Desalination 527 (2022) 115510

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Desalination
journal homepage: www.elsevier.com/locate/desal

Recovery of precious metals from industrial wastewater towards resource

recovery and environmental sustainability: A critical review
Ali Taghvaie Nakhjiri a, b, Hamidreza Sanaeepur a, *, Abtin Ebadi Amooghin a,
Mohammad Mahdi A. Shirazi c, d, **
a
Department of Chemical Engineering, Faculty of Engineering, Arak University, Arak 38156-8-8349, Iran
b
Department of Petroleum and Chemical Engineering, Science and Research Branch, Islamic Azad University, Tehran, Iran
c
Membrane Industry Development Institute, Tehran, Iran
d
Chemical Engineering Department, Faculty of Engineering, University of Kashan, Kashan, Iran

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Critical review on breakthroughs in the

recovery of various PMs from
wastewater
• Discussion about different approaches
for PM recovery
• Evaluation of the advantages and dis­
advantages of PM recovery techniques
• Future perspectives towards the sus­
tainable use of PMs

A R T I C L E I N F O A B S T R A C T

Keywords: Nowadays, the recovery processes of precious metals (PMs) from industrial wastewater streams have found
Precious metals significant attractions among various investigators worldwide. PMs are known as rare/noble chemical elements
Recovery that their fundamental characteristics such as ductility, electrical conductivity, and resistance against corrosion
Industrial wastewater
have made them promising for application in industrial-based activities such as jewelry, petrochemistry, and
Resource recovery
catalysis. The main objective of this review paper is to provide an opportunity for expert as well as non-expert
Environmental sustainability
readers to be familiar with the state-of-the-art breakthroughs in the recovery of PMs (i.e., gold (Au), silver (Ag),
platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), iridium (Ir), osmium (Os), Rhenium (Re) and so
on.) from wastewater streams. Apart from the explanation of industrial applications, the recovery process of PMs
using various approaches is aimed to be interpreted comprehensively. Eventually, the advantages and

* Corresponding author.
** Correspondence to: M.M.A. Shirazi, Chemical Engineering Department, Faculty of Engineering, University of Kashan, Kashan, Iran.
E-mail addresses: h-sanaeepur@araku.ac.ir (H. Sanaeepur), che.shirazi@gmail.com (M.M.A. Shirazi).

https://doi.org/10.1016/j.desal.2021.115510
Received 3 August 2021; Received in revised form 6 December 2021; Accepted 17 December 2021
Available online 20 January 2022
0011-9164/© 2021 Elsevier B.V. All rights reserved.
A. Taghvaie Nakhjiri et al.
disadvantages of applied techniques for the recovery of PMs are discussed, and different approaches as well as
future perspectives towards their sustainable use are introduced.
1. Introduction
1.1. Definition and characteristics of precious metals (PMs)
The term “precious metals (PMs)” is taken to involve silver (Ag), gold
(Au), palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh),
iridium (Ir), osmium (Os), and rhenium (Re). PMs are known as rare and
chemically inert elements that possess significant economic cost. PMs
have been mainly of paramount attention as the portfolio diversifier and
hedge against inflation [1]. PMs do not usually oxidize, corrode and
naturally tarnish. Thus, they have been used for fabricating jewelry stuff
and have also recently found extensive applications in the fabrication of
electronic devices and industrial-based catalysts. Therefore, PMs can be
extensively found in waste and wastewater samples [2,3].
Rarity is the most prominent characteristic of PMs. They just consist
of a small portion of the Earth’s crust, particularly when compared to
iron or copper [4]. All types of PMs possess significant densities (specific
gravities ranging from 10.5 for Ag to 22.6 for Ir), good resistance against
corrosion, appropriate physicochemical properties (i.e., ductility and
electrical conductivity), and light reflectivity. The chemical reactivity of
PMs is much lower than the majority of elements. They have a gleaming
appearance, which is the main reason for their application in the jewelry
industry. The great potential of ductility facilitates the appropriate
shaping of PMs into a good form without being broken. For example, Au
has both ductility and malleability properties, which means it can form
into both thin sheet or wire forms. The melting point of PMs is much
higher than conventional metals, which justifies their requirement for
Fig. 1. Overview of prevalent PMs and periodic table corresponding to them.
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Desalination 527 (2022) 115510
high amounts of heat to be molten and reshaped [5].
Among different types of PMs, Ag has the most significant electrical
and thermal conductivity and the reflection of visible light. Au is another
PM, which has good oxidation resistance and ductility. Pt possesses
some unique advantages, such as thermal stability and corrosion resis­
tance. Pd has a significant capability to absorb H2 (about 2800 times
higher than its volume), which makes it favorable for catalyst fabrica­
tion [6]. Additionally, Ir and Rh can operate in unfavorable and harsh
conditions, such as high temperature, and can resist the erosion of
different melting oxides [7]. Due to these reasons, we can conclude that
the PMs have become an indisputable part of humans’ life. Fig. 1 shows
commonly employed PMs and the periodic table corresponding to PMs,
following with their specifications.
1.2. What makes precious metals valuable?
For an element to gain “precious” status, three major parameters,
including rarity, value, and composition, are required [8]. It is believed
that the overall amount of pure Au ever mined could be similar to two
Olympic-sized swimming pools. The rarity of Pt and Pd is even more
than that of Au. Value is known as the second important parameter
attributed to a PM to be precious. Mainly, Au has been widely applied as
currency in every civilized society in history. Nowadays, Au bullion has
been verified for capitalists as a hedge against inflation in times of
economic inconsistency. Other lesser-prevalent PMs are favorable for
both their industrial/investment values. Composition is the third
parameter, which considerably affects the value of PMs. From the
A. Taghvaie Nakhjiri et al.
Fig. 2. Schematic illustration of WEEE production trend from 2019 to 2030.
Adapted with permission from [22].
chemical reactivity, PMs are less reactive compared to other elements
and possess more corrosion resistance. Therefore, when metal is rare,
economically valuable, and is naturally present in the nature, it has good
eligibility to be placed in the group of PMs [9].
Recently, the recovery of PMs from various types of wastewater
streams is of great importance for the conservation of resources and the
protection of the environment. Moreover, it is worth noting that PMs are
considered as valued substances in different industrial-based applica­
tions, which their scarcity, high cost, and difficulty in supplement
significantly affect the development of their industries all over the
world. Therefore, the recovery of PMs from wastewater streams provides
a promising alternative to overcome the challenges associated with their
sustainable supplement from natural sources [10,11]. The above­
mentioned reasons have motivated the authors of this paper to
comprehensively study the promising techniques to increase the re­
covery efficiency of PMs from various wastewater streams to open new
horizons for investigators and expert readers in over the world.
1.3. Outlines of this work
This work aims to provide a critical review for expert and academic
researchers about the recent breakthroughs in the recovery of PMs from
wastewater streams. Apart from the explanation of sources and indus­
trial applications, the recovery process of PMs using the primary ap­
proaches, including biosorption, coagulation, flocculation, leaching,
ionic liquids (ILs), ion exchange resin (IER), precipitation, electro­
chemical, membrane technology, hybrid techniques, and photocatalysis
is aimed to be interpreted comprehensively. After discussing the ad­
vantages and disadvantages of the abovementioned processes, disparate
approaches towards the sustainable applications of PMs and enhancing
their environmental sustainability, are evaluated comprehensively.
1.4. Main objective
Up to the knowledge of the authors, despite the existence of
numerous papers about the recovery of PMs from waste, no attempt was
comprehensively done to evaluate different approaches for their
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Desalination 527 (2022) 115510
recovery from wastewater streams. Therefore, filling the research gaps
and interpretation of physical, biological, chemical and hybrid tech­
nologies are of great interest. In this paper, almost all presented PM
recovery techniques are reviewed and their advantages/disadvantages
are explained introducing a new horizon towards their sustainable
supplement and application. It should be emphasized that its importance
may be considered as a hub where issues related to the economics (PM
role on global economy), sustainability (PM considered as heavy ele­
ments), waste management (wastes as PM source) and desalination
(separation of PM salts and complexes) meet together. This makes this
review paper complete and critical, and, as per authors “for expert as
well as non-expert readers”.
2. PMs in industrial effluent: origin, fate, and healthcare issues
2.1. Origin and sources of PMs
2.1.1. Urban mining and alloys industry
Rapid development in the modern industry has resulted in the
emergence of an outstanding increment in wastewater generation at the
production step and waste generation at the end of the product lifecycle.
The urban mining (UM), which is considered a vital process for the
permanent extraction of natural resources, has been accepted as an
attractive research topic due to the rapid growth rate, environmental
impacts, and market potential of waste and wastewater generated in
urban areas [12,13]. The recovery of PMs from urban mines has been of
paramount attention from both academic and industrial points of view
owing to their extensive use, high price, and scarcity in natural ores
[14]. Urban mines consist of considerable concentrations of PMs. Mining
wastes (MW), municipal solid wastes (MSW), waste electronical and
electronics equipment (WEEE), end of life vehicles (ELVs) are known as
the prominent sorts of urban mines [15–18]. It has been reported that
1 kg MSW consists of 5.3, 0.4, 0.059, and 0.0005 mg of Ag, Au, Pt, and
Ru, respectively. These precious metals not only can be found in soil but
also could be transferred to the urban wastewater via runoff and surface
water streams. Although negligibility, the amounts of Au and Pt in MSW
are more significant than their amounts in natural mine stones, making
A. Taghvaie Nakhjiri et al.
their recovery justifiable [19,20]. WEEE is regarded as a non-
homogenous combination of materials that usually includes thousands
of various components, which many of which possess significant toxic
potentiality [21]. Global WEEE manufacturing in 2019 reached
53.6 million tons and is estimated to increase up to 74.7 million tons in
2030 [22]. Hence, WEEE might be considered an essential source for the
recovery of PMs towards environmental sustainability and circular
economy. Fig. 2 schematically estimates the production amount of
WEEE from 2019 to 2030.
End-of-life vehicles (ELVs) can be categorized as harmful waste and
have considerable ability to pollute the environment (soil, surface water,
groundwater, etc.). They are an essential class of waste whose process­
ing is extremely hard due to their complex structure [23]. The appro­
priate management of ELVs as a rapid-growing waste seems to be vital
because their number is anticipated to be enhanced to nearly 80 million
units per year by 2020. The recovery process of PMs, therefore, is of
great necessity for environmental protection, resource recovery, and
sustainable development [24,25].
2.1.2. Jewelry industry
Au, Ag, and Pt are significant PMs for designing and fabricating
rings, necklaces, and bracelets, which their appropriate recovery from
jewelry waste and wastewater is of great importance [26]. It has been
reported that the jewelry industry is the principal applicant of nearly
80% of Au and 20% of Ag existed in the market. Hence, the dust and
wash-water of these metals produced from workshops is significantly
essential for the affordable recycling process. The main reason for Pt
popularity in the jewelry industry is the excellent resistance of this PM
against tarnishing when exposing to water or air. Additionally, the
silver-white color and excellent resistance of Pt against corrosion are
rare in PMs [27].
The loss of PMs such as Au and Ag in the production process
significantly influences the cost parameter. Recovery of scraps/wastes in
the jewelry industry is an essential issue for economic jewelry produc­
tion. The contents of PMs in scraps/wastes in the jewelry industry can be
high to medium grade [28]. In this sector, wastes produced from
workshops are gathered and then sent out for final processing [29,30].
The scrap substances that possess more excellent grades of PMs are
cleaned and then recycled. However, the polluted scraps and other
wastes that include lower amounts of PMs are collected and refined to
form pure metals [31]. Generally, jewelry polishing waste (JPW), floor-
sweeping waste (FSW), and hand-washing wastewater (HWW) are
considered as various sorts of waste manufactured in jewelry workshop
[28,30].
2.1.3. Electronic, batteries, fuel cell, and photovoltaic industries
The global manufacturing of electronic-based waste illustrates that
the amount of Au in almost 40 smartphones is equal to 1000 kg of the ore
[32]. Also, there is a significant amount of platinum-group metals.
Natural resources of these metals all over the world are limited
(≈66,000 tons) [33]. Additionally, It was reported that in 2019, nearly
53.6 million tons of precious/noble metals-including electronic waste (i.
e., outdated computers, etc.), were produced all over the world [34].
Thus, the surface and groundwater resources can be contaminated by
heavy metals and PMs due to improper disposal of this type of hazardous
waste. Therefore, finding a suitable technique for the recovery of
precious/noble metals from electronic-based waste, waste catalyst, and
industrial wastewater in this industrial sector, seems to be mandatory
owing to their potential harms to human health and economic
circularity.
When the “battery precious metals” are discussed, these consist of
cobalt (Co), lithium (Li), nickel (Ni), vanadium (V), and manganese
(Mn). Vanadium redox flow battery (VRFB) systems are considered the
most advanced types of flow batteries owing to their excellent revers­
ibility and relatively large power output. Albeit, the capital cost of VRFB
systems is a big challenge towards their extensive market
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Desalination 527 (2022) 115510
commercialization [35]. Co and Li are known as two commonly applied
PMs in the industrial-based fabrication of batteries. More than 50% of all
global Co production now goes into lithium-ion batteries. It is estimated
the Co demand enhances from 136 kilotons (kt) in 2017 to 272 kt in
2025. Compared to today’s levels, Co consumption in the batteries is
predicted to improve by a factor of 4 in 2030 [36,37]. Moreover,
lithium-titanate and lithium-iron-phosphate have attracted a lot of
attention in electric vehicle (EV) applications as they are Co-free
[38–42]. As a result, the recovery of PMs from industrial effluent
generated in these industries can enhance their sustainability.
2.1.4. Oil, gas, and petrochemical industries
Catalysts containing PMs play an important role in the downstream
processes of the oil and gas industry. The petrochemical industry
extensively applies PM-based catalysts to produce high-octane gasoline
from naphtha and different highly-activated organic chemical materials
(i.e., cyclohexane). It is prognosticated that >642 oil refineries world­
wide treat 87 million barrels per day (bpd) of crude oil applying
4.1 × 1013 kg of PM-based catalysts. On average, catalysts used in the
petrochemical industry consist of 0.25% Pt. Hence, approximately
1.025 × 1013 kg of Pt is expanded in this sector. The development of the
petrochemical industry depends on efficacious application and recovery
of PMs such as Pt, Pd, and Re in the employed catalysts. It is estimated
that each change-out in an oil refinery includes 25 to 50 MT of catalysts.
These catalysts contain PMs worth $2 to $4 million [43,44]. Therefore,
not only from the waste catalysts but also PMs recovery from the wash-
water and wastewater in petrochemical and refinery plants is an
emerging issue which should be investigated, even if the PMs concen­
tration in the liquid stream is in the trace range.
2.1.5. Ceramic and glass industries
Recovery of PMs, which can be presented in or related to ceramic
materials, is considered the secondary treatment approach for these
metals, apart from the primary ore refining. Nowadays, significant
quantities of ceramic materials, especially refractory ceramic materials
(i.e., barium titanate, titanium dioxide, alumina, zirconia, and silica),
are scrapped by different industries such as electronics. These materials
often consist of considerable PMs such as Pt, Ir, Pd, Ag, and Au. Also,
smaller quantities of Ru and Rh maybe exist.
One of the most critical challenges for recovering ceramic materials
(such as barium titanate) is their high melting points, which has made an
essential obstacle towards their recovery using traditional pyrometal­
lurgical techniques [45,46]. The recovery of PMs from ceramic and glass
has been of great attention as a promising approach. Old dish and
glassware may consist of Au, Ag, and Pt as well as other PMs. Traditional
techniques for Au recovery from ceramics that require potentially
poisonous chemical materials are not suggested [47]. The recovery
process of Ag from low temperature co-fired ceramic (LTCC) is a
distinctive approach to convert waste to wealth in the industrial scale. In
the process mentioned above, AgCl is recovered from industrial LTCC at
optimum condition applying 5 M HNO3 leaching for 150 min at 75 ◦ C
considering constant stirring accompanied by precipitation utilizing HCl
at a molar ratio of [HCl]/[AgNO3] = 2 [48].
2.1.6. Dental, medical and pharmaceutical industries
PMs have a long history of use in dentistry due to their remarkable
privileges of operation in the mouth. PMs must be in the form of alloys to
meet biocompatibility requirements following physical stability and
mechanical strength for in vivo application [49,50]. Most the precious
metal alloys (PMAs) in dentistry are applied for indirect restorations (i.
e., inlays, onlays, crowns, and bridges). Highly efficient PMAs can be
classified into three major groups, including Au-Pt, Au-Pd, and Au-Ag-
Cu alloys. Au-Pt alloys are prevalently utilized for both full- and
ceramo-metal applications. The alloys mentioned above were also
developed for Pt to act as a Pd substitute to decline the alloy cost
significantly. Despite significant value, Au-Pd alloys are extensively
A. Taghvaie Nakhjiri et al.
applied PMAs for ceramo-metal restoration. Ag is existed in some for­
mulations to improve the stability of the solid solutions. Au-Pd alloys
possess greater strength, modulus, and hardness than Au-Pt alloys
[51,52].
Brilliant chemical, physical and mechanical characteristics of Pt and
its alloys, including low corrosion and high biocompatibility, make them
promising for a wide range of medical applications. The biocompati­
bility of Pt makes it appropriate for temporary or permanent implan­
tation in the body. Unlike Ni and Cu, Pt does not corrode inside the body,
resulting in allergic reactions. Low-invasive medical approaches usually
apply electricity to diagnose and cure patients’ diseases. The high con­
ductivity of Pt makes it an efficient electrode material. This precious
metal is radiopaque. Therefore, it is visible in X-ray images, enabling
doctors to observe the situation of the device during treatment [53].
Ag is extensively applied in almost every industry, from electronics
to medical devices. This precious metal is more reflective than other
metals and possesses anti-microbial properties, leading to its application
in numerous medical purposes. Ag complexes have currently been of
great interest for designing novel metal-based anticancer treatments
[54].
2.2. Fate and environmental impact of PMs in industrial effluents
Any extracted resource used in human activities possesses potential
environmental effects. This sentence is also correct for PMs that their
environmental impacts can be even more apparent in the future owing to
the permanently increasing demands for PMs in both developed and
developing countries. Therefore, development and optimization of PM
recovery systems from an environmental aspect is an essential part of
environmental sustainability [55,56]. PMs are known as an essential
part of the natural biogeochemical cycle. Given our limited knowledge
of complex natural processes and their interactions with human change,
it is difficult to make accurate predictions of the magnitude with which
humans have altered the biogeochemical cycle. Human activities
possess the potential of changing the biogeochemical cycle in two ways,
including alteration the rate of metal availabilities and changing the
form of metal occurrences in the environment [57].
Some PMs and their compounds are poisonous and may cause serious
environmental and health-related problems for humans if not perfectly
managed. Conventional processes such as PM mining may result in se­
vere local health and environmental issues owing to the release of highly
poisonous metals and materials into the ground and surface water as
well as soil. Additionally, these processes cause environmental chal­
lenges globally because they are very energy-intensive [58]. Therefore,
developing proper and efficient recovery processes is of great impor­
tance to mitigate the detrimental influences of PMs on the environment.
2.3. Contamination of the aquatic environment by PMs
During the last decades, increasing amounts of Pt, Pd, and Rh have
emerged in disparate terrestrial and aquatic environments. Anthropo­
genic sources of Pt, Pd, and Rh, are industrial discharges and hospital-
based effluents [59]. Since platinum group metals (PGMs) are distrib­
uted in particle form (particularly in discharge streams of the chemical,
refinery and petrochemical industries), they are believed to be accu­
mulated in the aquatic system sediments (ASSs). It is reported that the
amounts of Pt, Pd, and Rh in high-polluted sediments are >20 ng⋅g− 1 for
Pt and Pd and >3 ng⋅g− 1 for Rh. In comparison, these values for light-
polluted sediments are often lower than 10 ng⋅g− 1 for Pt and Pd
whereby Rh is not often detectable [60,61].
It is worth mentioning that the amounts of PGMs in sediments are
still much lower (ng⋅g− 1 range) than other types of heavy metals (μg⋅g− 1
range) [61]. Natural processes are responsible for almost 18% of annual
Ag entrance to the environment. The rest, 82%, is released by anthro­
pogenic industrial-based activities. About 4% of the yearly released Ag
to the environment enters the atmosphere, 28% enters the aquatic
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Desalination 527 (2022) 115510
environments, and 68% enters terrestrial ecosystems. Ag can accumu­
late in high concentrations in the environment in different ways (e.g.,
combined with soil or water at hazardous waste sites) [62].
2.4. Toxicity on the human health
The PGM compounds have shown extensive toxic impacts on the
organisms. Great exposure of humans to PGMs (mainly Pt, Pd, and Rh)
will result in serious health problems, such as allergic diseases of the
respiratory passages, dermatoses, and eyes infection. The abnormal
cutaneous absorption of the ones mentioned above, reduces hemoglobin
amount in the blood, carbohydrate and lipid metabolism, liver func­
tions, and development of glomerulonephritis [63,64].
Ag is another important PM, which its toxicity on the human is of
great interest due to the existence of this metal in various applications. It
has been reported that the long-term exposure of Ag to the body may
cause severe allergic reactions and inflammations in different organs of
the body, such as dermatitis and stomatitis. Activation of allergic
mechanisms can be attributed to the gastrointestinal/cutaneous ab­
sorption of Ag due to its contact with sweat, saliva, or skin [65]. The
most severe influences related to the long-term exposure of Ag are
irreversible argyria (abnormal pigmentation of the skin) and argyrosis
(abnormal pigmentation of the eyes). Additionally, it has been reported
that the respiration of excessive amounts of soluble Ag component re­
sults in severe both upper (nose and throat) and lower (chest) respira­
tory tract irritation [66,67].
2.5. Advantages of the PMs recovery
In recent years, the demand for different types of PMs has consid­
erably improved, accompanying by significant growth of the economy
and its circularity. However, the economic or technological acquisition
of PMs is complex due to the lack of supply by limited producing
countries in different production areas. Sustainable supplementation of
PMs is still a severe challenge, and thus, advances in new recovery
technologies seem crucial to secure the sustainable use of resources and
the guaranteed resource recovery [11]. PMs are among the most
recoverable merchandise on Earth due to their high cost, making them
affordable to recover. Although the recovery process of PMs is related to
a long time ago, it remains a ‘hidden’ industry even today. More
remarkable recovery from natural resources, growing demand, sus­
tainable value, and versatility are essential factors justifying the recov­
ery of PMs around the world [27,68].
3. Recovery of PMs from industrial waste and wastewater
3.1. Physical techniques
3.1.1. Adsorption
Adsorption is an environmentally friendly and affordable technique
for the selective recovery of PMs from various resources [69]. For
aqueous PM sources, the separation process of the desirable precious
elements from the solutions can be used directly. However, for solid PM
sources, dissolution of desired precious elements applying appropriate
solvents is of significant requirement [70]. Among the wide variety of
adsorption procedures, magnetic solid-phase extraction (MSPE) has
been able to open new horizons towards the efficient recovery of PMs.
The MSPE process needs the addition of magnetic sorbent particles to
the target ions’ solution [70]. In this technique, the selection of applied
adsorbent materials to gain the best selectivity is of prime importance
[71]. Appropriate adsorbing agents must be distinguished by suitable
specific area, acceptable physicochemical stability, and good adsorption
performance. The majority of the magnetic particles (i.e., iron, nickel,
cobalt) and their alloys show excellent ferromagnetic properties [72].
Here, some of the recently published results on adsorptive recovery of
PMs are presented.
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

