic conditions using PEI-GA-DE to extract
copper—showed that the selectivity was low, resulting in a high copper concentration
after the process [71]. In addition, Abdel Salam et al., reported a limited applicability to
particular copper ion concentrations where some polluted samples are not treated due to
the low concentration of copper which could be the case. A study by Anastopoulos and
Kyzas reported that the efficiency of heavy metals removal via the adsorption method is
also dependent on the pH of the treated water, in which the optimum pH was reported to
be in the range of pH 2 to pH 6. As for cementation technology, DemirkIRan and Künkül
mentioned the fundamental problem is the excessive use of sacrificial metal. The excess
usage of a source always causes unsustainability which is considered a drawback and
a challenge to solve in order to improve the current solution in removing copper from
wastewater [1].
Some difficulties arise as a result of the type of reactor used, especially when using
electrochemical technology. Using a fluidized bed, for example, could result in poor
charge transfer and non-uniform potential distribution. In addition, the chemical-physical
treatment introduces new challenges such as incomplete removal, consumption of high
energy and converting the dissolved metals to solid sludge which requires further waste
treatment [72].

5. Conclusions
In conclusion, due to the negative effects of heavy metals on human health and living
creatures in the environment, the removal of heavy metals in general and copper from
industrial effluent is a very essential aspect of most contemporary environmental research.
Different treatment strategies such as physical, chemical, and biological treatments were
discussed based on the past few years. These methods that have been introduced are ad-
sorption, cementation, membrane filtration, electrodialysis, and photocatalysis. However,
there are some precautions that should be taken seriously as it is influenced by the param-
eters such as initial concentration of copper ions, pH values, economic parameters such
as operation cost, and the environmental effects and compatibility of each of the various
Water 2022, 14, 3086 12 of 15

methods conducted. More studies should be conducted in order to improve on certain areas.
This is because current cementation agents require a long time to remove greater copper
ions from wastewater; hence, future research in these areas should focus on evaluating new
cementation agents that can shorten the process time. Furthermore, the impact of pressure
as a control parameter has yet to be determined. Innovative strategies are required to pro-
duce economical, readily available, excellent, and long-lasting membranes for membrane
filtering. In the case of electrodialysis, innovative designs are required to improve separa-
tion efficiency. More research into the effect of temperature on the photocatalysis approach
is required. It is necessary to develop catalysts for a high-photon-efficiency process that
can use a wider range of spectrum. Recently, studies have demonstrated that biosorption
and natural adsorbents can be applied to treat copper pollutants from wastewaters. Conse-
quently, new forms of biosorbents must be evaluated to achieve maximum effectiveness.
Some of the benefits include low cost of raw material, good adsorption performance, and
environmentally friendly. Therefore, it is a promising technique for copper removal. For
further investigation into copper treatment in wastewater, various information gaps must
be investigated. First off, laboratory batch equilibrium studies have been the main focus
of the majority of copper biosorption research. This is due to two factors: (a) the lack of
bulk biomass for use at full scale, and (b) batch procedures, which are simple to conduct
in a lab setting but challenging in the field. Therefore, there is clearly a need for further
research into the development of low-cost biosorbents with excellent adsorption capacities
for copper treatment. Additionally, it seems that the pH impact is a limiting factor that
influences copper treatment possibilities. For instance, the starting solution’s pH must be
maintained above pH 3.6 to prevent competitive inhibition by protons or the desorption of
Cu2+ ions by ion exchange. Undesirably, pH adjustment may be expensive, thus it should
be carefully taken into account when designing the copper treatment procedure. Despite
having a significant potential to efficiently treat copper in wastewater, other procedures
including cementation, membrane filtration, electrodialysis, and photocatalysis may not be
fully implemented due to the expense.

