Ijerph 20 03885

International Journal of
Environmental Research
and Public Health
Review
Removal of Copper Ions from Wastewater: A Review
Yongming Liu 1 , Haishuang Wang 2 , Yuanyuan Cui 3 and Nan Chen 2, *
1 Shandong Provincial Geo-Mineral Engineering Co., Ltd., Jinan 250013, China

2 MOE Key Laboratory of Groundwater Circulation and Environmental Evolution, School of Water Resources
and Environment, China University of Geosciences (Beijing), Beijing 100083, China
3 Shandong Geological Exploration Institute of China Geology and Mine Bureau, Jinan 250013, China
* Correspondence: chennan@cugb.edu.cn; Tel.: +86-10-82322281; Fax: +86-10-82321081
Abstract: Copper pollution of the world’s water resources is becoming increasingly serious and
poses a serious threat to human health and aquatic ecosystems. With reported copper concentrations
in wastewater ranging from approximately 2.5 mg/L to 10,000 mg/L, a summary of remediation
techniques for different contamination scenarios is essential. Therefore, it is important to develop low-
cost, feasible, and sustainable wastewater removal technologies. Various methods for the removal of
heavy metals from wastewater have been extensively studied in recent years. This paper reviews
the current methods used to treat Cu(II)-containing wastewater and evaluates these technologies
and their health effects. These technologies include membrane separation, ion exchange, chemical
precipitation, electrochemistry, adsorption, and biotechnology. Thus, in this paper, we review the
efforts and technological advances made so far in the pursuit of more efficient removal and recovery of
Cu(II) from industrial wastewater and compare the advantages and disadvantages of each technology
in terms of research prospects, technical bottlenecks, and application scenarios. Meanwhile, this
study points out that achieving low health risk effluent through technology coupling is the focus of
future research.
Keywords: copper; wastewater; health; physical–chemical technology; biotechnology
1. Introduction
Citation: Liu, Y.; Wang, H.; Cui, Y.;
Chen, N. Removal of Copper Ions With the development of human life and industrial production, heavy metals pollution
from Wastewater: A Review. Int. J. is becoming more and more serious and has become an environmental problem, which
Environ. Res. Public Health 2023, 20, cannot be ignored [1]. Heavy metals mainly refer to elements with relative atomic masses
3885. https://doi.org/10.3390/ between 63.5 and 200.6, specific gravity greater than 5.0, and atomic density greater than
ijerph20053885 4.5 g·cm−3 [2–4]. They are mostly transition metals and include more than 40 kinds of heavy
metals, such as nickel, mercury, lead, copper, zinc, and cadmium. In response to the current
Academic Editor: Paul B. Tchounwou
study, heavy metals pollution in soil and water was found to be a widespread problem [1,5].
Received: 23 November 2022 With the rapid economic development and population explosion, the water resources
Revised: 15 February 2023 available for direct use on earth have been in shortage. Therefore, water pollution control
Accepted: 20 February 2023 has inevitably become a global concern [6,7]. In this study, the current status of heavy
Published: 22 February 2023 metal (Cu(II)) pollution, hazards, and treatment methods are reviewed with heavy metal
polluted wastewater as the main entry point. As an important part of the earth’s ecosystem,
water bodies are the most basic natural resources on which human beings depend, and
heavy metals in air and soil can be released into water through atmospheric deposition,
Copyright: © 2023 by the authors.
precipitation, and leaching [7,8]. Moreover, heavy metals are widely used in engineering,
Licensee MDPI, Basel, Switzerland.
paper, fine chemical, dye, paint, pharmaceutical, petrochemical, and textile industries,
This article is an open access article
distributed under the terms and
which inevitably leads to excess concentration of heavy metals in wastewater [9,10]. Heavy
conditions of the Creative Commons
metals are highly toxic elements, leading to the amplification of the entire food chain and
Attribution (CC BY) license (https:// adversely affecting human health and the environment [11,12]. Therefore, heavy metals
creativecommons.org/licenses/by/ pollution has received widespread attention.
4.0/).
Int. J. Environ. Res. Public Health 2023, 20, 3885. https://doi.org/10.3390/ijerph20053885 https://www.mdpi.com/journal/ijerph
Int. J. Environ. Res. Public Health 2023, 20, 3885 2 of 23
Copper is a typical transition metal, which occurs widely in nature and is the third
most used metal in the world, belonging to the group of heavy metals [12]. Copper, which
is usually considered a highly hazardous heavy metal [13], is an essential element required
by humans and plays a crucial role in enzyme synthesis, bone development, and tissues.
The different forms of copper are Cu(0) (metal), Cu(I) (cuprous ion), and Cu(II) (copper ion),
where Cu(II) is found to be the most toxic and occurring element in the environment. Cu(II)
is widely used in electroplating, paints and dyes, petroleum refining, fertilizer, mining
and metallurgy, explosives, pesticides, and steel industries and is considered one of the
most important hazardous heavy metals in these industrial effluent streams [14]. In terms
of human health, copper is an essential element for maintaining the vital activities and
physical health of the human body, and it has an important impact on the development
and physiological functions of the human blood and immune system, liver, heart, and eye
organs. Copper deficiency can lead to anemia and defects in connective tissue, but too
much copper can cause acute gastrointestinal symptoms, inactivation of enzyme systems
in the liver, and even motor disorders in some patients with copper overdose [15–17]. In
the aqueous environment, copper can permeate surface and groundwater systems and
may also be transferred to drinking water, threatening human health. Cu(II) pollution
has been on the rise in the global aqueous environment and has been identified as a
major heavy metal contaminant due to the health risk (Table 1) [18,19]. There are many
national and international reports on Cu(II) contamination in aqueous environments. Cu(II)
concentrations measured in freshwater ecosystems in the United Kingdom ranged from
0.02 to 133 mg/L, and it was one of the heavy metals of greatest concern [19]. In the
western part of the Netherlands, 39.1% of the area had excess Cu(II) concentrations in
surface water [20]. In China, the Keelung area, Poyang Lake, as well as Wuhekou in Taiwan,
were contaminated with heavy metals, and copper was the most prominent [21–23]. The
ingestion, skin contact, and inhalation of copper will lead to health risk for local residents.
Therefore, it is very important to understand the health risk probability for local residents
living around copper smelters, the pollution level leading to health risks, and different
treatment technologies. Therefore, the U.S. Environmental Protection Agency (EPA) and the
World Health Organization (WHO) estimate that the maximum Cu(II) content in drinking
water should be 1.3 and 3 mg/L, respectively [12]. Meanwhile, China stipulates in the
Groundwater Environmental Quality Standards and Surface Water Environmental Quality
Standards that the content of Cu(II) should be less than or equal to 1.5 and 1.0 mg/L
(GB 3838-2002; GB 14848-2017).
Table 1. Cu concentrations around the world.
Country/Region Concentration Paper

Water: 2114.00 ± 65.89 µg/L
China/Tibet, Rona [23]
Soil: 19.01–1763.1 mg/kg
China/Yunnan Copper Mine WWTP Sediments: 1200 mg/kg [24]
Cuba/Havana City Soil: 101 ± 51 mg/kg [25]
Tailings: 10,217 mg/kg
Uganda/Kilembe copper mine and tailing sites Sediments: 4110 mg/kg [26]
Water: 1.9–61 µg/L
India/Ghaziabad Soil: 122 mg/kg [27]
Brazil/Carajas-Amazon Water: 50–60 nmol/L [28]
China/Dexing copper mine sewage station 38.24–47.86 mg/L [29]
China/Liaodong Bay Water: 6.8–11.9 µg/L [30]
Based on the above, the technologies regarding the treatment of Cu(II)-contaminated

wastewater have been widely reviewed. The reported technologies for the removal of Cu(II)
contamination mainly include physicochemical techniques as well as biological techniques,
and surprising removal results have been obtained. Most of the existing review articles
focus only on an in-depth description of a technique, extending to the mechanism of action,
material selection, service life, and means of optimization. These articles are necessary for
Int. J. Environ. Res. Public Health 2023, 20, x FOR PEER REVIEW 3 of 24
physicochemical techniques, the applications of biotechnology in the treatment of Cu(II)-