functionalization of Ni0.6Fe2.4O4 (Fig. 3). Results revealed that at opti­

mum pH (=4), the maximum adsorption capacity of 283.9 mg⋅g− 1 was
achieved via a triple mechanism (i.e., ion exchange, complexation, and
reduction). The adsorption process submits to pseudo-secondary ki­
netics and Langmuir models because monolayer chemisorption is the
rate-determining step. As the spontaneous endothermic reaction was
carried out in the adsorption processes, the increased temperature was
highly favorable for Au(III) recovery from the wastewater sample.
In another work, Xue et al. [75] studied composite adsorbent for
removing PMs, including Au(III), Pd(II), Pt(IV), and Ru(III), from an
aqueous environment. In this work, the polyurethane polymer with the
form of foam was utilized as the matrix. Fig. 4 illustrated the schematic
of the fabrication procedure for this adsorbent. The obtained results
revealed that the poly-Cys-g-PDA@GPUF adsorbent (cysteine polymer
brush-grafted PDA@GPUF) showed a remarkable separation perfor­
mance for all investigated PMs. This composite adsorbent contained a
high concentration of hydroxyl, imine, and thiol groups on the surface,
which guaranteed its high adsorption performance. Experimental results
revealed that pH was a dominant operating parameter. At a pH value of
0, the maximum adsorption was achieved for Au(III), Pd(II), and Pt(IV),
while Ru(III) was highly adsorbed at a pH value of 3.0. The authors
concluded that the composite adsorbent (poly-Cys-g-PDA@GPUF) was
successfully and efficiently used in the pre-concentration step for sepa­
rating Au(III), Pd(II), Pt(IV), and Ru(III) in aqueous samples and
metallurgical slag.
Hu et al. [76] worked on a novel metal-organic framework (MOF)
Fig. 3. Recovery of Au(III) from wastewater using functionalized Ni0.6Fe2.4O4
adsorbent for Au(III) removal from the wastewater. The adsorbent (2,5-
adsorbent [74].
TP) was prepared with sulfur-containing ligands and Zn(II). Results
revealed excellent performance for Au(III) adsorption with the adsorp­
Hu et al. [73] studied a new adsorbent based on zeolitic imidazolate
tion ratio of 97% and maximum adsorption capacity of 1253.5 mg⋅g− 1.
framework-8 (ZIF-8) for separating the Au(III) from an aquatic envi­
The authors concluded that the facile synthesis, high selectivity, high
ronment. The authors discussed that the proposed adsorbent with a
adsorption capacity, and remarkable reusability highlight the 2,5-TP
porous structure could perform relatively stable under different oper­
adsorbent for Au(III) removal from wastewater (Fig. 5). Recently,
ating conditions with a high adsorption capacity of 1192 mg⋅g− 1
Yang et al. [77] studied the porous adsorbent with three-dimensional
(pH = 2.5 and T = 298 K). According to the results of experiments,
structure, which was made of graphene-like carbon (PGC) via catalytic
partial reduction of Au(III) and the electrostatic interaction significantly
process, known as 3D-PGCH. The new adsorbent showed a high capacity
dominate the adsorption process. The authors concluded that the
for removing Ag+ from an aquatic environment with an adsorption value
considerable adsorption capacity, outstanding stability, and facile
of 234.32 mg⋅g− 1 (pH: 4 and T: 303 K). Moreover, according to the
regeneration of the proposed adsorbent were the highlights of this
adsorption-desorption experiment, the 3D-PGCH adsorbent showed
research. Zhao et al. [74] studied a new adsorbent for recovery of Au(III)
proper reusability, even after four-cycle experiments.
from wastewater. In this work, mercaptothiadiazole was used for the

Fig. 4. Schematic procedure for fabricating of poly-Cys-g-PDA@GPUF adsorbent (Green, yellow, and red represent good, better, and bad selectivity, respectively)
[75]. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

6
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

Fig. 5. (a) XRD patterns of 2,5-TP, (b) ball-and-stick representation of 2,5-TP (C, gray; O, red; Zn, green; S, yellow; hydrogen atoms were omitted for clarity), (c)
three-dimensional framework of 2,5-TP, (d, e) SEM images, and (f) FT-IR spectrum [76]. (For interpretation of the references to color in this figure legend, the reader
is referred to the web version of this article.)