Author Contributions: Conceptualization, N.H.A.H. and M.I.H.b.M.T.; validation, A.C., A.H.N.,

A.A.A. and A.I.R.; writing—original draft preparation, N.H.A.H., M.I.H.b.M.T. and A.C.; writing—
review and editing, A.H.N., A.A.A., M.A.S., N.’I.N., N.D.N., S.S. and A.I.R.; funding acquisition,
N.H.A.H. and A.I.R. All authors have read and agreed to the published version of the manuscript.
Funding: The authors would like to express gratitude for the financial support received from the
Universiti Teknologi Malaysia, the project “The impact of Malaysian bamboos’ chemical and fibre char-
acteristics on their pulp and paper properties, grant number PY/2022/02318—Q.J130000.3851.21H99”.
The research has been conducted under the program Research Excellence Consortium (JPT (BPKI)
1000/016/018/25 (57)) provided by the Ministry of Higher Education Malaysia (MOHE).
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Al-Saydeh, S.A.; El-Naas, M.H.; Zaidi, S.J. Copper removal from industrial wastewater: A comprehensive review. J. Ind. Eng.
Chem. 2017, 56, 35–44. [CrossRef]
2. Horstkotte, B.; Alexovič, M.; Maya, F.; Duarte, C.M.; Andruch, V.; Cerdá, V. Automatic determination of copper by in-syringe
dispersive liquid–liquid microextraction of its bathocuproine-complex using long path-length spectrophotometric detection.
Talanta 2012, 99, 349–356. [CrossRef] [PubMed]
3. Doebrich, J.L. Copper: A Metal for the Ages; US Department of the Interior, US Geological Survey: Reston, VI, USA, 2009.
4. Wuana, R.A.; Okieimen, F.E. Heavy metals in contaminated soils: A review of sources, chemistry, risks and best available
strategies for remediation. Int. Sch. Res. Not. 2011, 2011, 402647. [CrossRef]
5. Nevin, R. Understanding international crime trends: The legacy of preschool lead exposure. Environ. Res. 2007, 104, 315–336.
[CrossRef] [PubMed]
6. Alexovič, M.; Balogh, I.S.; Škrlíková, J.; Andruch, V. A dispersive liquid–liquid microextraction procedure for UV-Vis spectropho-
tometric determination of chromium (VI) in water samples. Anal. Methods 2012, 4, 1410–1414. [CrossRef]
Water 2022, 14, 3086 13 of 15

7. Husak, V. Copper and copper-containing pesticides: Metabolism, toxicity and oxidative stress. J. Vasyl Stefanyk Precarpathian Natl.
Univ. Ser. Soc. Hum. Sci. 2015, 2, 39–51. [CrossRef]
8. Barakat, M. New trends in removing heavy metals from industrial wastewater. Arab. J. Chem. 2011, 4, 361–377. [CrossRef]
9. Tran, T.Q.; Chinnappan, A.; Lee, J.K.Y.; Loc, N.H.; Tran, L.T.; Wang, G.; Kumar, V.V.; Jayathilaka, W.; Ji, D.; Doddamani, M. 3D
printing of highly pure copper. Metals 2019, 9, 756. [CrossRef]
10. Tortella, G.; Pieretti, J.; Rubilar, O.; Fernández-Baldo, M.; Benavides-Mendoza, A.; Diez, M.; Seabra, A. Silver, copper and copper
oxide nanoparticles in the fight against human viruses: Progress and perspectives. Crit. Rev. Biotechnol. 2022, 42, 431–449.
[CrossRef]
11. Pandey, G.; Madhuri, S. Heavy metals causing toxicity in animals and fishes. Res. J. Anim. Vet. Fish. Sci. 2014, 2, 17–23.
12. Huster, D. Wilson disease. Best Pract. Res. Clin. Gastroenterol. 2010, 24, 531–539. [CrossRef] [PubMed]
13. Chouyyok, W.; Shin, Y.; Davidson, J.; Samuels, W.D.; LaFemina, N.H.; Rutledge, R.D.; Fryxell, G.E.; Sangvanich, T.; Yantasee, W.