contaminated wastewater are included, which are hardly covered in previous reviews of
similar type. Therefore, our current review focuses on the mechanistic differences,
application adaptability, and technological advantages of different technological tools.
an in-depth
This investigation
study provides by researchers,
theoretical support and but they are not
technical conducive
guidance for to a comprehensive
basic research on
understanding of the field
Cu(II)-contaminated wastewater. by beginners. This review provides a comprehensive overview
of the currently available copper treatment technologies and summarizes their potential
advantages
Table and disadvantages,
1. Cu concentrations which
around the world.can help researchers select targeted water treatment
methods. In particular, the advantages and disadvantages of various technical approaches
differ greatly inCountry/Region
terms of application scenarios, costs, Concentration
and technologies. Taking into Paper account
Water: 2114.00 ± 65.89 μg/L
the prevalence of Cu(II)Rona
China/Tibet, contamination and the valence variability, which distinguishes [23]
Soil: 19.01–1763.1 mg/kg
it fromChina/Yunnan
arsenic, chromium, and
Copper Mine WWTP
vanadium, the biological removal
Sediments: 1200 mg/kg
techniques and mech-
[24]
anisms for Cu(II) are very
Cuba/Havana different, and therefore,Soil:
City a summary
101±51 mg/kgof this research[25]
direction
is also needed to provide ideas for subsequent researchers.Tailings: 10217 In this paper, in addition to
mg/kg
theUganda/Kilembe
presentation copper
on physicochemical techniques,Sediments:
mine and tailing sites the applications
4110 mg/kgof biotechnology
[26] in the
treatment of Cu(II)-contaminated wastewater are Water: included,1.9–61μg/L
which are hardly covered in
India/Ghaziabad Soil: 122 mg/kg [27]
previous reviews of similar type. Therefore, our current review focuses on the mechanistic
Brazil/Carajas-Amazon Water: 50–60 nmol/L [28]
differences, application adaptability, and technological
China/Dexing copper mine sewage station
advantages of different technologi-
38.24–47.86 mg/L [29]
cal tools. ThisChina/Liaodong
study provides Bay theoretical support and technical
Water: guidance for basic
6.8–11.9μg/L [30]research
on Cu(II)-contaminated wastewater.
2. Restoration Techniques
2. Restoration Techniques
So far, several technologies have been developed and utilized for Cu(II) removal
So far, several technologies have been developed and utilized for Cu(II) removal from
from water and wastewater, and according to the reaction mechanism, the available
water and wastewater, and according to the reaction mechanism, the available studies clas-
studies classified these technologies as physicochemical (membrane separation, ion
sified these technologies as physicochemical (membrane separation, ion exchange, chemical
exchange, chemical precipitation, electrochemistry, adsorption) and biological
precipitation, electrochemistry, adsorption) and biological (biosorption, bioprecipitation,
(biosorption, bioprecipitation, biomineralization) [2,9,14,31] (Figure 1).
biomineralization) [2,9,14,31] (Figure 1).
Figure 1. Treatment technology of Cu(II)-polluted wastewater.

Figure 1. Treatment technology of Cu(II)-polluted wastewater.
2.1. Physical–Chemical Technology
2.1. Physical–Chemical
2.1.1. Technology
Membrane Separation
2.1.1. Membrane
Membrane Separation
separation methods mainly use the selective permeability of membranes to
concentrate
Membraneandseparation
separate heavy metals,
methods and the
mainly usecommon membrane
the selective separation
permeability technologies
of membranes
toareconcentrate
microfiltration,
and ultrafiltration,
separate heavy nanofiltration,
metals, andreverse osmosis, membrane
the common and electrodialysis [32].
separation
Microfiltration, Ultrafiltration, and Nanofiltration

The main difference between microfiltration, ultrafiltration, and nanofiltration is
the pore size of the membrane: microfiltration (MF, 0.2–1 µm), ultrafiltration (UF, MW:
pore size (100–1000 nm) was not an absolute barrier for heavy meta
ultrafiltration hybrid matrix hollow fiber membranes impreg
nanoparticles, the removal of Cu(II) exceeded 92% at a specific permea
L m−2h−1kPa−1, and the hybrid matrix membranes showed an adsorp
mg/g at pH 8. Ultrafiltration had a low ability to remove small molecu
and was also
1000–1,000,000, limited
5–0.2 µm), in the
nanofiltration (NF, removal
MW: 100–1000, of0.5–5
metal ions; osmosis
nm), reverse therefore,
(RO, MW < 100, 0.2–0.3
ultrafiltration nm) [33] using
(PEUF) (Figure 2). Metal sulfide precipitation
polymer–metal combined with
interactions andmi-memb
crofiltration processes have been studied for Cu(II) recovery from acid mine drainage [34].
used for
However, heavy metals
microfiltration was rarely removal.
used for heavyThemetalsremoval
removal becauseof Cu(II)
its large poreby PEU
investigated
size (100–1000 nm) with
was notpolyvinylamine as ametals
an absolute barrier for heavy chelating agent ultrafil-
[3]. By preparing [35]. Surfa
tration hybrid matrix hollow fiber membranes impregnated with ZnO nanoparticles, the
potential
removal in removing
of Cu(II) exceeded 92%metal contamination.
at a specific permeate flow rate However,
of 0.115 L m− it2 hshould
−1 kPa−1 , be no
of metal
and the hybridremoval needs to
matrix membranes be further
showed improved,
an adsorption capacity ofand the atsurfactant
88 mg/g pH 8. w
Ultrafiltration had a low ability to remove small molecular weight organics and was also
removal effect should be selected from the perspective of environm
limited in the removal of metal ions; therefore, polymer-enhanced ultrafiltration (PEUF)
metalpolymer–metal
using recovery value. In addition,
interactions and membrane thefiltration
utilizationwas usedof recovered
for heavy metals metals o
removal. The removal of Cu(II) by PEUF up to 97% was investigated
the presence of surfactants should be studied from an electrochemica with polyvinylamine
as a chelating agent [35]. Surfactants show great potential in removing metal contamina-
other
tion. technical
However, point
it should of view.
be noted that theAt the ofsame
process metal time,
removalthe method
needs to be furtherusing su
very advantageous
improved, and the surfactantforwithmaximizing the treatment
the best metal removal effect should of multiple
be selected from target
the perspective of environmental protection or metal recovery value. In addition, the
pressureof recovered
utilization membrane metalsseparation
or metal solutionsprocesses
in the presence(e.g., microfiltration
of surfactants should be and
removal
studied fromof an heavy metals
electrochemical, was limited
ultrafiltration, bytechnical
or other their point
largeof pore
view. At size
the allow
same time, the method using surfactant mixtures is very advantageous for maximizing the
heavy metal ions [36]. The current solution is to
treatment of multiple target metals. With low-pressure membrane separation processes
ultrafiltration/microfiltration
(e.g., microfiltration and ultrafiltration), theprocesses
removal of heavy ormetals
to was combine membran
limited by their
large pore size allowingprocesses
electrochemical the passage of toheavy metal ionsconductive
prepare [36]. The currentmembranes
solution is to de- to ac
velop hybrid ultrafiltration/microfiltration processes or to combine membrane separation
membrane
and for processes
electrochemical metal to ions removal
prepare [36].
conductive Reverse
membranes osmosis
to achieve technology
low-pressure
consumption
membrane for metalandionsmay
removalremove ions osmosis
[36]. Reverse from the body,has
technology which
a highdo not need
energy
consumption and may remove ions from the body, which do not need to be removed [33].
Figure 2. Membrane technology including MF, UF, NF, and RO.