(γγ-Fe2O3), have attracted greater interest due to their high surface area,
Table 1 resulting in faster kinetics and improved adsorption efficiency [78].
Some examples of magnetic adsorbents for the recovery of PMs.
Table 1 presents different employed magnetic adsorbents for the PM
Adsorbent Adsorbate Eluent Maximum Ref. recovery from solutions.
loading capacity
Fig. 6 presents a schematic demonstration for the adsorption process
Fe3O4 nanoparticles • Pd(II) • 0.5 M HNO3 for • [79] of Pd2+ ions applying two mechanisms including simple electrolysis
1
• Rh(III) all of metal ions 0.103 mmol⋅g− system (Ni/Al2O3-E) and physical mixing method (Ni/Al2O3-PM). It is
• Pt(IV) simultaneously
demonstrated that the emergence of synergistic impact due to the
•
1
• 1 M NaHSO3 0.149 mmol⋅g−
for Rh(III) • presence of strong magnetic attraction following with ions exchange is
• 0.5 M NaClO4 0.068 mmol⋅g− 1
an important factor in efficacious adsorption of Pd2+ ions applying the
for Pt(IV)
1
Ni/Al2O3-E compared to Ni/Al2O3-PM. Whereas, the surface –OH
Iron‑carbon Au 0.52 g⋅g− [80]
–
groups and soft magnetic properties can be considered as the prominent
composite
Thiol-modified Au 1–2 M HCl + 2% [81] factors for the unacceptable adsorption capacities obtained by pristine
Fe3O4@SiO2 thiourea Al2O3 and NiO, respectively. It is worth noting that the NiAl2O4 in Ni/
nanoparticles Al2O3-E system has a considerably greater magnetic field to attract Pd2+
Fe3O4 modified with AgNPs 1% (w/v) – [82] ions compared to agglomerated NiO-Ni0 in the Ni/Al2O3-PM. Further­
chitosan thiourea + 10%
(v/v) HNO3
more, Pd2+ ions possess the potential of exchanging with the hydrogen
Graphene-like Au and Pt – – [83] atoms of bridging and non-framework –OH groups of Al2O3 in both
carbon-coated systems (Ni/Al2O3-E and Ni/Al2O3-PM) [88].
cobalt metal The adsorption performance of Pd2+ ions in Ni/Al2O3-E system can
nanoparticles
be evaluated applying four prevalent adsorption isotherm models
Thiourea modified • Pt(IV) 0.7 M • 43.34 mg⋅g− 1 [84]
Fe3O4 • Au(III) thiourea + 2% • 118.46 mg⋅g− 1 including Langmuir, Freundlich, Temkin and Dubinin–Radushkevich
nanoparticles • Pd(II) HCl • 111.58 mg⋅g− 1 (D–R), which their equations are presented as follows [89,90]:
Tris (2-aminoethyl) • Ag(I) • 2 M HCl • >97.3 mg⋅g− 1 [85]
amine- Au(III) • 0.1 M • >167 mg⋅g− 1 qm KL Ce
• Langmuir qe = (1)
functionalized thiourea + 1 M 1 + KL Ce
Fe3O4 H2SO4
nanoparticles 1

1 Freundlich qe = KF Ce nf (2)
Superparamagnetic Ag+ – 61.5 mg⋅g− [86]
magnetite carbon
materials Temkin qe = B ln AT Ce (3)
1
Fe3O4 modified with • Ag+ 1 M HNO3 • 90.3 mg⋅g− [87]
( )
ethylenediamine • Zn2+ • 80.8 mg⋅g− 1
D–R qe = (qS ) exp − kad ε2 (4)

In these equations, qe is the amount of adsorbed Pd2+ ions per gram

The existence of remarkable privileges such as high selectivity,
simplification of operation, high performance, and high speed, the
ability to adsorb extensive varieties of impurities/metals, the opportu­
nity for advanced automation, and their easy recovery has attracted the
attention of many researchers. Compared to different sorts of magnetic
particles, iron oxides, including magnetite (Fe3O4) and maghemite
of Ni/Al2O3-E, qm is the highest amount of adsorption capacity achieved
from the proposed isotherm, Ce is the of Pd2+ ion concentration at
equilibrium, nf is the heterogeneity factor and ε is the Polanyi potential.
Additionally, B is described as the sorption heat constant. Finally, KL, KF,
AT and kad are the constants of the Langmuir, Freundlich, Temkin and

7
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

Fig. 6. Schematic mechanism of Pd2+ ion adsorption applying simple electrolysis system (Ni/Al2O3-E) and physical mixing method (Ni/Al2O3-PM).
Printed with permission from [88].

Table 2 Table 3
Important isotherm parameters for Pd2+ ions adsorption in Ni/Al2O3-E system Common employed cationic, anionic, and neutral (non-ionic) polymeric floc­
[88,90,91]. culants for PM recovery in water/wastewater treatment industry [99–102].
Adsorption isotherm Parameters Unit Value Cationic polymeric Anionic polymeric Neutral (non-ionic)
flocculants flocculants polymeric flocculants
Langmuir qm mg g− 1 40.3
KL L mg− 1 0.0139 • Solphonium polymers • Carboxylic acid • Polyvinyl alcohol
RL – 0.418 • Natural cationic polymers • Polyacrylamides
Freundlich KF – 1.43 biopolymers (i.e., chitosan) • Phosphonic acid • Cellulose derivatives
nf – 1.63 • Poly(styrene) derivatives polymers
Temkin KT g− 1 0.173 • Dimethylamine polymers • Sulphonic acid
1
B kJ mol− 7.91 • Cationic polyacrylamides polymers
D–R qm – 7.51 • Ploy(alkylamines) • Modified lignin
Kad – 0.0121 sulphonates
1
E kJ mol− 6.43 • Cationic
polyacrylamides
• Sulfated
D–R models, respectively. polysaccharides
Among the abovementioned evaluated isotherms, it was demon­
strated that the adsorption of Pd2+ ions onto Ni/Al2O3-E system has been
technique. However, considerable operational costs because of high
described by Langmuir and Freundlich isotherm models better than
chemical consumption and the need for manufactured sludge treatment
other isotherm models [91]. Temkin adsorption model has been of great
to recover PMs are the main drawbacks of this procedure [94–96].
interest to explain adsorption heat and indirect adsorbent–adsorbate
Table 3 presents the comprehensive data about prevalent employed
interactions on heterogeneous surfaces in adsorption systems. Neglect­
cationic, anionic, and neutral (non-ionic) polymeric flocculants for PM
ing the variations in concentration, Temkin adsorption isotherm as­
recovery in industrial wastewater treatment. For example, Kawakita
sumes that the adsorption heat of all molecules declines in the linear
et al. [97] studied the selective precipitation of Au(III) using the mixture
situation when the layer is covered. The positive amount of parameter B
of polyphenol and persimmon extract as the coagulant. When hydro­
demonstrates the endothermic inherence of the adsorption process.
chloric was used in the range of ≤0.5 mol⋅dm− 3, Au(III) was recovered
Additionally, D–R adsorption isotherm considers the porous structure of
quantitatively. The authors concluded that the high value for selectivity
the adsorbent. Table 2 presents important isotherm parameters for Pd2+
of persimmon extract could be explained by reducing Au(III) to
ion adsorption onto Ni/Al2O3-E system.
elemental form. Same as other PMs, it is necessary to remove Ag from
the discharged wastewater in different industries due to its toxicity for
3.1.2. Coagulation and flocculation
humans and animals. Thus, Folens et al. [98] studied the coagulation-
Coagulation is defined as an essential process with great potential for
flocculation technique for Ag removal from industrial wastewater. The
application in various industrial-based activities such as water and
authors discussed that this technique could favorably be used for
wastewater treatment, food and beverage production, PM recovery, and
removing PMs from industrial effluent owing to the limited required
petroleum refining. In rural and third-world countries, coagulant-
investment and its robustness. In their research, the Central Composite
flocculent systems are of great interest as an efficacious point-of-use
Design technique was used for optimizing the Ag separation from the
(POU) treatment process to increase the water quality for human and
wastewater sample and lowering the operation cost. During the exper­
animal consumption. Despite the general application of coagulant/
iments, PAC (poly‑aluminum chloride) and an anionic polyelectrolyte
flocculent agents, it seems vital a better perception of their action mode
were used as the coagulation and flocculation agents. The obtained re­
to address water quality and wastewater treatment concerns and in­
sults revealed that the concentration of Ag considerably reduced from
crease the performance of the treatment and recovery processes. Co­
2.50 mg⋅l− 1 to 0.027 mg⋅l− 1. The authors also tried another coagulant (i.
agulants and flocculants are considered chemical substances with
e., sodium poly-acrylated aluminum chloride) which was more effective
excellent capability to improve aggregation and sedimentation of sus­
by reducing the Ag concentration up to 0.004 mg⋅l− 1. It was discussed
pended particles in solution [90,92,93]. The selection of appropriate
that the achieved reduction in the Ag concentration could meet the
coagulant-flocculent facilitates the destabilization of a colloidal system
required standard in Belgium, which is ≤0.08 mg⋅l− 1. The authors
and allows the formation of a floc network to remove PMs and heavy
concluded that a high amount of trapped Ag in the formed sludge, which
metals by physical techniques.
was ~42 m% rich in Ag, can be remarkably beneficial for the recovery of
Flocculation is interpreted as an operation that flocculent polymers
Ag from industrial wastewater.
construct bridges and interconnect the unstable particles to form larger
Coagulation–flocculation is identified as a prevalent procedure
particles [94]. The requirement of lower time for suspended solid pre­
method for the treatment of heavy metals and recovery of various PMs
cipitation, sludge stability, and ability of bacterial inactivation can be
from wastewater sources. In this method, cationic inorganic metal salts
mentioned as the most essential privileges of coagulation-flocculation
(CIMS) are often applied as coagulants and neutral (non-ionic) or