Selective removal of copper (II) from natural waters by nanoporous sorbents functionalized with chelating diamines. Environ. Sci.
Technol. 2010, 44, 6390–6395. [CrossRef] [PubMed]
14. Hecht, S.A.; Baldwin, D.H.; Mebane, C.A.; Hawkes, T.; Gross, S.J.; Scholz, N.L. An Overview of Sensory Effects on Juvenile Salmonids
Exposed to Dissolved Copper: Applying a Benchmark Concentration Approach to Evaluate Sublethal Neurobehavioral Toxicity; NOAA: Silver
Spring, MD, USA, 2007.
15. Hirotsu, K.E.; Chen, J.K. Metals in Coins. In Metal Allergy; Springer: Berlin/Heidelberg, Germany, 2018; pp. 197–209.
16. Da˛browski, A.; Hubicki, Z.; Podkościelny, P.; Robens, E. Selective removal of the heavy metal ions from waters and industrial
wastewaters by ion-exchange method. Chemosphere 2004, 56, 91–106. [CrossRef] [PubMed]
17. Bhattacharyya, K.G.; Gupta, S.S. Adsorptive accumulation of Cd(II), Co(II), Cu(II), Pb(II), and Ni(II) from water on montmoril-
lonite: Influence of acid activation. J. Colloid Interface Sci. 2007, 310, 411–424. [CrossRef] [PubMed]
18. Shrivastava, A. A review on copper pollution and its removal from water bodies by pollution control technologies. Indian, J.
Environ. Prot. 2009, 29, 552–560.
19. Alila, S.; Costa, A.I.; Vieira Ferreira, L.F.; Boufi, S. Modified biopolymer adsorbent for the removal of dissolved organic pollutants.
Int. J. Environ. Technol. Manag. 2010, 12, 163. [CrossRef]
20. Velasco-Garduño, O.; Martínez, M.E.; Gimeno, M.; Tecante, A.; Beristain-Cardoso, R.; Shirai, K. Copper removal from wastewater
by a chitosan-based biodegradable composite. Environ. Sci. Pollut. Res. 2020, 27, 28527–28535. [CrossRef]
21. Grassi, M.; Kaykioglu, G.; Belgiorno, V.; Lofrano, G. Removal of emerging contaminants from water and wastewater by adsorption
process. In Emerging Compounds Removal from Wastewater; Springer: Berlin/Heidelberg, Germany, 2012; pp. 15–37.
22. Nordin, A.H.; Ahmad, K.; Xin, L.K.; Syieluing, W.; Ngadi, N. Efficient adsorptive removal of methylene blue from synthetic dye
wastewater by green alginate modified with pandan. Mater. Today: Proc. 2021, 39, 979–982. [CrossRef]
23. Lucaci, A.R.; Bulgariu, D.; Popescu, M.-C.; Bulgariu, L. Adsorption of Cu(II) Ions on Adsorbent Materials Obtained from Marine
Red Algae Callithamnion corymbosum sp. Water 2020, 12, 372. [CrossRef]
24. Duan, J.; Lu, Q.; Chen, R.; Duan, Y.; Wang, L.; Gao, L.; Pan, S. Synthesis of a novel flocculant on the basis of crosslinked Konjac
glucomannan-graft-polyacrylamide-co-sodium xanthate and its application in removal of Cu2+ ion. Carbohydr. Polym. 2010, 80,
436–441. [CrossRef]
25. Gökçekus, H.; Türker, U.; LaMoreaux, J.W. Survival and Sustainability: Environmental Concerns in the 21st Century; Springer Science
& Business Media: Berlin/Heidelberg, Germany, 2011.