Figure 2. Membrane technology including MF, UF, NF, and RO.
Nanofiltration technology for the separation of Cu(II) from aqueous solutions has
proven to be a viable technology for effective Cu(II) removal over a wide range of oper-
Nanofiltration technology for the separation of Cu(II) from
aqu
ations. Nanofiltration (NF) is used as a pressure-driven membrane technology located
proven to be a viable technology for effective Cu(II) removal ove
between ultrafiltration (UF) and reverse osmosis (RO). NF allows the passage of water
molecules and most monovalent ions while rejecting most organic molecules, multivalent
ions, and colloidal particles [37]. It has a lower working pressure than RO due to the loose
selective layer and a better ion selectivity than UF due to the appropriate pore size [38]. This
special separation capability has led to the wide application of nanofiltration membranes
for hardness removal, heavy metal ion removal, and dye\salt separation. Nanofiltration
membranes are usually composite products, and the substrates may include polyethersul-
fone (PES), polysulfone (PSF), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN),
and polytetrafluoroethylene (PTFE), which provide the required mechanical strength to the
membrane. In addition, the functional layer is critical to the filtration effectiveness of the
composite membrane. The key factors include the thickness of the polymer layer, the pore
size, and the selection of the support layer, which determines the membrane flux, selective
permeability, and retention performance. To this end, the methods of preparing functional
layers are important, including interfacial polymerization [39], cross-linked coatings [40],
layer-by-layer self-assembly techniques [41], and surface hyperbranched modifications [33].
Qi et al. [42] prepared a novel positively charged nanofiltration membrane using 2-chloro-
1-methylpyridine as the active agent and harvested more than 96% Cu(II) removal by
covalently grafting polyimide polymers with surface carboxyl groups. Tian et al. [43]
prepared a composite nanofiltration membrane to achieve an ideal rejection rate of Cu(II)
exceeding 98%. Polymer-anchored co-deposition method consisting of positively charged
hollow fiber nanofiltration membranes with a bridge network structure showed excellent
removal efficiency for a high concentration of heavy metal ions (4000 mg/L) [44].
The spatial site resistance effect and Donnan exclusion are the two main separation
mechanisms of NF [42,44]. Among them, the spatial site resistance effect, namely the
sieve effect, is related to the molecular geometry (width). The Donnan effect refers to the
repulsion of ions due to the surface charge of the nanofiltration membrane. Therefore, the
surface charge of the NF membrane is modified to neutral or microcharge to enable the
membrane to remove a large range of heavy metals, and adsorption mechanisms other than
size exclusion and charge rejection are introduced to improve the rejection efficiency of the
membrane [45]. Nanofiltration technology has good stability, low chemical consumption,
energy efficiency, small carbon footprint, easy management and maintenance, and it can
achieve zero emissions [46]. However, there are still many challenges in its application,
such as membrane fouling, membrane pore size, and membrane material biodegradability.
There is an emerging research trend to develop a natural/biodegradable polymer-based
membrane with sustainable, high flux, and separation efficiency [33]. Fouling is a complex
phenomenon resulting from the interaction between feed solution, membrane properties,
and operating conditions [37]; therefore, membrane cleaning is essential to maintain mem-
brane permeability and selectivity. This can be mitigated by electrolysis [47], ultrasonic
cleaning [48], chemical cleaning [49], and backflushing [50]. Physical cleaning can alleviate
membrane contamination and reduce the frequency of chemical cleaning, thus extending
the membrane life and reducing operating costs. Although membrane fouling cannot be
avoided, contamination can be reduced by adequate selection of membrane pore size and
material and by controlling operating condition factors, such as transmembrane pressure,
temperature, and flow rate [51].
Membrane separation processes have been identified as a viable option for the removal
of heavy metals from aqueous solutions because they are easy to construct and control,
and valuable metals can be recovered. However, high operating pressures, pH sensitivity,
and the driving force of foreign ions limit their application. Therefore, understanding the
separation behavior of a specific membrane process under various operating conditions is
important to design a viable membrane process.
Reverse Osmosis and Electrodialysis

In reverse osmosis, the applied pressure difference is greater than the osmotic pressure
difference across the membrane; therefore, water molecules are forced to flow in the
opposite direction to the natural osmosis phenomenon [52]. Electrodialysis is an electro-

membrane method, whereby ions are transferred by an electric current applied to the
membrane [53]. Reverse osmosis and electrodialysis have continuous channels through
which water and ions move. Membrane charge and chemical affinity cause solutes to be
split on the two outer sides of the membrane. On the upstream side of the reverse osmosis
membrane (reflux side), the ion concentration increases through the diffusion boundary
layer toward the membrane (concentration polarization), and on the downstream side,
a permeate is produced [54]. Reverse osmosis and electrodialysis also have three main
aspects in common: the difference in concentration between the two sides of the membrane,
the pressure difference across the membrane, and the presence of an electric current [54].
Reverse osmosis is the reverse process of osmosis and generally refers to the process
of allowing the solvent to pass through a semi-permeable membrane and retain some
or all of the solute under external pressure. There are two conditions to achieve reverse
osmosis: first, the operating pressure must be greater than the osmotic pressure of the
solution; second, there must be a highly selective, highly permeable semi-permeable mem-
brane. In the treatment of heavy metals wastewater, the retention mechanism of reverse
osmosis is mainly the sieving mechanism and electrostatic repulsion. Therefore, the reten-
tion effect of heavy metals is also related to the valence state of heavy metal ions [54,55].
Aromatic polyamide ultra-low-pressure reverse osmosis membranes have the ability to
separate Cu(II), obtaining >95% metal rejection in synthetic and real industrial wastewa-
ters [56]. Reverse osmosis membranes were combined with an electro-coupling process to
achieve remediation of Cu(II)-contaminated water, and the effects of electrolysis voltage,
pH, and electrolysis time on metal recovery efficiency, and the relationships between trans-
membrane pressure drop (∆P), addition rate, and initial Cu concentration and operating
efficiency, membrane stability, and water reuse potential, were investigated [57]. Numerous
scientific experiments have demonstrated the excellent effectiveness of reverse osmosis
membranes for Cu(II) removal, especially for high-Cu(II) contamination loads and contam-
inant ions’ coexistence [58,59]. Pilot-scale membrane bioreactor systems in combination
with reverse osmosis had a very high heavy metals removal efficiency [59]. In addition,
the combination of reverse osmosis and nanofiltration for efficient heavy metals removal
was well reported. The combination of nanofiltration and reverse osmosis membranes was
effective in removing Cu(II) from the water of a textile coating plant [60]. However, the
RO process is also subject to membrane fouling and blockage problems, and vibrational
shear-enhanced treatment techniques combined with conventional RO membranes extract
valuable heavy metals from concentrates [61]. The main drawback of reverse osmosis is the
high power consumption due to pump pressure and membrane repair, which is the focus
of future research.
In electrodialysis, the water flows through thin channels next to an ion exchange
membrane, and the applied current pulls ions from one set of channels through the IEM to
other channels [54]. Electrodialysis is an electrically driven separation process, which can
be easily scaled up and used in combination with other processes [62]. Electrodialysis has
proven to be very effective in the removal of Cu and Fe from working solutions [63]. Ion
exchange membranes, which are the core of ED systems, are semi-permeable to ions due to
the fixed ionic groups on their backbone [62]. The preparation of ion-exchange membranes
with desirable permeability, low resistance, improved thermal, chemical, and mechanical
properties, and high cost effectiveness is the focus of research in this technology. In addition,
electrodialysis exhibits high selectivity in separations and high energy efficiency at high
operating costs.
2.1.2. Ion Exchange