8
A. Taghvaie Nakhjiri et al.
Fig. 7. Overview of the sequential recovery for Au and Cu (Step 1 is for Au recovery at natural pH (7.5 ± 0.2) using Amberjet™ 4200, and step 2 is for Cu recovery at
pH ~5 using Amberlite IRC-86), and the influence of pH on adsorption capacity for Au and Cu (by using Amberjet™ 4200 (a) and Amberlite IRC-86 (b) resins) [114].
anionic polymers are often used as flocculants [103]. On the other hand,
by the addition of inorganic coagulant, the hydrolysis process of metal
salts will be accelerated in wastewater to form cationic species that are
adsorbed via negatively charged colloidal particles. This process even­
tuates in the occurrence of simultaneous surface charge reduction and
microflocs formation [104]. Coagulation process is not always ideal in
saturation because it may result in the formation of small flocs at low
temperatures or create fragile flocs when exposed to extreme physical
forces. To overcome this challenge, non-ionic polymeric flocculants are
widely used for the accumulation of microfloc ages with slow deposition
[105]. Generally, the recovery of PMs using cationic, non-ionic and
anionic polymers in coagulation–flocculation includes the following
steps [92,103]:
(1) Flocculant dispersion through the solution
(2) Flocculant diffusion across the solid-liquid interface
(3) Adsorption of the flocculant on the particles surface
(4) Collision of those particles that carry an adsorbed flocculant with
other particles
(5) Adsorption of the flocculant on other particles to generate
microflocs
(6) Growth of the microflocs to bigger flocs by consecutive collision
and adsorption
9
Desalination 527 (2022) 115510
3.2. Chemical techniques
3.2.1. Ion-exchange
The ion exchange (IE) technique is considered as a robust alternative
and one of the most investigated methods for the recovery of PMs. The
first tries in this regard date back to the early 1990 [106]. IE process
includes a reversible ionic exchange that occurs between liquid and solid
phases of ionic exchangers during two steps, including (1) adsorption/
metal loading and (2) elution. In the first step, targeted ions are
exchanged with movable ions. During the second step, the loaded tar­
geted ions are released back to the liquids and therefore facilitate the
recovery of the ion exchangers [107,108]. Ionic exchangers are usually
divided into the following classes [109]:
(1) Inorganic ionic exchangers such as aluminosilicate minerals and
zeolites
(2) Synthetic organic-based materials such as resins, membranes, etc.
IERs have recently received greater attention due to their irrefutable
futures, such as excellent loading capacity, easy operational control,
acceptable mechanical stability, and appropriate exchange rate
[107,109]. IERs are capable of separating PGMs from low-leach solu­
tions due to their excellent capability to bind metal ions even from a
complex solution with low-targeted concentration [110]. Nikoloski and
Ang [109] comprehensively reviewed the application of different IERs
for the recovery of PMs from HCl solutions. This review gave some
A. Taghvaie Nakhjiri et al.
Fig. 8. Schematic of the novel technique for recovery of PMs in the work by Dong et al. [115]: (a) the 1st step for the Na-ion intercalation in the NTP electrode, with
the NaCl solution or CH3COONa solution as the electrolyte, the chloride evolution or oxygen evolution reaction occurs on the counter electrode, (b) the 2nd second
step for the metal removal/recovery, Na-ion released from the NTP electrode owing to the potential differences, and metal ions are reduced to metallic nanoparticles.
guidelines to recover the value-added PMs from the solution environ­
ment using ion exchange and resins.
To reduce the overall operation cost, Gomes et al. [111] studied the
application of spent resins from an industrial demineralizing plant for
the recovery of Au. According to the experimental results, which were
based on recovery performance and the ease of regeneration, Purolite A-
100 resin - a weak base anion exchanger (stable until 60 ◦ C) - was used
for the experiments. The authors claimed that a 25-fold Au concentra­
tion was achieved during the saturation/elution process. Furthermore,
the utilized anionic resin showed proper performance for the recovery of
silver. However, the Ag recovery was less than that of Au.
Applying the ion exchange technique, Alguacil et al. [112] studied
Au(III) recovery from Au(III)-HCl solutions by the anionic ion exchange
Lewatit MP-64 resin. The authors investigated the effect of several
operating parameters, including T (temperature), CHCl and CAu(III)
(concentration of acid and gold, respectively), and the amount of used
resin. The authors used the obtained results from batch experiments to
run a continuous vertical column. According to the discussion in this
research, recovery of fine gold particles was accomplished when sodium
borohydride was used to process Au(III) incorporated solutions. Kono­
nova et al. [9] investigated the recovery of platinum group metals, i.e.,
Pt(II, IV), from chloride solutions. The authors discussed that the uti­
lized resins were chosen according to their properties and sorption ca­
pacity for other PMs, such as silver, gold, and palladium. Several
experiments under various conditions (CPt: 0.25–1.0 mmol/L, CHCl:
0.01–4 mol/L) were carried out. The obtained results revealed that the
utilized anion exchangers possess high Pt removal performance. How­
ever, more discussion on the obtained results was expected in this
research. In another research, Yahorava et al. evaluated the recovery of
PGMs and Au from different wastewater streams generated in one of the
PM refineries in South Africa. The results demonstrated that the ion
exchange technique is significantly efficient for the recovery of PMs, and
the concentration of PGMs could decrease to lower than 1 mg⋅L− 1 [113].
Kononova et al. investigated the recovery of Pt (II, IV) applying chloride
solutions. They concluded that the powerful basic anion exchangers (i.
e., Lewatit MP 600 WS) had the highest selectivity in the Pt sorption
process applying fresh chloride solutions. In contrast, weak basic vinyl
pyridine anion exchangers, such as AN-251, demonstrated the greatest
affinity towards Pt sorption from remained solutions [9].
Recently, the recovery of PMs from bioleaching wastewater was
investigated by Choi et al. [114]. The authors claimed that the novelty of
their work was focused on finding a promising solution for this bottle­
neck, i.e., separation and recovery of Au from the wastewater generated
in the bioleaching process using IERs. The obtained results revealed that
10
Desalination 527 (2022) 115510
Amberjet™ 4200 resin showed a great affinity towards Au with a
remarkable adsorption capacity of >98% over a wide range of pH (pH
value range: 2–10). On the other hand, the Amberlite IRC-86 resin could
highly recover Cu at a pH of 5. The authors suggested a two-step
sequential process for separating and recovery of Au and Cu from bio­
leaching wastewater. Using the newly developed technique, almost
98.7% Au and 78.9% Cu were successfully recovered (Fig. 7). In another
recent research, Dong et al. [115] worked on a new strategy for Au and
Ag recovery from wastewater. The proposed strategy was based on using
a reductive ion exchange (RIE) to use NaTi2(PO4)3 (NTP), which is a
faradaic electrode material (Fig. 8). The authors concluded by using the
newly developed process, the concentration of reducible metals signif­
icantly dropped at both the ppm and ppb levels by two orders of
magnitude (Fig. 9). As a result, the separated and recycled PMs can be
investigated as recovered sources towards environmental sustainability
rather than metal pollutants.
3.2.2. Photocatalysis
Since the conventional techniques of PMs dissolution and recovery
suffer from noteworthy drawbacks such as severe environmental
contamination and significant energy consumption, finding a better
method to overcome the disadvantages above, seems to be vital [10].
The photocatalysis process has been known as a promising technique for
recovering PMs from various waste and wastewater streams. It has been
demonstrated by several investigators that the photocatalysis process
has an excellent capability to produce reactive free radicals in a reaction
system with mild conditions. For example, Chen et al. [116] studied
photocatalytic reduction of several metals, including Ag(I) and Cu(II),
using a suspension of TiO2 assisted with Degussa P25. The obtained
results revealed a remarkable removal for Ag(I). Herrmann et al. [117]
investigated the reduction of Ag(I) to metallic Ag on TiO2 powder via the
photo-assisted process. The authors explored the effect of temperature
and initial concentration of Ag(I) on the photocatalytic reduction pro­
cess. According to the obtained results, the authors concluded that this
technique could be promising for recovering Ag from dilute wastewater
streams. Park et al. [118] explored the possibility of Au recovery from
wastewater using the ZnO nanopowder. The nanocatalyst (ZnO) was
synthesized using the solution-combustion method. The obtained results
revealed that the efficiency of Au recovery was ~6 fold higher in com­
parison with the commercial TiO2 nanocatalyst. Using the new nano­
catalyst for the photocatalytic process could lead to 99.6% Au recovery
from real plating wastewater. Yin et al. [119] introduced a new mag­
netic, thiol-functionalized composite for photocatalytic and selective
recovery of Ag+ from real wastewater. The new catalyst,
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

Fig. 9. (a) The setup of the metal removal/recovery experiment. From left to right: a volumetric flask with metal-bearing water, a peristaltic pump, and a glass tube
with a roll of NTP film inside; (b) scheme showing the mechanism of the metal removal using NTP films; Comparison of the metal concentration before and after the
treatment using AgNO3, Cu(NO3)2, Pb(NO3)2, and KAuCl4 as the metal precursors: (c) with an initial concentration of 100 ppm, (d) with initial concentration of
100 ppb. The scale bars were obtained by averaging three measurements, (e) Concentration-volume relation with each point represents the metal concentration of
500 mL metal-bearing water (100 ppm initially) after treatment. The images show the recovered Ag particle on the filtration membrane, which can be pressed into a
silver coin with a purity of 98.8%. A typical coin (1 yuan, RMB) is used for comparison [115].

Fe3O4@SiO2@TiO2-IIP, showed a high capacity for Ag adsorption of
35.475 mg⋅g− 1 under the optimum conditions (i.e., process time of
80 min and pH of 6). Under the optimum conditions, the selectivity
factors for silver were 10.626, 27.829, 13.276, and 68.109 for Li+, Co2+,
Cu2+, and Ni2+, respectively. The authors discussed that Ag(I) could be
reduced to Ag(0) in the presence of methanol, as the sacrificial agent,
and TiO2. The adsorbed silver could efficiently be separated from the
imprinted composite via ultrasonification. It was concluded that the
photocatalytic recovery of Ag in this research could enjoy considerable
Ag selectivity, highly efficient photoreduction of silver, sustainable
regeneration conditions, and excellent magnetic separation ability for
Ag from real wastewater. In another work, Kim et al. [120] studied the
recovery of Au from wastewater generated in an electronic waste fac­
tory. The authors suggested a new, electron donor-free route using a
direct Z-scheme tannin–TiO2 heterostructure for sustainable and selec­
tive Au recovery under solar irradiation. The obtained results revealed
that the proposed heterostructure could provide an 11-time higher
adsorption capacity and significant selectivity for Au under the light in
comparison with the dark. Therefore, it was concluded that the photo­
catalytic process is a promising pathway for promising and sustainable
Au recovery from industrial wastewater.
Additionally, the photocatalytic method for recovery of PMs from
wastewater has numerous positive points such as ease of operation, low
energy consumption, lack of secondary contamination, and excellent
efficiency. Therefore, it has become a great option to overcome
environment-based pollution and energy crisis because of its direct use
of solar light-driven reaction and excellent catalytic stability [121,122].
The recovery process of PMs using the photocatalysis method is done
based on two following steps:
(1) Dissolution of PM0 into PMx+ from waste streams
(2) Reduction of PMx+ to PM0 from the leachate
Industrial dissolution of PM0 into PMx+ includes the application of
corrosive/poisonous aqua regia and cyanidation, which seriously en­
dangers the environment [123,124]. To overcome the toxic character­
istics of aqua regia and cyanidation, investigators have studied the non-
poisonous leaching agents (i.e., thiourea and iodine) to treat the Au
dissolution, while they do not have good efficiency for the dissolution of
PGMs [125,126]. In this case, investigation about the feasibility of

11
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

Fig. 10. Dissolution of various PMs applying photocatalysis process: (a) Dissolution rate of Ag, Au, Pd, Pt, Ru, Rh, and Ir in the acetonitrile (MeCN)/dichloromethane
(DCM) combined system. (b) The dissolution rate of Al, Fe, Cu, Ag, Au, Pd, Pt, Ru, Rh, and Ir in MeCN based on photocatalytic conditions. (c) The dissolution rate of
Au in various solutions. (d) Illustrations of selective retrieving metal from the CPU board. (f) Depiction of selective dissolution process of metals catalyst (1% Cu/
TiO2, 1% Ag/TiO2, 1% Au/TiO2, and 1% Pt/TiO2). (h) Flow-sheet of stepwise recovery of Fe, Ni, Cu, Ag, Au, and Pd from e-waste powder. The amount of metals
obtained by selective photocatalysis (e) CPU board, (g) metals catalyst, and (i) e-waste powder.
Reprinted with permission from [121].

thioacetamide application as another safe and non-poisonous leaching 3.2.3. Precipitation

agent for Au dissolution can be considered as a future trend to develop
the researches about PM recovery. However, in the current reduction
processes of PMx+ to PM0, investigators often apply materials capable of
tolerating acid to recover PM ions [127].
The fact of the matter is that the dissolution trend of PMs is more
complex compared to their reduction process because the PMs are
chemically inert that need robust oxidizing reagents. Apart from the
discussed advantages, the photocatalysis process suffers from some
other drawbacks. This method can dissolve one or two PMs, and its
associated reagent composition is complex, which is resulted in
increasing the difficulty of the operation and the cost of recovery [121].
Fig. 10 presents an illustration of the dissolution of various PMs applying
the photocatalysis process.
Precipitation is the formation of an insoluble metal from its solution
using a reactive precipitant agent such as hydroxides or sulfides [93,94].
Precipitation is one of the principal PM recovery techniques, which
often adjusts the pH value to a basic condition to decrease the solubility
of PMs/heavy metal ions’ solubility in the wastewater [128,129].
Despite the high efficiency of PM recovery by sulfide precipitation, hy­
droxide precipitation is more desirable owing to better accessibility and
affordability of the precipitant agents (lime and limestone) in different
countries [96,130]. The recovery of precipitated PMs is implemented
first by a solid separation process from the aquatic environment (i.e.,
coagulation, sedimentation, or filtration). Then, they are purified via a
chemical extraction technique [95,131]. The simplicity of operation and
low capital cost are considered as the main privileges of precipitation
technique, while the production of excessive sludge to recover metals,

12
A. Taghvaie Nakhjiri et al.
Fig. 11. (a) Illustration of the standard three-electrode setup (a working electrode (WE) consisting of the Pt nanoparticles to be recovered, a counter electrode (CE),
and a reference electrode (RE)), (b) demonstration of the particle growth during electrochemical treatment, (c) the improved setup, and (d) the process of simul­
taneous dissolution/electrodeposition of the dissolved Pt on another working electrode (WE2).
Reprinted with permission from [148].
low speed, inadequate settlement, and the aggregation of metal pre­
cipitates can be highlighted as significant drawbacks of this technique
[95,132,133]. Overall, scrap substances, including PMs with relatively
high concentrations (>1%), possess the potential of treatment by pre­
cipitation technique [11].
3.2.4. Electrochemical
Electrochemical recovery of PMs and noble metals is identified as a
treatment technique that applies an electric current to plate out the
metal ions on a cathode surface [96]. Electrodialysis, electro­
coagulation, and electrodeposition are the most prevalently employed
electrochemical-based treatment procedures to recover PMs and noble
metals from industrial saline wastewater sources [134,135] Electrodi­
alysis is a membrane-based separation technique, which applies an ion-
exchange membrane to transport salt ions from one solution to another
solution considering the effect of an electric potential difference
[93,136]. Electrodialysis may produce two solutions, including: (1) a
concentrated solution of ions and (2) a solution consisting of nearly pure
water, which can be reused, for example, in the plating process [137].
Electrocoagulation is defined as the destabilization process of suspended
or dissolved pollutants in an aqueous environment using electrical
current into the medium. In this method, the generation of coagulant
ions takes place at the surface of the anode, and the release of H2 gas
occurs from the cathode to assist the floatation process of the flocculated
particles outside the water [138–141]. Electrodeposition is another
electrochemical method that includes the reduction of cations and their
deposition at the cathode and, consequently the oxidation process of
anions at the anode [142].
Electrodeposition is an environmentally friendly technique without
permanent residues for the PMs and heavy metals’ recovery. This
method has various advantages such as appropriate process control, the
requirement of very low chemical materials, excellent selectivity, and
13
Desalination 527 (2022) 115510
the production of negligible sludge. However, some drawbacks such as
high capital and operational costs and costly electricity supplements
have limited its wide applications in PM recovery [143,144].
In an analytical study, Chen and Lim evaluated the conversion pro­
cess of soluble PMs into a solid form applying an electrochemical
deposition approach. They found that the existence of humic acid (HA)
with low concentration (<20 mg⋅L− 1) did not considerably influence the
recovery while increasing the concentration of this acid to 50 mg⋅L− 1
declined the PM recovery [145]. Barragan et al. developed an investi­
gation to evaluate the efficiency of electrochemical techniques to
recover two PMs, including Cu and antimony (Sb). They discussed that
this technique was significantly efficient and could recover 96 and 81 wt
% of Cu and Sb in the e-waste sample [146]. Shah et al. experimentally
evaluated the electrochemical recovery of Ag from an aqueous solution
including 100 mg⋅L− 1 Ag (I). They perceived the brilliant efficacy of the
electrochemical technique due to recovering about 96.5% of Ag from its
solution when stainless steel anode and aluminum cathode were applied
as a set of the electrodes [147].
Fig. 11 schematically illustrates the standard three-electrode setup (a
working electrode (WE) consisting of the Pt nanoparticles to be recov­
ered, a counter electrode (CE), and a reference electrode (RE)),
demonstration of the particle growth during electrochemical treatment,
depiction of the improved setup, and the process of simultaneous
dissolution/electrodeposition of the dissolved Pt on another working
electrode (WE2).
3.3. Biological techniques
3.3.1. Biosorption
Biosorption is a novel classification of adsorption implemented by
the application of biomaterials as biosorbent [20]. Combination of
biological procedures with various separation techniques eventuates in
A. Taghvaie Nakhjiri et al.
Fig. 12. Percentages of recent investigations on the recovery of different PMs using biosorption process.
Reprinted with permission from [20].
Fig. 13. Classification of industrial biosorbents based on their final cost. Inspired and redesigned from [20].
introducing promising and greener processes such as bio-oxidation, bio-
reduction, bio-sedimentation, and bio-coagulation, which possess the
great potential for the recovery of an extensive range of metals, partic­
ularly the PMs [149]. Currently, biosorption processes are known to be
effective in the removal of trace concentrations of toxic and radioactive
components (i.e., cadmium, nickel, and uranium) from contaminated
water and PM recovery even in very low concentrations (ppb)
[150–152]. In biosorption processes, the separation of ions/molecules is
carried out using biological materials such as microorganisms and bio­
masses [153]. Fig. 12 gives information about the percentage of recent
investigations on the recovery of different PMs (i.e., Au, Ag, and plat­
inum group metals (PGMs)) using the biosorption process.
Recently, the industrial-based application of biosorbents to recover
PMs and toxic/radioactive materials has significantly increased due to
their special privileges such as cost-effectiveness, operational compati­
bility, and comparable sorption capacity compared to conventional
commercialized adsorbents [154,155].
There are various approaches for the classification of biosorbents due
to the ability of each dead or alive cell for utilizing in the biosorption
14
Desalination 527 (2022) 115510
process. Overall, biomasses are categorized into dead and alive groups.
Most dead biomass has some brilliant characteristics, such as little me­
chanical strength and powder form, which have made them appropriate
for long-term biosorption/desorption cycles. The features mentioned
above, result in declining the loss during the recovery/separation pro­
cess of spent biosorbent [156,157]. Some published researches have
reported that despite the existence of some functional/operational re­
strictions, the use of dead biomasses in PM recovery is more efficient
compared to alive biomasses [158,159]. Critical parameters such as
availability and cost may significantly influence the suitability of bio­
sorption in industrial applications of biosorbents. Even though most
biosorbents are known as inexpensive sorbents, their preparation/pre­
treatment costs cannot be ignored [160,161]. For this reason, all bio­
sorbents must be fundamentally classified into two groups, including
cheap and expensive biosorbents. Fig. 13 schematically classifies the
biosorbents according to their final cost.
Reviewing the recent investigations proves that bacteria, algae, and
fungi are the most important microorganisms which have been exten­
sively applied for the recovery of various PMs [153,162,163]. Table 4
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