26. Srinivasan, R. Advances in application of natural clay and its composites in removal of biological, organic, and inorganic
contaminants from drinking water. Adv. Mater. Sci. Eng. 2011, 2011, 872531. [CrossRef]
27. Abd Hamid, S.; Shahadat, M.; Ballinger, B.; Azha, S.F.; Ismail, S.; Ali, S.W.; Ahammad, S.Z. Role of clay-based membrane for
removal of copper from aqueous solution. J. Saudi Chem. Soc. 2020, 24, 785–798. [CrossRef]
28. Xiao, M.; Hu, J.C.; Liu, W.L.; Nie, F.M. Application of biopolymer-based adsorbents in removal of heavy metals. In Proceedings of
the Advanced Materials Research; Trans Tech Publications Ltd: Bach, Switzerland, 2014; pp. 373–377.
29. Lu, S.; Gibb, S.W. Copper removal from wastewater using spent-grain as biosorbent. Bioresour. Technol. 2008, 99, 1509–1517.
[CrossRef] [PubMed]
30. Larous, S.; Meniai, A. Removal of copper (II) from aqueous solution by agricultural by-products-sawdust. Energy Procedia 2012,
18, 915–923.
31. Biswas, A.; Das, S.; Seth, S.; Maulik, S.; Bhargava, B.; Rao, V. Role of modifying genes on the severity of rare mutation of MYH7
gene in hypertrophic obstructive cardiomyopathy. J. Clin. Exp. Cardiol. 2012, 3, 1000225. [CrossRef]
32. García-Díaz, I.; López, F.A.; Alguacil, F.J. Carbon nanofibers: A new adsorbent for copper removal from wastewater. Metals 2018,
8, 914. [CrossRef]
33. Nassef, E.; El-Taweel, Y.A. Removal of copper from wastewater by cementation from simulated leach liquors. J. Chem. Eng.
Process Technol. 2015, 6, 1. [CrossRef]
34. Panão, A.S.; De Carvalho, J.M.; Correia, M.J. Copper Removal from Sulphuric Leaching Solutions by Cementation; Centre of Chemical
Processes, Technical University of Lisbon: Lisbon, Portugal, 2006.
35. Gunatilake, S. Methods of removing heavy metals from industrial wastewater. Methods 2015, 1, 14.
36. Molinari, R.; Poerio, T.; Argurio, P. Selective separation of copper (II) and nickel (II) from aqueous media using the complexation–
ultrafiltration process. Chemosphere 2008, 70, 341–348. [CrossRef]
Water 2022, 14, 3086 14 of 15

37. Barakat, M.; Schmidt, E. Polymer-enhanced ultrafiltration process for heavy metals removal from industrial wastewater. Desalination
2010, 256, 90–93. [CrossRef]
38. Camarillo, R.; Llanos, J.; García-Fernández, L.; Pérez, Á.; Canizares, P. Treatment of copper (II)-loaded aqueous nitrate solutions
by polymer enhanced ultrafiltration and electrodeposition. Sep. Purif. Technol. 2010, 70, 320–328. [CrossRef]
39. Al-Rashdi, B.; Johnson, D.; Hilal, N. Removal of heavy metal ions by nanofiltration. Desalination 2013, 315, 2–17. [CrossRef]
40. Akbal, F.; Camcı, S. Copper, chromium and nickel removal from metal plating wastewater by electrocoagulation. Desalination
2011, 269, 214–222. [CrossRef]
41. Feng, B.; Fang, Z.; Hou, J.; Ma, X.; Huang, Y.; Huang, L. Effects of heavy metal wastewater on the anoxic/aerobic-membrane
bioreactor bioprocess and membrane fouling. Bioresour. Technol. 2013, 142, 32–38. [CrossRef] [PubMed]
42. Al-Rashdi, B.; Somerfield, C.; Hilal, N. Heavy metals removal using adsorption and nanofiltration techniques. Sep. Purif. Rev.
2011, 40, 209–259. [CrossRef]
43. Oh-sik, K. Removal of Heavy Metals in Wastewater Using a Nano-Filtration Membrane Technology; Korea Environmental Industry and
Technology Institute: Seoul, Korea, 2011.