The ion exchange process has been successfully used to remove heavy metals from
industrial wastewater, especially from acidic wastewater. The ion exchange uses the free
ions carried by the solid phase exchanger itself to exchange with the heavy metal ions in the
liquid phase to separate the metal ions from the wastewater. Exchange resin is a common
exchange agent, and the exchange resins obtained by different preparation methods have
different affinities for metal ions, that is, they have selectivity for different metal ions [64].
Among the materials used in ion exchange, synthetic resins are usually preferred because
they are almost effective in removing heavy metals [65]. Adsorption selectivity and capacity
are the two most important properties of resins. The selectivity of adsorption comes
mainly from the interaction between the adsorbent and the functional groups on the
surface of the chelating resin, so the type of functional group plays a crucial role. The
functional groups on the surface of chelate resin not only affect the adsorption selectivity,
but they also dominate the adsorption mechanism. The tert-butyl 2-methylamino-N-
acetic acid functionalized chelating resin could remove trace copper from simulated nickel
electrolytes with high selectivity [66]. Magnetic cation exchange resin synergistically
removed Cu(II) and tetracycline (TC) from their mixed solutions and had great potential
for application with negligible loss of adsorption capacity over five adsorption–desorption
cycles [67]. The commercial resin MTS9600® containing dichloramine groups was used
to selectively separate nickel and copper from acidic effluents of sulfate media with 99%
copper removal at selected operating conditions (pH = 2.0) [68]. Ion-exchange technology
has been successfully applied in the recovery of hydrometallurgical lithium-ion battery
waste, and aminomethylphosphonic acid functional group chelating resin (Lewatit TP260)
was able to remove Fe, Al, Mn, and Cu from the leachate [69]. In fact, Murray and Örmeci
have developed nano- or submicron-sized adsorbents as alternatives to conventional
adsorbents, which were able to remove 46% ± 0.6% of copper from river water spiked with
500 µg/L and 38% ± 0.8% of copper from actual wastewater [70]. Moreover, in addition to
synthetic resins, natural zeolites were widely used for the removal of heavy metals from
aqueous solutions due to their low cost and high abundance. Additionally, it has been
shown that zeolites exhibit good cation exchange capacity for heavy metal ions under
different experimental conditions.
The main advantages of ion-exchange technology are high uptake of the target ma-
terial, fast reaction kinetics, efficient elution, and lifetime durability [71]. However, the
feasibility of the ion-exchange resin process depends heavily on the long-term reusability
of the resin and the possibility of recovering the target compound from the regenerated
solution. Typically, adsorbed Cu(II) was released by washing with concentrated acid
(1.0–2.0 M H2 SO4 ), which protonated the nitrogen sites. To improve the recovery of Cu(II),
additional washing with concentrated aqueous ammonia solution (1.0–2.0 M NH4 OH) is
required to completely release the metal [72]. The design of an efficient chelating resin
elution scheme needs to be refined in subsequent experiments to achieve efficient heavy
metal recovery.
2.1.3. Electrochemistry
Electrochemical technologies are used to achieve the desired purpose through a series
of chemical reactions, electrochemical or physical processes. They have some special
advantages compared to traditional wastewater treatment methods. (1) Electrochemical
technologies are versatile and can be used not only for the degradation and transformation
of pollutants but also for suspension systems or colloidal systems. They can play a role in
the treatment of wastewater, exhaust gases, and toxic waste. The main parameters of the
electrochemical process are potential and current, which are easy to measure and control.
(2) The electrochemical reaction process does not require the addition of chemicals to avoid
secondary contamination. (3) Electrochemical treatment equipment is relatively simple,
with high removal efficiency and low operation and maintenance costs. (4) The amount of
sludge (the precipitates produced during flocculation or deposition) produced is small, the
post-processing process is simple, and the operating area is small. According to different
electrode materials and electrode reactions, electrochemical methods can be mainly divided
into electrodeposition and electroflocculation.
Electrodeposition
Electrodeposition can recover metal ions by selective removal and can even be used to
produce new materials, and it is widely used in heavy metal wastewater treatment [73].
Carpanedo de Morais Nepel et al. [74] studied and optimized the recovery of copper
from real wastewater by pulsed electrodeposition, using fast current pulses (ton = 1 ms,
190 mA, 70 rpm, 37 ◦ C) in an experiment with a deposition efficiency of 84.36% and a
copper removal of 33.59% in 30 min, obtaining 100% purity of copper metal and crystalline
copper in the coating. However, electrodeposition has the disadvantages of low treatment
efficiency, long treatment time, and high energy consumption in the treatment of heavy
metal wastewater containing Cu(II) due to the reduction potential and mass transfer process
of metal electrodeposition, which limit its application.
Electroflocculation
Electroflocculation was able to generate a large number of cations at the anode of
the external power supply to generate a series of polynuclear hydroxyl complexes and
hydroxyl ions, from which suspended solids and organics were adsorbed. At the same time,
the cathode generated hydrogen, which gathered into micro foam and rose to the surface
to form a contact suspension layer, thus purifying the wastewater. Wu et al. [75] used DC
electrocoagulation flocculation to treat alkali–ammonia corrosion wastewater from printed
circuit boards with an electrode distance of 28 mm and a current density of 100–300 A·m−2 ,
which could effectively remove Cu(II) from alkali–ammonia corrosion wastewater, with
the recovery of Cu(II) exceeding 99%. Electroflocculation has many advantages, including
simplicity of operation, high removal efficiency, and low sludge (the precipitates produced
during flocculation) formation rate [76,77]. However, a major drawback of electrochemical
flocculation is that it requires a large amount of electricity proportional to the initial
concentration of heavy metals [78]. Therefore, reducing the heavy metal concentration
prior to electrochemical treatment will reduce the overall electricity demand. Mohammad
Rahimi et al. [37] modified a thermally regenerated ammonia battery (TRAB) using waste
heat and power generation and used it as a treatment process for solutions containing
high concentrations of Cu(II), showing that the initial Cu(II) concentration of 0.05 mol/L
resulted in a high copper removal rate of 77% and a maximum power density of 31 W·m−2 .
The modified TRAB was a promising technology for the removal of Cu(II) as well as for
the use of waste heat as a high-availability and free energy source for power generation in
many industrial sites.
2.1.4. Chemical Precipitation