Table 4
Presentation of comprehensive information about different bacteria, algae, and fungi for the recovery of PMs and their associated removal percentage.
PMs Microorganism Biosorbent type PM removal/recovery percentage/biosorption capacity Ref.

Au (III) Bacteria Shewanella haliotis 99% [164]

Shewanella putrefaciens CN32 57% [165]
Shewanella oneidensis MR-1 95.1% [166]
Fungi Baker’s yeast Saccharomyces cerevisiae 98% [167]
Aspergillus terreus SRD49 Biosorption capacity = 0.755 mmol/g [168]
Algae Sargassum muticum 100% [169]
Galdieria sulphuraria 90% [170]
Ag(I) Bacteria Bacillus licheniformis R08 73.6% [171]
Magnetospirillum gryphiswaldense MSR-1 91.26% [172]
Fungi Cochliobolus lunatus 87.44% [173]
Trichoderma harzianum 46.364% [174]
Algae Arthrospira (Spirulina) platensis Biosorption capacity = 0.293 mmol/g [175]
Pt (IV) Bacteria Shewanella putrefaciens 100% [176]
Providencia vermicola Biosorption capacity = 0.154 mmol/g [177]
Fungi Aspergillus sp. Biosorption capacity = 0.0281 mmol/g [178]
Algae Algal biomass beads (GLA-PEI) Biosorption capacity = 0.59 mmol/g [179]
Pd(II) Bacteria Escherichia coli Biosorption capacity = 0.199 mmol/g [176]
Enterococcus faecalis Biosorption capacity = 1.776 mmol/g [180]
Fungi Aspergillus sp. Biosorption capacity = 0.0402 mmol/g [178]
Algae Galdieria sulphuraria 95% [170]

important parameters to guarantee the techno-economic efficiency of

Table 5
biosorbents to recover PMs compared to other techniques [184].
Prominent mechanisms for biosorption of PMs, following with important func­
Sustainable supplement of PMs is known as a great necessity in
tional groups.
nowadays world. Therefore, study about the techno-economic feasibility
Biosorbent PM Prominent Functional group Ref. of biosorption approaches for manufacturing salable PMs from various
type mechanism
wastewater sources is of great importance [185]. Recent market en­
Freshwater green Ag Living cells: Hydroxyl groups [188] counters with an enhanced manufacturing cost due to increasing labor
alga reduction (Ag (I) to
and environmental regulations. The ability of biosorption techniques to
(Parachlorella Ag0 NPs)
kessleri) recover high-value PMs from different wastewater sources can have an
Modified bagasse Au Oxidation- Hydroxyl groups [189] undeniable impact on future PM supplements. Apart from noteworthy
reduction (redox) economic potential, biosorption approaches possess numerous envi­
Modified Au, Ion exchange, Thiocarbonyl [190] ronmental advantages as follows [186,187]:
persimmon tannin Pd electrostatic groups
gel interaction, and
chelation (1) Compared to other techniques, biosorption includes no solvents
Malt sprouts Pt Chelation Amine group [191] or detrimental chemical materials like strong acid or base
Magnetospirillum Ag Chemisorption and – [172] (2) Recycling and reusing of biomass in biosorption process signifi­
gryphiswaldense ion-exchange
cantly decreases the carbon footprint
Saccharomyces Ag Micro-precipitation, O− , P− or S− [192]
cerevisiae ion-exchange containing (3) Biosorption is considered as a passive approach with little energy
functional groups input
Modified rice straw Pd, Ion-exchange Amino groups [193]
Pt These positive points guarantee the environmental sustainability of
Raw date pits Au Reduction Alcoholic and [194]
phenolic
the biosorption technique. Generally, high-value recovery of PMs from
hydroxyl groups wastewater sources increases the economic/environmental sustainabil­
Aspergillus terreus Au Ion-exchange Hydroxyl and [168] ity by mitigating the risk of PM supplements.
SRD49 amine groups Table 5 aims to comprehensively compare the important mecha­
Modified microalgal Pd, Electrostatic Amino groups [195]
nisms for biosorption of PMs in recent years. Moreover, this table ren­
residue Pt interaction
Wine industry Ag Electrostatic Carboxylic, [196] ders the prominent functional groups responsible for the recovery of
wastes interaction lactonic, and PMs using different biosorbents.
phenolic groups Metal ions have two prominent entrance ways into the cell, the direct
Mercerized coconut Ag Ion-exchange Carboxylic [197] transport (energy-dependent) and indirect transport (by ligands) [198].
groups
It is believed that the transport process of PM across cell membrane is
similar to transportation of important cellular metabolic ions (i.e., so­
presents detailed information about different employed bacteria, algae, dium and potassium). Metabolic ion transport is done using some so­
and fungi to recover PMs and their associated removal percentage. dium/potassium pumps existed in the cell membrane, which supply the
Stringent environmental legislations accompanying with the techno- required energy for transportation [199,200]. The mechanism of direct
economical insufficiency of the traditional approaches have motivated transport is not completely discovered due to lack of enough informa­
the scientists around the world to make better efforts on exploring more tion, but it is known that proteins possess indisputable role in this
efficient/economical biosorbent for PM recovery from various types of transport mechanism. Inversely, for indirect transport mechanism, li­
waste streams [181–183]. Selection of an efficient biosorbent, which is gands (i.e., phosphate, peptides and amino acids) are the main reason
recover an extensive range of PMs in single and the multi-component for transfer of the metallic ions through the cell [38]. Fig. 14 schemat­
systems. The selection of efficient biosorbents may eventuate in a syn­ ically illustrates all involved mechanisms in the biosorption process of
ergistic or antagonistic influence on the recovery of PMs relying on PM PM ions. These mechanisms can be carried out in three steps as follows:
interactions with the biosorbent. Thus, evaluation of PMs-biosorbent
interactions and the performance of PM recovery are identified as two