44. Tran, A.T.; Zhang, Y.; Jullok, N.; Meesschaert, B.; Pinoy, L.; Van der Bruggen, B. RO concentrate treatment by a hybrid system
consisting of a pellet reactor and electrodialysis. Chem. Eng. Sci. 2012, 79, 228–238. [CrossRef]
45. Zhang, L.; Yanjun, W.; Xiaoyan, Q.; Zhenshan, L.; Jinren, N. Mechanism of combination membrane and electro-winning process
on treatment and remediation of Cu2+ polluted water body. J. Environ. Sci. 2009, 21, 764–769. [CrossRef]
46. Cséfalvay, E.; Pauer, V.; Mizsey, P. Recovery of copper from process waters by nanofiltration and reverse osmosis. Desalination
2009, 240, 132–142. [CrossRef]
47. Sudilovskiy, P.; Kagramanov, G.; Kolesnikov, V. Use of RO and NF for treatment of copper containing wastewaters in combination
with flotation. Desalination 2008, 221, 192–201. [CrossRef]
48. Fu, F.; Wang, Q. Removal of heavy metal ions from wastewaters: A review. J. Environ. Manag. 2011, 92, 407–418. [CrossRef]
49. Caprarescu, S.; Purcar, V.; Sarbu, A.; Radu, A.-L.; Ghiurea, M.; Maior, I. The use of electrodialysis for Cu2+ removal from
wastewater. Rev Roum Chim 2014, 59, 639–644.
50. Pedersen, K.B.; Ottosen, L.M.; Jensen, P.E.; Lejon, T. Comparison of 2-compartment, 3-compartment and stack designs for
electrodialytic removal of heavy metals from harbour sediments. Electrochim. Acta 2015, 181, 48–57. [CrossRef]
51. Chen, G. Electrochemical technologies in wastewater treatment. Sep. Purif. Technol. 2004, 38, 11–41. [CrossRef]
52. Cañizares, P.; Jiménez, C.; Martínez, F.; Sáez, C.; Rodrigo, M.A. Study of the electrocoagulation process using aluminum and iron
electrodes. Ind. Eng. Chem. Res. 2007, 46, 6189–6195. [CrossRef]
53. Bukhari, A.A. Investigation of the electro-coagulation treatment process for the removal of total suspended solids and turbidity
from municipal wastewater. Bioresour. Technol. 2008, 99, 914–921. [CrossRef] [PubMed]
54. Adhoum, N.; Monser, L.; Bellakhal, N.; Belgaied, J.-E. Treatment of electroplating wastewater containing Cu2+ , Zn2+ and Cr (VI)
by electrocoagulation. J. Hazard. Mater. 2004, 112, 207–213. [CrossRef]
55. Basha, C.A.; Bhadrinarayana, N.; Anantharaman, N.; Begum, K.M.S. Heavy metal removal from copper smelting effluent using
electrochemical cylindrical flow reactor. J. Hazard. Mater. 2008, 152, 71–78. [CrossRef]
56. Nouri, J.; Mahvi, A.; Bazrafshan, E. Application of electrocoagulation process in removal of zinc and copper from aqueous
solutions by aluminum electrodes. Int. J. Environ. Res. 2010, 4, 201–208.
57. Khelifa, A.; Moulay, S.; Naceur, A. Treatment of metal finishing effluents by the electroflotation technique. Desalination 2005, 181,
27–33. [CrossRef]
58. Holt, P.K.; Barton, G.W.; Wark, M.; Mitchell, C.A. A quantitative comparison between chemical dosing and electrocoagulation.