Dissolved metal ions are converted to an insoluble solid phase by chemical reaction
with a precipitant (e.g., base or sulfide), and the resulting precipitate can be separated from
the water by precipitation or filtration. Traditional chemical precipitation processes mainly
include hydroxide precipitation and sulfide precipitation. Chemical precipitation is most
widely used in industry, mainly because the simplicity of process control allows it to be
effective over a wide range of temperatures and at low operating costs [79]. Inorganic
precipitants commonly used for heavy metal precipitation are lime (Ca(OH)2 ), caustic soda
(NaOH), soda ash (Na2 CO3 ), sodium bicarbonate (Na(HCO3 )2 ), sodium sulfide (Na2 S),
and sodium hydride (NaHS) [80,81]. Chemical precipitation uses pH adjustment to convert
heavy metal ions into hydroxides, sulfides, carbonates, or other less soluble compounds,
which are then removed by physical means (e.g., precipitation, flotation, or filtration) [76].
Chemical precipitation has the advantages of low cost, simplicity of operation, as well as
non-metallic selectivity. Notably, the chemical precipitation method often introduces a
large number of inorganic ions into the wastewater, leading to high salinity when removing
Cu(II) due to the need to add additional agents or adjust the pH value, leading to an extreme
(acid/base) pH environment, which makes it difficult to achieve environmentally friendly
effluent quality. This makes chemical precipitation more suitable for high concentrations of
Cu(II) wastewater, such as acidic mine wastewater.
Hydroxide Precipitation
The precipitation of soluble metals into insoluble hydroxide form with lime in an
alkaline environment was proposed as early as the 1880s [77]. Currently, neutralization
precipitation of inexpensive CaO is the most widely used process in the treatment of waste
acid wastewater from copper smelting because of its low cost and simplicity of opera-
tion [82,83]. In pilot-scale experiments, the optimal pH for achieving maximum copper
precipitation with lime and caustic soda used in the hydroxide precipitation method was
determined to be around 12.0 [80]. Wang et al. used the bicarbonate-activated hydrogen
peroxide/chemical precipitation method to simultaneously perform Cu-EDTA depolymer-
ization and Cu(II) precipitation. It was found that the composition of the precipitate was
identified as CuCO3 , Cu2 (OH)2 CO3 , Cu(OH)2 , CuO, and/or CuO2 , and TOC removal
efficiency and Cu removal efficiency reached 78.4% and 68.3% after 60 min treatment,
respectively [81].
Sulfide Precipitation
Metal sulfide species are highly insoluble, especially for copper with logKsp values
between −49.2 and −35.9 [84]. This fact is an attractive advantage for environmental appli-
cations, especially in terms of chemical stability. By comparison, metal sulfide precipitation
is superior to metal hydroxide precipitation because of (1) the high reactivity of sulfides
with heavy metal ions and the very low solubility of metal sulfides over a wide pH range.
(2) The metal sulfide sludge (the precipitates produced during chemical reactions) is denser
and has better thickening and dewatering properties than metal hydroxide sludge; and
(3) metal sulfides are good selective precipitators and are insensitive to the presence of
complexes [33].
Other chemical precipitation methods, such as the classical alkaline precipitation
method, form difficult-to-eliminate heavy metal complexes due to the strong bonding ability
between Cu(II) and EDTA [85]. However, the process of metal separation and recovery
during chemical precipitation still needs to be further addressed [83]. For example, the
recovery of Cu(II)–EDTA in Cu–organic-compound contaminated wastewater was difficult
due to its high stability, resulting in a “replacement–precipitation” strategy, whereby the
affinities of the replacement agent (stronger Ca replacement agents (Ca and Fe)) were
investigated [85].
2.1.5. Adsorption
Adsorption methods include physisorption and chemisorption, where physisorption
is the adsorption of an adsorbent by van der Waals forces; chemisorption is the adsorption
of an adsorbent by chemical bonding; and biosorption is adsorption by proteins secreted
by organisms (bacteria, fungi, and algae). In general, the Gibbs free energy of physical
adsorption (physisorption) varies between −20 and 0 kJ/mol; however, chemisorption
ranges from −400 to −80 kJ/mol [86]. During the adsorption process, both adsorption
pathways can exist separately, occur simultaneously, or be dominated by one or the other.
Usually, we do not make a clear distinction between physical and chemical adsorption and
collectively refer to them as adsorption. Adsorption is a method for adsorbing heavy metal
ions using the well-developed pore structure, high specific surface area, and abundant
functional groups on the adsorbent surface, which is an efficient, operable, and economical
method for aqueous phase Cu(II) remediation [87]. In the adsorption process, the selection
of an adsorbent with excellent adsorption efficiency is key to the adsorption technique.
Many researchers have used various adsorbents, such as activated carbon, zeolite, activated
alumina, lignite coke, bentonite, ash, clay, and natural fibers, to remove heavy metal
ions from aqueous solutions. Adsorption efficiency and selectivity mainly depend on the
chemical and physical properties of the adsorbent [88]. The common types of adsorbents
can be classified according to the type of material as carbon-based adsorbents, natural
mineral adsorbents, and natural polymer adsorbents (Figure 3).
technique. Many researchers have used various adsorbents, such as activated carbon,
zeolite, activated alumina, lignite coke, bentonite, ash, clay, and natural fibers, to remove
heavy metal ions from aqueous solutions. Adsorption efficiency and selectivity mainly
depend on the chemical and physical properties of the adsorbent [88]. The common types
of adsorbents can be classified according to the type of material as carbon-based
adsorbents, natural mineral adsorbents, and natural polymer adsorbents (Figure 3).
Figure 3.
Figure Common adsorbent
3. Common adsorbent types
types in
in Cu(II)
Cu(II) removal
removal process.
process.
Carbon-Based Adsorbents
Carbon-Based Adsorbents
Biochar is a carbon-rich solid obtained by pyrolysis of biological waste under low-
Biochar and
temperature is a carbon-rich
limited oxygen solidconditions
obtained by [89].pyrolysis
With a highof biological waste under
specific surface low-
area, well-
temperature and limited oxygen conditions [89]. With a high
developed porous structure, and high thermal stability, biochar shows great potential for specific surface area, well-
developed
immobilization porous of structure,
heavy metals. and high
Zhouthermal
et al. [90]stability,
found biochar
that the shows great potential
main adsorption mecha-for
immobilization of heavy metals. Zhou et al. [90] found
nism of Cu(II) with biochar of tobacco stems was related to surface complexation. Chen that the main adsorption
mechanism
et al. [91] showed of Cu(II)thatwith biochar of adsorption
the maximum tobacco stems was related
capacity of cornto surface
stover complexation.
biochar for Cu(II)
Chen et al. [91] showed that the maximum adsorption capacity
was 12.5 mg/g. The adsorption capacity of Cu(II) was 71.4 mg/g in lobster shell-based of corn stover biochar for
Cu(II)
biocharwas via12.5cationmg/g. The adsorption
exchange, capacity of Cu(II)
mineral precipitation, was 71.4 mg/g
and interactions suchin as
lobster shell-
functional
based biochar via cation
group complexation exchange,
and π-electron mineral precipitation,
coordination with biochar [92]. and Theinteractions
disadvantagessuch as of
functional
raw biochar,group such as complexation and π-electron
surface hydrophobicity, coordination
low number with biochar
of functional groups, and [92].weakThe
disadvantages
metal binding ability, of raw biochar, such astosurface
limit its ability purifyhydrophobicity, low number
heavy metals wastewater of functional
[93]. Therefore,
groups, and weak metal binding ability, limit its ability
the development of green, simple, and economical modification methods to improveto purify heavy metals wastewater its
[93]. Therefore,
adsorption the development
capacity for heavy metal of green,
ions has simple,
become andaeconomical modification
priority. Biochar methods
can be activated
to improveor
physically itschemically,
adsorption depending
capacity foron heavy metal ions
the desired has become
surface properties,a priority.
and theBiochar can
activation
be activated
usually includes physically
physical oractivation
chemically, depending
(steam or carbonon the desired
dioxide) surface
as well properties,
as chemical and
activa-
the
tionactivation
(zinc chloride, usually includesacid,
phosphoric physical activation
potassium (steamand
hydroxide, or carbon
sodium dioxide)
hydroxide) as [94–96].
well as
chemical activation
Activated carbon is a(zinc black chloride, phosphoric
solid substance acid,topotassium
similar granular or hydroxide,
powderedand sodium
charcoal, a
hydroxide)
carbonaceous [94–96].
material Activated carbon
with highly is a blackporosity,
developed solid substance similar
high specific to granular
surface area, and or
powdered
relatively high charcoal,
mechanicala carbonaceous
strength [97].material
Amorphous withMnO-embedded
highly developed porous porosity,
rubber highseed
specific surface
shell biochar area, and
prepared relatively
by KMnO high mechanical strength
4 impregnation–coking [97].treatment
activation Amorphous MnO-
efficiently
purified
embedded Cu(II)-containing
porous rubber seed wastewater in a wide
shell biochar pH range
prepared (>2) and
by KMnO increased the equi-
4 impregnation–coking
librium adsorption
activation treatmentcapacity
efficientlyof purified
Cu(II) byCu(II)-containing
3.88 times (200.59wastewater
mg/g) [93]. inThea widemodification
pH range
of larch
(>2) andbiochar
increased with thewood ash as a adsorption
equilibrium modifier increasedcapacitythe of maximum
Cu(II) by 3.88 removal
timesof(200.59
Cu(II)
by 9.66–11.11 times (38.9 ± 2.4 mg/g, 33.8 ± 2.3 mg/g),
mg/g) [93]. The modification of larch biochar with wood ash as a modifier increased as the alkaline cations in woodthe
ash increased the cation exchange process occurring on the biochar
maximum removal of Cu(II) by 9.66–11.11 times (38.9 ± 2.4 mg/g, 33.8 ± 2.3 mg/g), as the surface [98]. Biochar
modification
alkaline cationsenhanced
in wood the ash
intrinsic properties,
increased such as
the cation surface area,
exchange processporosity, morphology,
occurring on the
and functional
biochar surfacegroups. The methods
[98]. Biochar of biochar
modification modification
enhanced include metal
the intrinsic impregnation,
properties, such as
magnetization,
surface and activation
area, porosity, [99]. Activated
morphology, and functionalcarbon groups.
adsorption Thewas widelyofused
methods due
biochar
to its porous surface structure and was environmentally benign
modification include metal impregnation, magnetization, and activation [99]. Activated and easy to handle [100].
However,
carbon the high cost
adsorption wasofwidely
activated carbon
used duelimited
to its its application,
porous surfaceand therefore,
structure andtherewasis
a need to find alternatives to investigate low-cost, effective,
environmentally benign and easy to handle [100]. However, the high cost of activated and economical adsorbents.
Waste
carbonrubber
limited tires
itsand a wide variety
application, of agricultural
and therefore, therewastes, such to
is a need as orange peel, banana
find alternatives to
peel, peat, wood,
investigate low-cost,pineeffective,
bark, soybean and cotton adsorbents.
and economical seed shells, shells,
Waste hazelnut
rubber tires shells,
andpeanuts,
a wide
rice husks,
variety wool, sawdust,
of agricultural compost,
wastes, such asand leaves,
orange have
peel, been peel,
banana madepeat,into wood,
activatedpinecarbon
bark,
adsorbents [101]. In addition, carbon nanotubes were considered an effective heavy metal
adsorbent because of their stability, large specific surface area, good mechanical properties,
and high adsorption capacity [102].
Mineral Adsorbents
Zeolite is a porous aluminosilicate crystal with a tetrahedral structure based on TO4
(T = Si or Al). Zeolites are widely used in the removal of heavy metals from water due to
their high affinity for specific contaminants [95]. Low-value materials are used to prepare
zeolites to reduce the environmental impact and cut costs, such as fly ash [96], kaolin [103],
red mud [104], and lithium silica powder [95]. Among other things, this enables the
resourceization of waste while adsorbing and recovering heavy metals, which has a win-
win effect. Furthermore, clay as an adsorbent has many advantages over other commercially
available adsorbents in terms of low cost, abundant availability, high specific surface area,
excellent adsorption properties, non-toxic nature, and ion-exchange potential [105]. Clays
and clay minerals (montmorillonite, kaolinite, and illite) have a small particle size and
complex porous structure with high specific surface area, which allows strong physical and
chemical interactions with dissolved substances. These interactions are due to electrostatic
repulsion, crystallinity, and adsorption or specific cation exchange [105]. Most clay minerals
are negatively charged and very effective, and they are widely used to adsorb metal cations
from solutions due to their high cation exchange capacity, high surface area, and pore
volume. The absorption of heavy metals by clay minerals involves a series of complex
adsorption mechanisms, such as direct binding of metal cations with the surface of clay
minerals, surface complexation, and ion exchange [105]. Kaolinite obtained from Longyan,
China, has good adsorption of Cu(II) under various conditions (metal ion concentration,
clay amount, pH). It reaches maximum adsorption rapidly, within 30 min for Cu(II) [106].
However, the adsorption capacity of natural materials is low and needs to be modified to
improve the separation efficiency and selectivity [107].
Polymer Adsorbents
Polymer adsorbent has a variety of functional groups on its surface, and these groups
can combine with heavy metal ions in water to achieve the removal of metal ions from
water. Natural polymer adsorbent mainly refers to chitosan, starch, lignin, cellulose,
and other natural macromolecular substances with adsorption capacity. Chitosan is the
second largest natural macromolecular compound besides cellulose [12], mainly found
in insect shells, shrimp shells, crab shells, or cell walls of some micro-organisms, and
the abundant amino and hydroxyl groups on its surface can be used to chelate heavy
metal ions. Benavente et al. [108] prepared chitosan materials from shrimp shell waste
with a maximum adsorption capacity of 79.94 mg/g of Cu(II). The limited functionality,
solubility in acidic media, poor mechanical properties, and high swelling rate of typical
chitosan-based adsorbents limit their applications, which can be functionalized by chemical
oxidation, esterification, lipidation, and diazotization of chitosan backbone [13,109].
2.2. Biotechnology
The biological removal process of Cu(II) in the water environment mainly includes
biosorption, bioaccumulation and biomineralization, and phytoremediation. The removal
of Cu(II) by micro-organisms can be divided into two processes. One process involves
the resistance gene of micro-organisms, which enables micro-organisms to survive and
grow in the presence of Cu(II), and at the same time, Cu(II) can be accumulated in cells
through cell membranes. The other process involves Cu(II), which can be adsorbed to
organisms through physical and chemical actions by secreting EPS and other substances
with adsorption capacity (Figure 4).
Biosorption, that is, heavy metals removal using cheap biological materials, such as
algae, fungi, and bacteria, is becoming a potential alternative method for removing toxic
metals from water [110]. One of the main advantages of biosorbents is that they are non-
toxic and safe for the environment. Biosorption of heavy metals by metabolically inactive
abiotic biomass of microbial or plant origin was an innovative and alternative technology
for the removal of heavy metals from aqueous solutions [111]. Due to its unique chemical
composition, biomass sequestered metal ions by forming metal complexes from the solution.
The main mechanism involving the biosorption of metals (Pb2+ , Ni2+ , Cd2+ , Cu2+ , and Zn2+ )
using dead, dry aquatic plants as simple biosorbent materials for metal removal was the ion
exchange between monovalent metals present in macrophyte biomass as counter ions and
heavy metal ions and protons absorbed from water [110]. Seaweeds have a high binding
affinity for heavy metals, and their cell walls have different functional groups (e.g., carboxyl,
hydroxyl, phosphate, or amine), which can bind metal ions [112]. The seaweed U. lactuca
from the Mediterranean coast of Egypt had a high polymetallic biosorption capacity, with
a maximum biosorption efficiency of 64.51 mg/g for Cu(II) [113]. Compared with the
physical and chemical methods, bacterial biosorption is a milder treatment method for
toxic pollutants, which are not easily removed, such as heavy metals. These metal-tolerant
bacteria can bind cationic toxic heavy metals to negatively charged bacterial structures and
live or dead biomass components. Moreover, these bacterial biomasses can effectively act
as biosorbents for metal bioremediation under polymetallic conditions due to the large
surface area to volume ratio [114]. The biosorption process is based on the properties of
microbial cell walls, consisting of different polysaccharides, proteins, and lipids, which
provide a variety of functional groups (carboxyl, hydroxyl, phosphate, amino, sulfur) that
can interact chemically with pollutants in a variety of ways [115]. For example, Cu2+ can
react with these functional groups and result in organic metal precipitates [115]. These
precipitates are removed from the bulk solution by adsorption on microbial cells. Similar
Int. J. Environ. Res. Public Health
metal2023, 20, x FOR
cations, suchPEER REVIEW
as Ni(II), Cd(II), Cr(III), Cr(VI), and Co(II), can usually be removed by 12
Escherichia coli C90, which is a commonly used method [110]. Microbial-based biosorption
has several advantages in the removal of metal ions because it is selective for specific
metals. Inthrough
addition,physical
the smalland
size of micro-organisms
chemical provides
actions by a large
secreting specific
EPS and surface
other area
substances
and volume for heavy metal adsorption. Additionally, due to the reusable nature of the
adsorption capacity (Figure 4).
biosorbents, the method is economically feasible and leaves minimal waste.
Figure 4. Biotechnology for copper removal.