15
A. Taghvaie Nakhjiri et al.
Fig. 14. Involved mechanisms in the biosorption process of PM ions. (a) Contact of existed metal ions in the solution with dead/alive biosorbents, and (b) diffusion of
metal ions into the liquid film and their adsorption on the surface of sorbent.
Reprinted with permission from [20].
(1) The existed metal ions in the solution are contacted with the
dead/alive biosorbents. Based on the system, biosorption process
can happen by precipitation outside the cell.
(2) Diffusion of metal ions into the liquid film and their adsorption on
the surface of sorbent considering one of the biosorption mech­
anisms such as precipitation, physisorption, ion exchange, etc.
(3) For living cells, the uptake process can be accompanied with
bioaccumulation and transport across the cell membrane. Albeit,
coincidence of these phenomena depends on some parameters
such as temperature, pressure and metabolic inhibitors.
3.3.2. Bioleaching
Bioleaching is identified as a promising bio-hydrometallurgical
technique to recover various types of PMs. The existence of note­
worthy positive points such as acceptable performance, high level of
safety, low operating cost, reasonable energy consumption, simplicity of
process control, and environmentally friendly characteristics have
motivated many researchers worldwide to utilize this approach pro­
gressively [201]. From an economic point of view, traditional proced­
ures need more significant capital investments than the bioleaching
process [202]. Bioleaching process can be carried out using various
types of microorganisms such as fungi and bacteria. These microor­
ganisms may be classified into three main groups as follows [203,204]:
(1) Chemolithoautotrophic bacteria
(2) Organic acid-producing fungi
(3) Cyanogenic bacteria
Acidithiobacillus ferrooxidans can be regarded as the most famous
chemolithoautotrophic bacteria, which plays the role of a catalyzer in
the oxidation reaction of ferrous to ferric iron ions [205]. Bacillus spe­
cies are the most efficient bacteria, and Aspergillus niger and
16
Desalination 527 (2022) 115510
Penicillium simplicissimum genera are the most effective fungi for in­
dustrial applications in bioleaching processes. Moreover, it is worth
noting that Chromobacterium violaceum and Bacillus megaterium are the
best cyanogenic bacteria for bioleaching processes [201,206].
Acidolysis, redoxolysis, and complexolysis are three prevalent
mechanisms to recover PMs and heavy metals by the bioleaching pro­
cess. Acidolysis is defined as the protonation process of oxygen atoms
that covers the metallic component surface. Redoxolysis is the second
major mechanism of the bioleaching process, which is interpreted as the
solubilization mechanism of PMs and heavy metals during redox
(oxidation-reduction) reactions.
Complexolysis is the third active mechanism in the bioleaching
process which is identified as a principal mechanism for PM recovery by
cyanogenic bacteria. In the final phase of microorganism growth, cya­
nide (CN) is generated by glycine decarboxylation [207]. Numerous
sorts of CN-producing bacteria are capable of detoxifying the CN to
β-cyanoalanine by β-cyanoalanine synthase. This positive point has
made the bio-cyanidation process promising in terms of accessibility of
lower detrimental CN in wastewater [204,208,209].
Cyanide leaching is another promising procedure to recover PMs (i.
e., Au and Ag) from ores. In this technique, ores containing Au particles
are dissolved in CN solution, and then Au is separated from the Au-
loaded solution [210]. CN and oxygen concentrations, temperature,
pH value of the solution, and leaching time are main parameters influ­
encing the dissolution of PMs by CN solutions. PM recovery through CN
leaching has numerous privileges such as prevalent application in in­
dustrial processes, excellent dissolution efficiency, and well-known
chemical mechanism. Even though CN leaching is the most common
procedure for the recovery of Au and Ag, this technique suffers from
some disadvantages such as toxicity and slow melting of PMs [30].
Fig. 15 schematically demonstrates the floor-sweeping jewelry waster
(FSJW) sample, spherical metals in tailing product, and the effect of
A. Taghvaie Nakhjiri et al.
Fig. 15. Illustration of (a) FSJW sample, (b) spherical metals in tailing product, and (c) the effect of leaching time on Au/Ag dissolution efficiency.
Reprinted with permission from [30].
leaching time on Au/Ag dissolution efficiency, respectively.
Fig. 16 shows the homogenous/heterogeneous reaction pathways for
Pd leaching. As illustrated, the occurrence of heterogeneous reaction is
only on the surface of the Pd nanoclusters, which have been adsorbed on
the carbon support. Based on this reaction pathway, the surface atoms of
Pd nanoclusters take part in the oxidative addition of arylbromides (the
initial step of the Suzuki couplings). Then, Pd is converted to Pd(II) and
catalyzes the remaining steps of the cycle. According to the homogenous
reaction pathway, the leaching process of Pd takes place from the sup­
port to the solution after becoming a soluble Pd(II) species. After that, it
catalyzes the rest of the reaction [211,212]. Although poly(vinyl­
pyridine) (PVPy) is an important factor for deactivating homogeneous
Pd, the potential of PVPy to deactivate heterogeneous Pd must not be
ignored. It is worth pointing out that PVPy is often in the form of large
insoluble polymer particles and its interaction with the nanoclusters on
the carbon support may hardly take place. Moreover, the reaction of
light soluble reactants is faster than the PVPy. Therefore, it is perceived
that the feasibility of PVPy interaction with heterogeneous Pd is very
low [212].
17
Desalination 527 (2022) 115510
3.4. Membrane technology
In recent decades, membrane-based separation techniques have been
extensively applied in different industries such as water and wastewater
treatment, the energy sector, food and juice processing, and biotech­
nology. The existence of significant advantages such as the absence of
phase change, enhanced product quality, mild thermal treatment, and
simplicity of control as well as chemical-free approaches have made the
membrane-based processes more attractive compared to other conven­
tional technologies (i.e., precipitation, extraction, evaporation, centri­
fugation, absorption, and cryogenic distillation) [38,213–219]. The
recovery of PMs from wastewater and aquatic environment using
membrane-based technologies is a novel approach to increase efficiency.
3.4.1. Emulsion, supported, and bulk liquid membranes (LMs)
The liquid membrane process (LMP) has been of great attraction to
overcome the operational challenges of the abovementioned conven­
tional technologies. This technique has opened new horizons in the field
of PMs and heavy metals recovery [220]. Comparison with traditional
membrane-based technologies, LMPs have some important advantages
such as easy and continuous operation, high recovery performance,
A. Taghvaie Nakhjiri et al.
Fig. 16. Schematic representation of the homogenous and heterogeneous mechanisms of Pd leaching.
Reprinted with permission from [212].
extraction and stripping in one stage, and large interfacial area. Owing
to the existed justifications, the recovery of PMs applying LMP has been
subjected to a broad investigation by numerous researchers all over the
world [221–224].
The fundamental principle of the LMP is based on the partitioning of
solute between feed, membrane, and receiving phases that may be
carried out by either supported liquid membrane (SLM) or emulsion
liquid membrane (ELM). In the SLM, a liquid is immobilized inside the
membrane’s micropores. The responsibility of porous membrane is to be
as a support for the liquid film. Despite SLM, the ELM process includes a
three-phase dispersion system (also identified as a double emulsion
system). The ELM system is an emulsion with three compartments,
including internal, liquid membrane, and external phases. In this pro­
cess, applying external forces, such as centrifugation or electric field,
results in the demulsification of the emulsion into two immiscible pha­
ses. The liquid membrane phase, which consists of the surfactant and
extractant, may be well recycled to the emulsion production step.
Additionally, the emulsion’s internal phase, including the concentrated
solute, may be exposed to more purification in the PM recovery process
[221,225-229]. Fig. 17 schematically compares the configurations of the
conventional membrane process with LMP in the field of PM recovery.
Recovery of PMs using liquid membranes dates back to the 1990s
[231]. Weerawat et al. [232] studied the recovery of Pd from the aquatic
environment using an SLM system. Two extracting reagents, including
thioridazine HCl and oleic acid-solubilized in chloroform, were used to
coat the hollow fiber supportive membrane in this research. The strip­
ping agent, i.e., sodium nitrite, was fed through the shell side of the
module with the counter-current flow arrangement with the feed. The
obtained results showed that after 30 min operation, ~29% of Pd ions
could be recovered (by use of 0.0005-M thioridazine and 0.05-M oleic
acid). The authors examined the system for other PMs, and result
revealed the order in recovery efficiency of Pd(II) > Pt(IV) > Cu(II) > Au
(III). It was concluded that the proposed SLM showed remarkable long-
term stability and could recover Pd up to 65%.
Gold separation from the aquatic environment was investigated by
Kargari et al. [233]. The authors utilized the ELM for Au(III) recovery
via a batch process. This work enjoyed using a biodegradable emulsifier,
i.e., LK-80 (HLB value: 4.5), which makes favorable towards
18
Desalination 527 (2022) 115510
environmental sustainability. The LK-80 emulsifier is natural and its
composition consists of a complex mixture (including fatty alcohols,
acids, and esters in the range of C7 to C41). All experiments carried out
under constant temperature of 25 ◦ C. The gold-contain solution was
prepared by dissolving metallic gold with 99% purity in mixture of
HNO3 and HCl. Studying various operating conditions, the authors dis­
cussed that under optimum operation, almost all Au(III) ions could be
recovered. Taguchi method was then used for studying the interactions
among the operating parameters and optimizing the experimental re­
sults. The authors concluded that a good agreement was observed be­
tween the experimental results and the Taguchi model. The same team
continued the research on the recovery of PMs from water/wastewater
streams using different LM systems. It investigated other subjects,
including the effect of mass transfer, type of surfactant, mathematical
modeling, etc. The obtained results for all conducted experiments
revealed the promising application of LMs for PM recovery from water
and wastewater [234–238].
Reverse mixed micelles were investigated as a carrier to facilitate the
uphill transport of Pt and Pd via BLM system. The authors used spent
catalyst for the feed sample. The reverse micelles were prepared using
cationic hydrophobic and nonionic surfactants at ambient temperature.
This could make the proposed process an energy efficient alternative for
recovery of PMs. This reverse micelle was then used as a carrier to
facilitate the PM extraction into BLM. Results revealed that the pre-
concentration factor for Pt and Pd was found to be 10. The authors
concluded that the obtained results revealed an environmentally
friendly approach for PMs recovery from spent catalysts [239]. Noah
et al. [240] explored a new, highly selective ELM for Pd recovery from
electroplating wastewater. In this research, the authors used Cyanex 302
for recovery of Pd and Cr. The essential operating parameters, such as
concentration of carrier, the concentration of stripper, extraction time,
and pH, were investigated. The obtained results revealed that under the
optimum conditions (5 min of extraction time, 0.2 M of Cyanex 302, 1:3
treat ratio, pH 3 of the feed stream, and 1.0 M thiourea in 1.0 M H2SO4 of
stripping agent), the percentage of the PM recovery was ~97% with
almost 100% selectivity over Cr one.
In another research, Laki and Kargari [241] comprehensively studied
the application of the ELM process for recovery of Ag from dilute
A. Taghvaie Nakhjiri et al.
Fig. 17. Schematic comparison of conventional membrane process with LMP.
Reprinted with permission from [230].
aqueous solution. The obtained results highlighted the importance of
membrane composition (extracting agent: Cyanex-302, diluting agents:
paraffinic and naphthenic hydrocarbons (C10-C14), surfactant:
Montane®-80 (sorbitan monooleate), and stripping agent: nitric acid)
and the emulsion pH for efficient and maximum recovery of Ag.
Extraction of Ag+ increased with an increase in strip phase and carrier
concentration. It was concluded that the maximum Ag recovery (~99%)
was achieved when 5% (v/v) was used for the concentration of
Montane®-80, the strip phase concentration was 0.4 M nitric acid, and
the phase ratio was set at 1:1.
Recently, researches have been focused on innovative ELMs for the
recovery of PMs from wastewater streams. For example, Masry et al.
[242] studied fabrication of a nano-ELM for the recovery of Ag(I) from
wastewater. The authors utilized CYANEX 925 in kerosene in the carrier
and KSCN (potassium thiocyanate) for the stripping phase. The span 80
was used as the surfactant. The obtained results showed that the Ag
recovery could reach the value of 9.27 × 10− 4 M Ag+ from the Na2S2O
solution. Moreover, adding the complexing agent (ammonium hydrox­
ide) to the system could enhance the Ag recovery. The authors
concluded that the proposed nano-ELM system was much more efficient
than conventional ELM systems (Fig. 18). Furthermore, recent trends in
ELMs for the recovery of PMs have been focused on greener systems
towards environmental sustainability. Kumar et al. [243] reviewed the
19
Desalination 527 (2022) 115510
recent achievements in using greener solvents for ELM systems in
recovering the PMs. The green ELM processes are some advantages such
as environmentally benignant, resource efficiency, economic in nature,
no toxicity to human health, minimizing of waste generation, easily
available of raw materials, reduction in the use of toxic organic solvents,
use of renewable feedstock, and better future scope.
LMP has been identified as an emerging technique for potential use
in different situations like PM recovery, micro-contaminants removal,
and bioseparation. The challenges towards the application of LMPs are
not only restricted to the related equipment or installation. The
industrial-based application of LMs has been limited due to some func­
tional and operational bottlenecks such as emulsion stability and
membrane failure in ELMs. Therefore, recent investigations have been
conducted to decrease membrane leakage and rupture by using
bifunctional surfactants to improve elasticity. In the case of SLMs, sol­
vent/carrier loss occurs due to the dissolution and large pressure gra­
dients obligating solvent out of the pores of the porous support. Carrier
loss is occurred due to irreversible reactions or condensation of the
solvent in one of the membrane sides [244].
3.4.2. Membrane distillation (MD)
Membrane distillation (MD) is a non-isothermal membrane separa­
tion which uses a hydrophobic microporous membrane for separating
A. Taghvaie Nakhjiri et al.
Fig. 18. (a) Schematic of the nano-ELM system and the related mechanisms for
recovery of Ag from wastewater, (b) a scheme for the preparation of ELM and
the subsequent NELM process, and (c) particle size distribution of the NELM
using a dynamic light scattering (DLS) analyzer [242].
two streams, including the feed (hot) and permeate (cold) streams
[245]. This process has widely been used for desalination, water treat­
ment, biotechnology, and food processing [246–248]. Due to unique
features of this technology, such as high selectivity (~100% theoretical
solute rejection for non-volatile contaminates), less tendency to mem­
brane fouling, using low grade or renewable energy sources, etc., MD
could attract the researchers’ attention for use in wastewater treatment
Fig. 19. General scheme describing the application of MD process for water recovery from mining industry [255].
20
Desalination 527 (2022) 115510
[249]. A wide range of wastewater from different industries has been
treated using various MD processes. For example, published literature
demonstrated the promising application of MD processes for treating
high salinity wastewater, hot dyeing effluent in the textile industry,
heavy metal contaminated wastewater, etc. [250–254]. Among the
investigated wastewater sample, mining drainage and effluent have
been highlighted [255]. Fig. 19 shows the concept of MD application in
the PMs’ mining. Compared to other membrane-based approaches, such
as NF and RO, the MD process has some other considerable advantages,
including low operating pressure, high water recovery, excellent re­
covery efficiency, and smaller carbon footprint. However, the existence
of some operational and functional drawbacks, such as energy-
intensiveness, has decreased the popularity of this technique for appli­
cation in the PM recovery process [256,257].
Recently, Chen et al. [258] studied the performance of the direct
contact MD (DCMD) process, equipped with commercial PTFE mem­
brane (0.45 μm), for the treatment of PMs processing effluent, a yellow
solution (Conductivity: 199.2 mS⋅cm− 1 and initial pH: 3). The feed and
permeate temperatures were adjusted at 60 and 20 ◦ C, respectively,
while the cross flow velocity for the both sides was adjusted at
8.3 cm⋅s− 1. The authors investigated the contribution of pH of the
wastewater samples on the performance of the DCMD process. Using a
real effluent sample, the authors discussed that quality water and high
purity HCl could be reclaimed. Severe reduction in the permeate flux
was observed, which was mainly due to Cr(III) and silica scaling
(Fig. 20). However, it could be maintained by adjusting the initial pH of
the feed stream. The authors claimed that this research had opened a
new pathway for resource recovery from acidic wastewater in the PMs’
mining.
In another work, Chen et al. [259] discussed that various heavy
metals and silica could make the Ag recovery from wastewater of PM
production challenging. They used the DCMD process to study the
membrane performance for water and ion recovery from a real silver
leaching wastewater sample. The conducted experiments revealed that
the existence of Al3+ could cause higher silica scaling. Moreover, the
amount of formed Al(OH)3 was proportional to the initial pH of the feed
stream in the DCMD process. It was also effective in reducing the con­
centration of the dissolved silica. At a pH value of 11, almost 83% of the
dissolved silica could be removed. The results of this research could shed
some light on the role of silica scaling in wastewater treatment of PMs
using the DCMD process. In a very recently published work, the per­
formance of the DCMD process was studied for treating a real acidic Pt
leachate sample [260]. The fouling study revealed that the flux decline
happened as a result of deposing both silica and organic matters. It was
discussed that the mass-to-charge ratio (m/z) range change of organic
compounds could significantly affect the membrane fouling, as well. The
authors discussed that further studies are required to explore the effect
of operating parameters on the performance of the MD process for
wastewater treatment in PMs’ processing.
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

Fig. 20. Performance of the DCMD process for wastewater treatment from PM recovery: silica and chromium (III) in membrane scaling [258].

3.4.3. Forward osmosis (FO)
Forward osmosis (FO) is a membrane-based process for water and
wastewater treatment [261]. This process utilizes a semi-permeable
membrane and is driven using the natural energy of osmotic pressure.
The osmotic pressure can cause water transport through the membrane
while retaining almost all dissolved contaminants that makes it favor­
able for wastewater treatment [262]. FO can also be hybridized with
other processes, such as MD, to hybridize the overall resources recovery
process towards environmental sustainability [263].
Although the FO process has been of great interest in the removal or
recovery of different salts and heavy metals from industrial wastewater
and other sources [264], its application towards wastewater treatment
in PMs processing is relatively new. Gwak et al. [265] explored the
application of the FO-based process for recovery of Pd from PCB (printed
circuit board) wastewater. The authors discussed that one of the
novelties of this work was utilizing a dilution-needed waste solution
with high conductivity as the draw solution. As a result, the proposed FO
process did not need an external supply of draw solution. This could
remove the re-concentration step for the diluted draw solution,
enhancing the overall sustainability of the process. According to the
results of the conducted experiments, the permeate flux of
39.4 L⋅m− 2⋅h− 1 could be achieved. Moreover, the Pd fouling on the
membrane surface was not considerable. The modeling results revealed
that the Pd concentration could reach 17.2-times-high. Finally, it was
claimed that the zero cost for the supply and re-concentration of the
draw solution and the enhanced energy efficiency in recovery of PM
from wastewater stream are the most important highlights of this work.
3.4.4. Pressure-driven membrane processes
Reverse osmosis (RO) is a well-developed pressure-driven membrane

Fig. 21. Ag recovery from mining wastewaters using the hybrid cyanidation-RO/NF process [271].