Colloids Surf. A Physicochem. Eng. Asp. 2002, 211, 233–248. [CrossRef]
59. Vunain, E.; Mishra, A.; Mamba, B. Dendrimers, mesoporous silicas and chitosan-based nanosorbents for the removal of heavy-
metal ions: A review. Int. J. Biol. Macromol. 2016, 86, 570–586. [CrossRef] [PubMed]
60. Mahdavi, S.; Jalali, M.; Afkhami, A. Heavy metals removal from aqueous solutions using TiO2 , MgO, and Al2 O3 nanoparticles.
Chem. Eng. Commun. 2013, 200, 448–470. [CrossRef]
61. Afolabi, F.O.; Musonge, P.; Bakare, B.F. Adsorption of Copper and Lead Ions in a Binary System onto Orange Peels: Optimization,
Equilibrium, and Kinetic Study. Sustainability 2022, 14, 10860. [CrossRef]
62. Katiyar, R.; Patel, A.K.; Nguyen, T.-B.; Singhania, R.R.; Chen, C.-W.; Dong, C.-D. Adsorption of copper (II) in aqueous solution
using biochars derived from Ascophyllum nodosum seaweed. Bioresour. Technol. 2021, 328, 124829. [CrossRef] [PubMed]
63. Shishkin, A.; Mironovs, V.; Vu, H.; Novak, P.; Baronins, J.; Polyakov, A.; Ozolins, J. Cavitation-dispersion method for copper
cementation from wastewater by iron powder. Metals 2018, 8, 920. [CrossRef]
64. Shahrivar, E.; Karamoozian, M.; Gharabaghi, M. Modeling and optimization of oxide copper cementation kinetics. SN Appl. Sci.
2020, 2, 1–13. [CrossRef]
65. Huang, Y.; Wu, D.; Wang, X.; Huang, W.; Lawless, D.; Feng, X. Removal of heavy metals from water using polyvinylamine by
polymer-enhanced ultrafiltration and flocculation. Sep. Purif. Technol. 2016, 158, 124–136. [CrossRef]
66. Zhu, W.-P.; Gao, J.; Sun, S.-P.; Zhang, S.; Chung, T.-S. Poly (amidoamine) dendrimer (PAMAM) grafted on thin film composite
(TFC) nanofiltration (NF) hollow fiber membranes for heavy metal removal. J. Membr. Sci. 2015, 487, 117–126. [CrossRef]
67. Tran, T.-K.; Chiu, K.-F.; Lin, C.-Y.; Leu, H.-J. Electrochemical treatment of wastewater: Selectivity of the heavy metals removal
process. Int. J. Hydrog. Energy 2017, 42, 27741–27748. [CrossRef]
Water 2022, 14, 3086 15 of 15

68. Rikame, S.S.; Mungray, A.A.; Mungray, A.K. Modification of anode electrode in microbial fuel cell for electrochemical recovery of
energy and copper metal. Electrochim. Acta 2018, 275, 8–17. [CrossRef]
69. Kanakaraju, D.; Ravichandar, S.; Lim, Y.C. Combined effects of adsorption and photocatalysis by hybrid TiO2/ZnO-calcium
alginate beads for the removal of copper. J. Environ. Sci. 2017, 55, 214–223. [CrossRef] [PubMed]
70. Zheng, P.; Pan, Z.; Li, H.; Bai, B.; Guan, W. Effect of different type of scavengers on the photocatalytic removal of copper and
cyanide in the presence of TiO2 @ yeast hybrids. J. Mater. Sci. Mater. Electron. 2015, 26, 6399–6410. [CrossRef]
71. Larsson, M.; Nosrati, A.; Kaur, S.; Wagner, J.; Baus, U.; Nydén, M. Copper removal from acid mine drainage-polluted water using
glutaraldehyde-polyethyleneimine modified diatomaceous earth particles. Heliyon 2018, 4, e00520. [CrossRef] [PubMed]
72. Maarof, H.I.; Daud, W.M.A.W.; Aroua, M.K. Recent trends in removal and recovery of heavy metals from wastewater by
electrochemical technologies. Rev. Chem. Eng. 2017, 33, 359–386. [CrossRef]