Figure 4. Biotechnology for copper removal.
Biosorption is a metabolism-dependent mechanism, which enables the adsorption
of contaminants Biosorption, that
onto cellular is, heavy[116].
polymers metals removal involves
Biosorption using cheap biological
several materials, suc
mechanisms,
includingalgae, fungi, and
ion exchange, bacteria,
surface is becoming
complexation, a potential
and alternative method
physical adsorption. forion
In general, removing
exchangemetals
plays an important
from role inOne
water [110]. metalofbiosorption due to the electrostatic
the main advantages interactions
of biosorbents is that they are
that occur between
toxic the for
and safe positive charge of freeBiosorption
the environment. metal ions and the negative
of heavy metals charge of the
by metabolically ina
microbialabiotic
cell wall [117]. In bacteria, the reactivity of the cell wall toward metals is
biomass of microbial or plant origin was an innovative and alternative techno mainly
due to thefor
presence of proactive
the removal functional
of heavy metalsgroups, such as solutions
from aqueous carboxyl, phosphoryl,
[111]. Due tohydroxyl,
its unique chem
amino, and sulfhydryl groups, which can immobilize cations when
composition, biomass sequestered metal ions by forming metal complexes deprotonated [118]. from
Unlike bioaccumulation, biosorption is rapid and reversible [119], but its efficiency depends
solution. The main mechanism involving the biosorption of metals (Pb2+, Ni2+, Cd2+, C
on a variety of environmental conditions, especially the pH, which determines the charge of
and Zn2+) using dead, dry aquatic plants as simple biosorbent materials for metal rem
the microbial cell wall, but also on the ionic strength, the level of dissolved organic matter,
was the ion exchange between monovalent metals present in macrophyte biomas
and the metal concentration. Some authors claimed that the ion-exchange mechanism
counter
on the cell surfaceions
mayand heavy metal
be related to theions
metaland protons
removal absorbed in
mechanism from watersolutions.
aqueous [110]. Seaweeds
Electronegative elements may be responsible for metal biosorption [120]. Moreover,different
a high binding affinity for heavy metals, and their cell walls have metals functi
groups (e.g., carboxyl, hydroxyl, phosphate, or amine), which
can also be adsorbed by extracellular polymers secreted by most environmental bacteria, can bind metal ions [
which haveThea seaweed U. lactuca
high affinity fromInthe
for copper. Mediterranean
addition coastsome
to adsorption, of Egypt had a high polyme
micro-organisms
biosorption capacity, with a maximum biosorption efficiency of 64.51 mg/g for C
[113]. Compared with the physical and chemical methods, bacterial biosorption is a m
treatment method for toxic pollutants, which are not easily removed, such as h
metals. These metal-tolerant bacteria can bind cationic toxic heavy metals to negati
charged bacterial structures and live or dead biomass components. Moreover, t
also removed copper by intracellular chelation precipitation, which reduced interference