21
A. Taghvaie Nakhjiri et al.
Fig. 22. The extraction mechanism of PMs applying (a) non-functionalized ILs, (b) the combination of non-functionalized IL and a chelating agent, and (c) task-
specific ionic liquids (TSILs).
Reprinted with permission from [275].
technology. In the RO process, water flows through a semi-permeable
dense membrane and goes to the permeate side, while PMs and other
heavy and noble metals can be retained in the feed side. In RO, cationic
species are separated from water by applying a higher hydrostatic
pressure than the osmotic pressure of the feed [266,267]. The need for
small space, acceptable selectivity, and high separation performance can
be determined as the advantages of the RO technique for PMs’ recovery
from wastewater. Despite the abovementioned positive points, the ex­
istence of important drawbacks such as high capital and operational
cost, fouling, and low permeate flux in terms of highly polluted waste­
water samples, as well as high operating pressure, have restricted the
broad application of RO technique for PM recovery [268–270].
Koseoglu and Kitis [271] studied the RO and NF membranes, which
were hybridized by cyanidation to recover Ag from mining wastewater
samples. In this research at the lab scale, RO and NF membranes were
utilized to concentrate and recover Ag cyanidation of silver ions and
AgCN formation. According to the obtained results, due to irreversible
sorption of Ag on the membrane surface, a large amount of Ag was
wasted when the RO membrane was used. However, the RO membrane
could provide higher Ag rejection than the NF membrane (Fig. 21).
Thus, it was concluded that the RO membrane was more efficient in the
recovery of PMs from mining wastewater. Moreover, the high-quality
permeate water can be reused in the leaching process. It makes the
hybrid process more favorable towards sustainable wastewater treat­
ment of PMs’ mining.
3.5. Ionic liquids (ILs) for PM recovery
Ionic liquids (ILs) are known as important organic solvents that can
be applied in the liquid-liquid extraction (LLE) processes to recover/
extract a wide range of PMs. PM recovery using ILs includes anionic-
cationic exchange, which profoundly depends on factors such as the
chemical structures of anionic PM complexes in aqueous solutions and
characteristics of the applied ILs [272]. Anionic exchange reaction
(AER) and ionic pairing reaction (IPR) are two prominent reactions
occurring in the recovery/extraction process of PMs using ILs. Both re­
actions may independently take place based on the following
22
Desalination 527 (2022) 115510
operational patterns [273,274]:
(1) Occurring to either one
(2) Subsequent occurrence by initiating from the AER
(3) Simultaneous occurrence
Physical, chemical, and thermodynamic parameters have been
recently acknowledged to have a direct impact on the recovery/
extraction efficiency of PMs using ILs [274]. Therefore, investigations
about these parameters would be of interest for the design and incre­
ment of recovery processes. Fig. 22 demonstrates the extraction mech­
anism of PMs applying non-functionalized ILs, the combination of non-
functionalized IL and a chelating agent, and task-specific ionic liquids
(TSILs).
3.5.1. Investigation of physical parameters
Hydrophobicity/hydrophilicity of ILs can be considered as one of the
most important physical parameters which affect their solubility and
consequently the recovery/extraction efficiency of PMs. The hydro­
phobic nature of IL anions significantly deteriorates the exchange of
anionic PM-ligand complexes [276]. To put the issue into the perspec­
tive view, IL anions with hydrophilic nature possess better interaction
with aqueous solutions and can be conveniently exchanged with anionic
PM-ligand complexes [277]. The hydrophobicity and hydrophilicity
nature of ILs can significantly affect the dissolution of PMs in the organic
phase [272]. The dissolution propensity of IL anions in water is in the
order of SO42− ˃ Cl− ˃ Br− ˃ NO3− ˃ SCN− ˃ Tf2N− [278]. Therefore, it is
corroborated that IL extractants with hydrophilic nature possess the
excellent potential to extract anionic PM-ligand complexes using the
IPR. In contrast, the recovery process of PMs by IL extractants with
hydrophobic nature is carried out by the AER [272,279].
3.5.2. Investigation of chemical parameters
3.5.2.1. Different sorts of ILs. It is acknowledged that the chemical
structure of the cation and the anion size considerably affect the
extraction/recovery process of PMs [277,280]. Organic cations (i.e.,
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

Table 6
Detailed summarization about PM extraction/recovery process by means of ILs.
Operation Aqueous solution Applied ILs (as extracting agent) Solvent Extraction/recovery Ref.
percentage (%)

LLE Chloride solution • 1-Octyl-3-methylimidazolium tetrafluoroborate ([C8mim] Not Not applicable [285]
Ag(I) and Pd(II) weight: [BF4]) applicable
50–500 mg/kg of water • 1-Octyl-3-methylpyridinium tetrafluoroborate ([3MOPYR]
[BF4])
• 1-Octyl-4-methylpyridinium tetrafluoroborate ([4MOPYR]
[BF4])
• 1-Octyl-4-methylpyridinium trifluoromethylsulfonate
([4MOPYR][TfO])
• 1-Octyl-4-methylpyridinium nonafluorobutylsulfonate
([4MOPYR][NfO])
• 1-Octyl-4-methylpyridinium bis(trifluoromethyl) sulfonyl
imide ([4MOPYR][Tf2N])
• 1-Butyronitrile-4-methylpyridinium bis(trifluoromethyl)
sulfonylimide ([4MPYRCN][Tf2N])
• 1-Butyronitrile-1-methylpiperidinium bis(trifluoromethyl)
sulfonylimide ([MPIPCN][Tf2N])
• 1-Methyl-1-[4, 5-bis (methylsulfide)] pentylpiperidinium bis
(trifluoromethyl)sulfonylimide ([4MPIPS2][Tf2N])
• 1-Methyl-1-[4, 5-bis (methylsulfide)] pentylpyrrolidinium bis
(trifluoromethyl)sulfonylimide ([4MPYRROS2][Tf2N])
LLE HCl solution Trihexyl (tetradecyl) phosphornium chloride (Cyphos®IL101) Toluene 97 [286]
Pd(ІІ) concentration: 106.4 to
851.4 ppm
Precipitation and LLE HCl solution For precipitation: Not 98 [287]
Au(III) complex • 1-Octyl-3-methylimidazolium chloride ([OMIM][Cl]) applicable
anion concentration: • 1-Octylpyridinium chloride ([OPYR][Cl])
1020.3 ppm • 1-Methyl-1-octylpyrrolidinium chloride ([MOPYRRO][Cl])
For LLE:
• 1-Octyl-3-methylimidazolium bis(trifluoromethyl)
sulfonylimide ([OMIM][Tf2N])
• 1-Octylpyridinium bis(trifluoromethyl)sulfonylimide
([OPYR][Tf2N])
• 1-Methyl-1-octylpyrrolidinium bis(trifluoromethyl)
sulfonylimide ([MOPYRRO][Tf2N])
Precipitation and LLE HCl solution • [OMIM][Tf2N] Not 91.2 [288]
Pt(IV) complex • [MOPYRRO][Tf2N] applicable
anion concentration: 41 to • 1, 2-Dimethyl-3-octylimidazolium bis(trifluoromethyl)
3360.4 ppm sulfonylimide ([OdMIM][Tf2N])
• 1, 12-Bis(3-methylimidazolium-1-yl) dodecane bis
(trifluoromethyl) sulfonylimide ([C12(MIM)2][Tf2N]2)
LLE HCl solution Hexadecylpyridiniumchloride ([HPY][Cl]) Chloroform 99 [289]
Pt(II)
concentration: 10 ppm
LLE HCl solution 1-Butyl-3-methylimidazole-2-selone (BMIMSe) [2MIM] 99.7 [290]
Pt (II) [Tf2N]
concentration: 21.3 ppm [OMIM]
[Tf2N]
LLE HCl solution Tri-n-octylmethylammonium chloride (Aliquat336) Benzene 95–99 [291]
Au(III) concentration: 182 ppm
Pd(II) concentration: 194 ppm
Pt(IV) concentration: 196 ppm
Microemulsion HCl solution Trihexyl(tetradecyl) phosphornium chloride (Cyphos®IL101) Not Au(III): 96.4 [292]
Au(III), Pd(II) and Pt(IV) applicable Pt(IV): 79.6
concentration: 100 ppm Pd(II): 63.1
Hollow fiber supported Gold refining wastewater Aliquat336 Sunflower oil 99 [293]
liquid membrane Pt(IV) concentration: 5 ppm
LLE Synthetic solution, Au(I) • 1-Butyl-3-methylimidazoliumbromide ([C4mim][Br]) Not 99.9 [282]
concentration:100 ppm • 1-Hexyl-3-methylimidazoliumbromide ([C6mim][Br]) applicable
• 1-Octyl-3-methylimidazolium bromide ([C8mim][Br])
LLE HCl solution Octyl-trimethylammonium bromide ([N8881][Br]) n-Hexanoic 95 [294]
Au (III) concentration: 39.4 to acid
275.8 ppm
LLE Synthetic water Aliquat336 Cyclohexane 99 [295]
Pd(II) concentration: 2 to 10%
(v/v)

imidazolium and pyridinium) possess excellent ionic bonding with
numerous anions [272]. Disulfide, nitrile, and ammonium functional
groups are able to have strong interaction with Ag. However, the
interaction of the alkenyl group with Ag is weak. For Pd recovery, only
disulfide and alkenyl groups illustrate excellent potential [281,282].
The ILs–Ag extraction mechanism is anionic exchange. Lee proved
that ILs consisting of disulfide/nitrile functional groups have brilliant
efficiency for Ag recovery [282]. To recover Au from waste/wastewater
stream, imidazolium and bis (trifluoromethyl) sulfonylimide can be
considered as the most prevalent cation and anion, respectively. Imi­
dazolium has the capability of combination with different kinds of an­
ions such as bromide, dodecylsulfonate, and hexafluorophosphate

23
A. Taghvaie Nakhjiri et al.
Fig. 23. Oxidation-complexation reaction mechanism for the extraction of Au from its containing particles with BmimN(CN)2 as an IL extracting agent and CHI3 as a
catalyst.
Reprinted with permission from [297].
[283]. Ammonium, phosphonium, and pyridinium are other prevalent
classifications of cations employed for Au recovery [277,284].
Numerous ILs can be operationally applied to extract/recover PMs.
Table 6 presents a comprehensive overview of published literature on
the extraction process of PMs from aqueous solutions using the ILs. As
can be demonstrated from Table 6, [C4mim][Br], [C8mim][Br] and
[C8mim][Br] are identified as promising ILs with great potential to
recover almost 99.9% of Au using LLE process. In case of Pt recovery,
BMIMSe, Aliquat336 and [HPY][Cl] have shown excellent efficacy with
the ability to recover 99.7%, 99% and 99% of Pt, respectively, if being
used in LLE process. Finally, it is shown that Cyphos®IL101 can be
considered as a promising IL that can extract/recover 99% and 63.1% of
the existed Pd from solution using LLE and microemulsion techniques,
respectively.
3.5.2.2. Investigation of ILs-PMs interaction energy. The amount of
overall energy transfer during the electrostatic force interactions,
dispersion force, and hydrogen bonding may be considered to measure
the interconnection of an IL cation with an anionic PM-ligand complex.
The energy similar to the energy mentioned above, is explained by the
released energy when two gaseous species close together to form a pair.
Furthermore, the interaction force depends on some characteristics of
both species, including charge density and size. In doing so, the greater
charge density considerably increases the strength of pairing. On the
other hand, an increment in the size of species results in a long charge
distance, which declines the interaction strength [272,296].
As an example, the oxidation-complexation reaction mechanism for
the extraction of Au, as one of the most important PMs, with an IL is
presented in Fig. 23. As could be observed, first, iodine-free radicals are
induced in the light from the CHI3 catalyst. Then, I radicals capture the
electrons on Au0 to form Au+, which in the next step combines with the
anion of IL to create a metal-ligand complex. Finally, the cation of IL
forms a stable ion pair with the product of the previous step through
different intermolecular forces like electrostatic attraction, hydrogen
bonding, and cation-π bonding. This ion pair can shed the metal from the
gold particle surface and enhances the dissolution reaction of Au+-anion
ligand in the presence of I radicals. This finally promotes the dissolution
of Au particles into the IL system. In addition, a new IL formed from the
ion exchange reaction of I with the cations of pristine IL is precipitated in
the form of crystals [297].
As can be observed in Eqs. (5) and (6) for Au recovery from the so­
lutions via a reaction with ILs, formation of ion pair takes place by two
mechanisms including ion pairing (IP) and anionic exchange (AE). These
mechanisms can be interpreted as follows [273]:
( )
Cin − Cfin
−
IP : AuX4(aq) +
+ C(aq) +
→C(IL) −
+ AuX4(IL) = 100 × (5)
← Cin
24
Desalination 527 (2022) 115510
(
Cin − Cfin
)
−
IE : AuX4(aq) + A−IL →C(IL)
+ −
+ AuX4(IL) + A−aq = 100 × (6)
← Cin
The IE/IP extraction mechanisms are a coupled process that takes
place at the same time. The interrelation of these two mechanisms is
implemented by the dissolution products of IL, which describe the
cation-anion relationship of IL in the aqueous phase [273].
Distribution coefficient (D) is calculated using Eq. (7). It has been
corroborated that tetrahalogenoaurate ions for Tf2N-based IL have lower
affinity compared to ILs created with Dca− , Br− and SCN− anions.
Evaluation of UV–vis spectrum of the [THN+][Br− ] phase after AuCl4−
extraction illustrated great similarity to that of [TON+][AuBr4− ] and
proved the existence of AuBr4 in the IL phase. Therefore, based on Eq.
(8), AuCl4− is extracted in [THN+][Br− ] as an AuBr4− complex [273].
( )
Cin − Cfin Vw
D= (7)
Cfin VIL
[ ]
4[THN(TON)+ ][Br− ](ІІ) + AuCl−4(aq) →[THN(TON)+ ] + Au − Br−4 (ІІ)
←
+ Cl−4(aq) + 3[THN(TON)+ ][Cl− ](ІІ) (8)
where Vw and VIL are the volume of water and IL phases, respectively.
Eq. (9) considers the partial substitution of Cl− by Dca− anions in IL
phase following with the release of one Dca− anion in the aqueous phase
[273]:
[ ]
[THN(TON)+ ][DCa− ](ІІ) + AuCl−4(aq) →[THN(TON)+ ] + AuClx (DCa)−4− x (ІІ)
←
+ (3 − x)[THN(TON)+ ][Cl− ](aq) + x[THN(TON)+ ][DCa− ](ІL)+ + DCa−
(9)
The extraction mechanism of tetrahalogenoaurate ion in all ILs is quasi-
similar. Hence, lower amounts of D achieved with Tf2N− based ILs in
comparison with those of achieved for Dca− and Br− based ILs. It is
conveniently described by the higher hydrophobicity of Tf2N− anion,
which results in harder IE with AuX4− [273].
3.5.3. Investigation of thermodynamic parameters
It is known that a temperature increase can significantly affect the
kinetics of complex species and IL viscosity [298,299]. In the LLE pro­
cess, high temperature decreases the amount of IL viscosity, which
consequently eventuates in improving the transfer of anionic PM-ligand
complexes in the organic phase and providing further interactions with
IL cations [300]. It is worth noting that various mechanisms of PM re­
covery from wastewater prominently rely on the relative solubility of
the components in each available phase [301]. The ILs’ hydrophobicity
may have an undeniable effect on the mass transfer of anionic PM-ligand
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