with cellular activity and enzymatic denaturation [121].
Bioaccumulation is an accumulation of contaminants regulated by microbial metabolic
activity [119], which occurs when the rate of contaminant adsorption by micro-organisms
is higher than the rate of contaminant loss through excretion. Among others, CPx-type
ATPases played a role in the copper uptake capacity of some strains [122]. In turn, the
bioaccumulation efficiency depended on the concentration of contaminants accumulated
by the micro-organism. For example, Amycolatosis tucumanensis was able to accumulate up
to 25 mg/g (dry weight) of copper, 60% of which was intracellular [123], and this particular
bacterial species was able to efficiently trap copper within the cytoplasm by binding low
molecular weight cysteine-rich proteins (metallothioneins) [124]. Depending on the location
of metal uptake/accumulation, biosorption can be divided into extracellular precipitation,
cell surface adsorption, and intracellular accumulation. In metabolism-dependent biosorp-
tion, living cell systems underwent biosorption and accumulated intracellularly [125].
Moreover, Kluveromyces marxianus, Candida spp., and Saccharomyces cerevisiae could remove
73–90% of copper during growth [126]. Another way was metal uptake by metabolism-
independent biosorption, which occurs through physicochemical interactions between
functional groups on the bacterial surface and metal ions. The binding of metal ions to bac-
terial cell surfaces in metabolism-independent biosorption involves various mechanisms,
such as physical interactions (electrostatic or van der Waals interactions), chemical inter-
actions (replacement of attached metal cations by ion exchange), complexation, diffusion,
surface adsorption, or precipitation [127,128]. Bacteria reacted to harsh environments, such
as heavy metal contamination sites, by releasing extracellular polymers (EPS) from the
cell surface, which have a high affinity for copper [128]. In addition, proteins capable of
chelating metal ions were detected in the supernatant of cells exposed to Cu(II) according
to CELLO v2.5 [129].
The biomineralization mechanism relies on the ability of micro-organisms to create
local supersaturation conditions, where metals are precipitated in solution by coming into
direct contact with bacterial cells or their extracellular compounds. Thus, metals can be
directly precipitated with anions released by micro-organisms, such as phosphates, which
are less soluble for metals, or by replacing suitable cations from the lattice. In addition,
micro-organisms can indirectly contribute to the “immobilization” of metals by influencing
certain physicochemical parameters, which control the “solubility” of metals. For example,
sulfate-reducing bacteria precipitate metals in the form of insoluble sulfides.
Long-term exposure to metal contamination results in microbial communities adapted
to survive and persist in contaminated environments. In this sense, micro-organisms
have developed complex and specific cellular mechanisms composed of a wide network
of specialized proteins, transport proteins, and proteins involved in the regulation of
gene expression in response to both metal deficiency and excess [130]. These cellular
mechanisms, which maintain the optimal concentrations of metals, are called homeostasis.
Micro-organisms play an important role in the uptake of metals from the environment
by using a variety of mechanisms. These mechanisms differ between genera and/or
microbial species, and little is known about them at the molecular level when in equilibrium
condition [129].
Micro-organisms can mediate the immobilization of copper through biosorption,
bioaccumulation, and biomineralization, as well as its activation through redox, acidolysis,
or complexation decomposition of copper-containing phases [118]. Therefore, biological
methods have advantages in the adsorption and release of copper. Microbial remediation
of heavy metals has been used in the removal of heavy metal contamination due to its
outstanding advantages of high efficiency and low cost. However, there are still many
bottlenecks in its wide application. The molecular mechanisms of heavy metals detoxifi-
cation need to be further elucidated to enhance the accumulation of heavy metal ions by
micro-organisms. Extracellular/intracellular sequestration, active export, and enzymatic
detoxification are the main resistance mechanisms of living micro-organisms to heavy
metal ions, which would reduce their toxicity and convert them to inactive forms. Hydro-
gen sulfide precipitated heavy metal ions, and reductase altered the redox state of heavy
metal ions, improving microbial resistance to heavy metal ions while achieving heavy
metal remediation. There is a close internal inter-relationship between microbial resistance
mechanisms to heavy metal ions and their repair capacity [131].
Plants are also able to tolerate and even resist copper toxicity under different environ-
mental conditions. These include the release of organic acids into the soil to reduce copper
bioavailability [132], complexation with cytosolic ligands to detoxify intracellular copper,
and sequestering copper in intracellular compartments (e.g., vesicles) where the metal is
least harmful. The tolerance of plants to copper is different among species and different
varieties of the same species. In addition, severe copper phytotoxicity symptoms were
observed in some copper-contaminated sites [133], and bacteria can enhance the tolerance
of some plants to copper toxicity and can be used for revegetation in these areas.
3. Copper-Containing AMD Treatment Technology

Mining and processing plant flotation technologies also generate large amounts of acid
mine wastewater (AMD) containing Cu(II), and these water characteristics distinguish them
from conventional Cu(II)-containing wastewater, which not only contains large amounts of
heavy metals (Cu(II)) but also has a low pH and is difficult to treat. The current treatment
options for AMD are classified as passive or active processes [134]. The addition of various
acid neutralization and metal precipitation chemicals (caustic soda (sodium hydroxide),
lime and limestone, magnesium oxide, and hydroxide) to AMD water is a common active
treatment method, which can meet wastewater discharge limits in a short period of time.
The choice of chemical reagents depends on site specificity (seasonal variation), AMD
influent loading, and metal concentration [135]. The advantages of the method are that
it is fast and does not require additional operating sites. However, active treatment is
usually considered expensive compared to passive treatment, and there are problems with
disposal of aqueous sludge containing heavy metals. This method is mainly used for
“active remediation” of short-term contamination.
Passive treatment is based on the advantages of naturally occurring geochemical
and biological processes to improve the quality of AMD with minimal operational and
maintenance requirements [136]. Moreover, passive treatment includes artificial wetlands,
anaerobic sulfate reduction bioreactors, anoxic limestone drains, open limestone chan-
nels, limestone leaching beds, and slag leaching beds [135]. Passive systems can provide
long-term, efficient, and effective treatment for many acid mine drainage (AMD) sources,
provided they are properly planned and constructed, and require regular inspection and
maintenance [137]. Most passive treatment systems employ multiple methods, often in
series, to promote acid neutralization, oxidation, and precipitation of the resulting metal
flocs. The conditions and chemistry of AMD, flow rates, acidity and alkalinity, metals,
and dissolved oxygen concentrations are key parameters, which must be characterized
before selecting the appropriate treatment technique. Passive treatment results in long cycle
times and slow results but low environmental risk and low cost for long-term treatment of
contaminated sites.
4. Conclusions and Outlooks for Cu(II) Removal and Recovery

Among the various pollutants, Cu(II) is one of the harmful heavy metals. It is dis-
charged daily into wastewater streams from various industries, such as electroplating,
paints and dyes, petroleum refining, fertilizers, mining and metallurgy, explosives, pesti-
cides, and steel. Epidemiological studies have found an association between copper mining
activities and various health diseases (e.g., headaches, cirrhosis, kidney failure, and even
cancer) in people living near copper mining areas [138], and copper presents a high risk
of cancer. Both maximum contaminant level goal (MCLG) and maximum contaminant
level (MCL) for copper are 1.3 mg/L, meaning that there is no known or expected risk to
health in drinking water below this level (https://www.epa.gov/, accessed on 9 October
2022). Potential ecological risk factors (PERF) and potential ecological risk index (PERI) are
commonly used to assess environmental risk [139]. PERF ≤ 40 and PERI ≤ 150 are defined
as low for both single and environmental risks.
Despite presenting a large environmental risk in water, Cu(II) is a critical metal to
many industries, and removing Cu(II) from wastewater and considering the feasibility of
Cu(II) recovery are promising strategies. This review explores the recent advances in Cu(II)
removal technologies in water and wastewater. Although all heavy metal wastewater
treatment technologies can be used to remove heavy metals, they have their inherent ad-
vantages and limitations in Cu(II) removal and even the separation and recovery prospects
of Cu(II).
(i) Membrane separation is the most widely used technology for Cu(II) treatment in
industry, which is able to concentrate and purify heavy metals while removing contam-
inants for later recovery. However, membrane fouling is always an obstacle limiting its
process efficiency, so there is a need to develop cost-effective, efficient, and environmentally
friendly flushing technologies.
(ii) The ion-exchange method has a high contaminant removal capacity, fast removal
rate, efficient elution, and lifetime durability. The efficient elution is beneficial for Cu(II)
recovery, but the long-term reusability of the resin and the possibility of recovering the
target compounds from the regenerated solution limit the application.
(iii) Electrochemical technology has the advantages of simplicity of operation, high
removal efficiency, and low sludge (the precipitates produced during flocculation or de-
position) formation, but the high cost of electricity and separation increases the cost of
its application.
(iv) Chemical precipitation is cost effective, simple, and non-metallically selective, but
the high stability of the precipitate makes recovery difficult, resulting in a “replacement–
precipitation” strategy, which requires research into more affinity-based replacement agents.
(v) The adsorption method has the advantages of simple operation, low cost, easy
availability of materials, fast reaction rate, and good treatment effect, but in practice, the
general adsorption materials may have low adsorption capacity, poor stability, and difficult
separation after adsorption and need to improve the performance through physical or
chemical modification.
(vi) The bioremediation method of removing Cu(II) from wastewater by algae, fungi,
and plants is environmentally friendly and has little secondary pollution. However, the
physicochemical properties of water can affect the performance of biosorbents. Biomineral-
ization precipitation also seems to be effective in the removal of Cu(II), but the problem
with this technique is the generation of metal-rich sludge (bioactive sludge), which makes
the recovery of precipitated metals difficult. In addition, biological methods have high
additional costs, such as the need for nutrients and regulation of the environment (pH,
temperature), to maintain the biological process.
By combining the advantages and disadvantages of different technological approaches,
coupling between technologies to achieve efficient copper removal and recovery as well
as to obtain low health risk effluent is the focus of future research (Tables 2 and 3). The
review of technologies shows that conventional heavy metal treatment technologies are
universal and can be useful in the removal of many heavy metals. However, different
functional groups or selective resins have advantages in the removal of Cu(II), so we can
optimize the material or technical means for this purpose. Meanwhile, the future research
should focus on reducing system costs, improving efficiency, and developing intelligent
systems. All technologies have their merits, and their use depends on their feasibility. Most
studies have reported batch and laboratory-scale systems. Therefore, continuous systems
and pilot-scale studies are needed to demonstrate industrial applications. In addition,
real wastewater should be studied more than synthetic wastewater to investigate the real
interaction of the technology with compounds in solution. Likewise, research should focus
on commercialized technologies in the area of pollutant removal, so that the next generation
of wastewater treatment can be developed in a sustainable, efficient, and cost-effective
manner. Health risk assessment is also an important issue in the pollution management
process. Considering the high toxicity response factor of copper (TR = 5) for different water
bodies, we have to obtain an effluent with discharge concentrations lower than MCL to
effectively avoid possible health risks.
Table 2. Summary of copper removal efficiency based on different treatments.
Techniques Materials/Reactors Removal Efficiency of Cu References

Hydrophilic polyurethane modified cellulose
92% [140]
acetate ultrafiltration membranes
Cellulose acetate based biopolymeric mixed
Membrane separation 84–88% [141]
matrix membranes
Chitosan-cellulose acetate-TiO2 based
97% [142]
membrane
Y zeolite ion exchangers 64% [143]
Ion exchange
Ion exchange resin 99.14% [144]
Bipolar disc reactor 90.1% [145]
Continuous electrochemical cell 91% [146]
Electrochemical reaction
Bioelectrochemical and
99.9% [147]
electrochemical systems
OM in waste distillery
92% [148]
slops—precipitation/coagulation
Chemical precipitation
Synthetic nesquehonite 99.97% [149]
struvite 99.9% [150]
Hexagonal boron nitride 92% [151]
Adsorption Zeolite, bentonite, and steel slag 98.47–99.98% [152]
Agro-industrial waste 89% [153]
Stenotrophomonas maltophilia 88% [154]
Biotechnology Microalgae >95% [155]
Aspergillus australensis Biomass 79% [156]
Table 3. Summary of different copper ion removal technologies [3,157,158].
Technology Advantages Disadvantages Application Scenarios Cost

Suitable for both high- and
Excellent performance in
low-concentration
scale-up applications, such as Membrane fouling, capital cost,
copper-polluted water;
Membrane excellent heavy metal removal, maintenance and operational
selection of the right
filtration high efficiency, ease of cost, less efficient in case of
polymer/micellar agent is
operation, and low space lower metal ion concentration
required to improve the
requirements
rejection efficiency Treatment cost of
Membrane scaling problems, membrane fouling
low water permeability, high RO
Effective removal of metals operating pressure due to
Reverse osmosis Use in drinking water
from wastewater internal concentration
polarization, low water flux, and
high energy consumption
Fouling and maintenance costs,
Selective removal of heavy Treatment of water bodies High cost of
high capital cost of equipment
metals, high treatment polluted by a specific metal synthetic resin,
Ion exchange and instruments, high
capacity, high metal element, not suitable for pollutant
operational as well as resin
removal rate large-scale application recovery costs
regeneration cost
Table 3. Cont.
Technology Advantages Disadvantages Application Scenarios Cost

Electrochemical methods, such
as electrodialysis,
Reduced chemical
electrocoagulation,
consumption, recovery of pure
Low current effect and electrodeposition, and
Electrochemical metals, effective removal of
selectivity, high power capacitive deionization, are Electricity costs
reaction desired metals, suitable for
consumption capable of removing Cu(II) by
initial high concentration
different mechanisms and are
contamination remediation
therefore suitable for a wide
range of copper concentrations
High chemical requirement, pH
maintenance at optimum level,
handling of colloidal particle
Low metal concentration in
sludge disposal problem. A For the treatment of
the effluent achieved. This
Chemical large number of factors, such as concentrated copper
approach can be adapted to Sludge disposal cost
precipitation temperature, pH, precipitant wastewater, the preferred
handle large quantities of
concentration, etc., have to be method is precipitation
wastewater. Simple to use
monitored when implementing
this technique, which is
quite difficult
Chemical regeneration
requirement, fouling and
corrosion of treatment plant,
Highly effective for removing disposal of exhausted
heavy metals within adsorbents, preparation of the When treating diluted
permissible limits; the adsorbent involve high costs, wastewater, adsorption is Cost of desorption
Adsorption
desorption process can such as in the case of activated preferred due to its simplicity and regeneration
produce a concentrated Cu(II) carbon, loss of adsorption and effectiveness
stream with recovery potential capacity by the adsorbent in each
cycle, frequent regeneration,
which reduce the simplicity of
the adsorption process
Author Contributions: Conceptualization, validation, writing—original draft preparation, and for-

mal analysis, Y.L.; investigation, resources, data curation, H.W.; writing—review and editing, Y.C.;
writing—review and editing, visualization, supervision, project administration, N.C. All authors
have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: This research did not involve human or animal studies.
Informed Consent Statement: This research did not involve human studies.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare that there are no conflicts of interest. We do not have
any possible conflicts of interest. Author Yongming Liu is employed by a company; however, the
experimental data and results of the study are not in any way related to the company.
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International Journal of

1 Shandong Provincial Geo-Mineral Engineering Co., Ltd., Jinan 250013, China

Keywords: copper; wastewater; health; physical–chemical technology; biotechnology

Table 1. Cu concentrations around the world.

Country/Region Concentration Paper

Based on the above, the technologies regarding the treatment of Cu(II)-contaminated

physicochemical techniques, the applications of biotechnology in the treatment of Cu(II)-

Figure 1. Treatment technology of Cu(II)-polluted wastewater.

Microfiltration, Ultrafiltration, and Nanofiltration

Figure 2. Membrane technology including MF, UF, NF, and RO.

Reverse Osmosis and Electrodialysis

opposite direction to the natural osmosis phenomenon [52]. Electrodialysis is an electro-

2.1.2. Ion Exchange

2.1.4. Chemical Precipitation

Figure 4. Biotechnology for copper removal.

also removed copper by intracellular chelation precipitation, which reduced interference

3. Copper-Containing AMD Treatment Technology

4. Conclusions and Outlooks for Cu(II) Removal and Recovery

Table 2. Summary of copper removal efficiency based on different treatments.

Techniques Materials/Reactors Removal Efficiency of Cu References

Table 3. Summary of different copper ion removal technologies [3,157,158].

Technology Advantages Disadvantages Application Scenarios Cost

Technology Advantages Disadvantages Application Scenarios Cost

Author Contributions: Conceptualization, validation, writing—original draft preparation, and for-

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