Fig. 24. Schematic demonstration of metal ion removal mechanism through EC–MF hybrid technique.
Reprinted with permission from [324].

complexes due to the following reasons [276]: 3.6.2. Electrocoagulation (EC) and microfiltration (MF)
Fouling is the most essential bottleneck of the membrane-based
(1) Restriction of the amount of water in organic phases systems applied to wastewater treatment, particularly PM recovery
(2) Restriction of the cationic exchange mechanisms from the aquatic environment [312–314]. Different investigations have
proved that the pretreatment of the inlet wastewater sources may sub­
stantially decrease the fouling challenge and consequently increase the
3.6. Hybrid technologies
separation efficiency. Various techniques such as electrocoagulation
(EC), ion exchange, and adsorption have been recently used to pretreat
Modifying conventional technologies for the recovery of PMs has
inlet wastewater sources. Appropriate application of these techniques
recently been of great interest to increase the efficiency of conventional
can decrease dissolved organic substances, improve rejection efficiency,
methods and decline their operational disadvantages [302]. In recent
and minimize membranes fouling [315–317]. EC is identified as a
years, hybrid techniques have been widely used to integrate chemical
promising technique to enhance the rejection efficiency of the mem­
(more effective) processes with biological (more eco-friendly) processes
brane by aggregating the dissolved organics. This technique has also
to take advantages of both methods. In hybrid techniques, a sequence
been of great attraction to remove a wide variety of metals and pollut­
takes place that the PM-contaminated wastewater is treated biologically,
ants from wastewater due to numerous advantages such as high effi­
accompanying by a chemical process or vice versa, which decreases the
ciency, eco-friendliness, simplicity of design, and low space requirement
consumption of chemical reagents and modifying the environmental
[318,319].
profile [203,303].
EC-MF is considered a novel hybrid system, which attracted the
attention of researchers in recent decades in the field of PM recovery.
3.6.1. Microbial fuel cell (MFC) and microbial electrolysis cell (MEC)
Scientists have concluded that the combination of EC technique with
MFC-MEC is known as a promising hybrid technique that has been
different PM recovery procedures (such as MF) can eventuate in
increased the recovery performance of PMs in recent years [304–306].
obtaining brilliant outcomes [320,321]. For instance, Mavrov et al.
MFC is defined as a process that obtained electrons during microor­
experimentally investigated the efficiency of PM and heavy metal
ganism metabolism can remove different sorts of metal ions in waste­
removal applying EC-MF hybrid technology. They observed that iron-
water and collect them on the surface of the cathode. Unlike the MFC
based EC-MF technology significantly improves the recovery efficiency
technique, which generates an electric current from the microbial
of various types of metals to >98% [322]. In another research, Chellam
decomposition of organic components, MEC is a method that needs
and Sari evaluated an aluminum-based EC-MF hybrid system to remove
external voltage to produce H2 or CH4 from organic substances and
metals/contaminants from potable water resources. They resulted that
metal removal [307–309]. The use of the MFC-MEC hybrid method for
the aluminum-based EC substantially decreases the fouling of MF by
the recovery of PMs has gained considerable development in recent
enforcing the formation of a cake consisting of particles larger than in
years. The initial concentration of metal, temperature and pH value are
the raw water [323]. Fig. 24 schematically demonstrates the metal ion
the important factors that significantly affect the metabolic mechanism
removal mechanism through EC–MF hybrid technique.
of microorganisms and hence, the performance of the MFC-MEC hybrid
method. Additionally, the voltage utilized in MEC may influence the
3.6.3. Activated carbon adsorption (ACA) and microfiltration (MF)
performance of the MFC-MEC hybrid technique in the recovery of PMs
The combination of ACA with MF is considered as another hybrid
from various aquatic/solid effluents [303,310,311].

25
A. Taghvaie Nakhjiri et al.
Fig. 25. Industrial plants of IERs and EPRP used for the recovery of PMs: (a) IERs, and (b) EPRP [331,332].
technique to enhance the recovery efficiency of PMs and also the
removal performance of different types of micropollutants from waste­
water sources. In this system, those small species on a molecular scale,
which cannot be appropriately rejected by the membrane, are appro­
priately adsorbed on the surface of activated carbon particles, and
therefore, may be separated by the MF process [325]. Powdered acti­
vated carbon (PAC) and granular activated carbon (GAC) are prevalent
adsorbents for the ACA process, which have been of paramount atten­
tion in the field of PM recovery from wastewater sources. Compared to
GAC, PAC is more desirable due to its larger surface area and affinity for
an extensive range of metals and dissolved organics. In the ACA–MF
hybrid process, continuously dosing of PAC to the membrane reactor or
at the beginning of the MF cycle is operationally feasible, which leads to
a superior efficiency compared to GAC [326].
3.7. Examples of commercial plants towards PM recovery
In recent years, various approaches recovery of PMs have been
developed from lab and pilot scales to industry. From economic point of
view, resin plants have shown a great potential of application for the
recovery of PMs in industrial scale. These plants apply high-retention-
capacity resins, which can saturate up to 60 g of PMs for each applied
IERs. After the saturation of resins with PMs during long service, oper­
ated resins are changed with new resins. In order to increase the techno-
economic aspect of these plants, the saturated resins are treated via heat
treatment and can then be re-used [327,328]. E-waste PM recovery
plant (EPRP) is designed to recover various types of PMs such as Ag, Au,
Pt, and Pd from E-wastes like CPU, RAM, and circuit boards. EPRP are
capable to recover about 99.99% of the existed PMs in the E-wastes.
Noteworthy characteristics of EPRP are as follows [329,330]:
(1) Great extraction technology
(2) Precise evaluation
(3) High safety and eco-friendliness
(4) Significant recovery of PMs (from 97 to 99.99%)
(5) Faster operation
In some circumstances, direct process for recovery of PMs from
different sorts of wastewaters is impossible. In this case, three steps must
be implemented. First of all, UV oxidation technique is applied to
convert unrecoverable ions of PMs to recoverable form. Then, the re­
covery is taken place based on two subsequent steps including electro-
26
Desalination 527 (2022) 115510
winning accompanying with IE process. By doing these steps, almost
99.9% of PMs become recoverable. Fig. 25 presents the industrial plants
of IERs and EPRP.
4. Discussion and perspectives
4.1. Comparison and feasibility of techniques
Today, much attention is paid to the recovery of PMs to preserve
natural resources and reducing waste and wastewater without high
costs. In this regard, increasing demand, reducing resources and the
global need for development have led to extensive research in the field
of optimization of recovery solutions. Since the precious metals obtained
after the recovery processes do not show any quality loss and these
methods are combined with reducing greenhouse gas emissions and
energy consumption, centralized research is necessary to develop new
technologies for the recovery of them [333]. Understanding the ad­
vantages and disadvantages of employed techniques for the recovery of
PMs from various aquatic and non-aquatic environments can be of great
interest and opens new horizons to better selecting the most promising
procedure to increase the recovery efficiency. Table 7 comprehensively
presents the advantages and disadvantages of all employed techniques
towards the recovery of PMs. Although each of the physicochemical
methods has its own advantages, they also have significant disadvan­
tages in recovering PMs from wastewater [161].
Generally, one of the most important factors to compare recovery
methods and choose the best and the most practical one is the economics
of the treatment process (cost of equipment, treatment facilities,
chemicals, filters, operation cost, expert labor, etc.). Most importantly,
the type of the selected process, local conditions, amount of treatment,
and the amount and composition of impurities strongly affect the cost of
treatment of contaminated wastewater [334–336]. Moreover, to select
the type of separation process, it is necessary to make an accurate
comparison by considering the influencing factors such as initial
precious metal concentration (mg/L), required dose (g/L), pH and metal
removal efficiency [94].
Compared to other techniques, chemical precipitation is mature and
well-developed. This process can enjoy the simplicity of operation and
low operation cost. However, using toxic and harmful chemicals as well
as generation of large amount of sludge are the major concerns. Simi­
larly, coagulation/flocculation processes are well-known in wastewater
treatment. However, they suffer from the low efficiency in removing
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

Table 7 photocatalysis process has been known as a promising technique for

Detailed information of the advantages and disadvantages of prevalent tech­ recovering PMs from various waste and wastewater streams. It has been
niques for the recovery of PMs. demonstrated by several investigators that the photocatalysis process
Method Advantages Disadvantages Ref. has an excellent capability to produce reactive free radicals in a reaction
Chemical • Simplicity of • Disposal [27,141,337–339]
system with mild conditions. The photocatalytic method for recovery of
precipitation operation problem PMs from wastewater has numerous positive points such as ease of
• Low cost • Generation of operation, low energy consumption, lack of secondary contamination,
• Able to large amounts and excellent efficiency. Therefore, it has become a great option to
remove various of sludge
overcome environment-based pollution and energy crisis because of its
metals • Toxic and
harmful direct use of solar light-driven reaction and excellent catalytic stability.
chemicals Brilliant advantages of this method can overcome the high price and
Coagulation/ • Economically • Low [94,95,340,341] motivate numerous investigators to use the method.
flocculation affordable efficiency of Adsorption process, on the other hand, is almost inexpensive and
• Sludge ion/metal
settling removal from
mature in comparison with the above-mentioned options. Carbon-based
wastewater adsorbents are widely available. This process for recovery of PMs can be
• Formation of even more environmentally friendly when the adsorbent is made of
large particles waste cellulosic materials. Moreover, adsorption is flexible method with
• Sludge
acceptable insensitivity to poisonous contaminants. This makes this
production
Electrochemical • High speed • High running [143–145,342,343] process feasible for recovery of PMs from a wide range of industrial
• Great cost wastewaters. However, the adsorbent regeneration is still a challenging
efficiency in • Formation of issue. In contrast, membrane technology, a chemical-free approach for
the recovery of large particles wastewater separation, can provide high separation efficiency with
certain metal
negligible generation of solid waste. Moreover, membranes can process
ions
• No large amount of wastewater, even with very low content of PMs at a
consumption of short operation time. However, membrane fouling which can cause a
chemicals considerable permeate flux reduction over time is a serious bottleneck.
Ion-exchange • High • High cost [106–109,113,344]
Biological processes, such as bioleaching and biosorption, are sustain­
selectivity • Not efficient
• No adsorbent for wide able and completely environmentally friendly approaches with proper
loss applications recovery efficiency. However, their operation is time consuming and
• High costly.
regeneration of Overall, according to the properties of the target wastewater stream
materials
which contains PMs, hybrid processes for an efficient and cost effective
Adsorption • Flexibility of • Adsorbents [78,345–347]
design need recovery is a better option. When large amount of diluted wastewater
• Simplicity of regeneration with low concentration of PMs should be addressed to the recovery
operation • Low target, pressure-driven membrane technologies (i.e., RO and NF) in
• Insensitivity selectivity
combination with adsorption can be investigated as a promising option.
to poisonous • Regeneration
contaminants of used
This hybrid strategy can also enjoy the continuous separation/recovery
absorbent performance. LMPs can be employed in a batch mode with high
Photocatalysis • No sludge • Generation of [10,119,121,122]
production unfavorable by-
product
Table 8
• High
Potential resources of PMs from disparate wastewaters.
operation cost
Membrane • High • High [224,268–270,348–352] PMs Concentration Correspondent Ref.
technology efficiency investment and resource
• Generation of maintenance
Pt, Pd, Rh, • 81 mg Pt/lit Industrial wastewater [357]
low solid waste cost
Cu, Zn • 29 mg Pd/lit
• Low • Low flow
• 7 mg Rh/lit
consumption of rates
• 24 mg Cu/lit
chemical • Occurrence of
• 102 mg Zn/lit
materials fouling
Au, Pt, Pd • 4.2–5.8 mg Au/lit Metallurgic effluent [11]
Biological • Possibility of • The existence [154,271]
• 12.9–15.3 mg Pt/lit
process (i.e., application for of various
• 131–137 mg Pd/lit
biosorption, PM recovery operational
Cr, Ni • 48 mg Cr/lit Metallurgic effluent [358]
bioleaching) • Good ambiguities
• 30 mg Ni/lit
recovery
Au, Ag, Cu, • 16 mg Au/lit Industrial wastewater [359]
efficiency
Ni • 250 mg Ag/lit
• 14,200 mg Cu/lit
• 22,500 mg Ni/lit
metals/ions from wastewater. Electrochemical technique is a fast and Pt, Gd Based on an average stream of Hospital wastewater [360]
selective technique for recovery of PMs from aquatic environment. 500 m3/day:
However, formation of large particles and high operation cost are the • 13.7 kg Pt/yr
main bottlenecks for scaling up of this process. The ion exchange (IE) • 182.5 kg Gd/yr
Cu, Zn, Ni, • 1527 mg Cu/lit Electroplating [361]
technique, however, is considered as a robust alternative and one of the
Cr • 689 mg Zn/lit wastewater
most investigated methods for the recovery process of PMs. To reduce • 462 mg Ni/lit
the overall operation cost, some investigators studied the application of • 264 mg Cr/lit
spent resins from an industrial demineralizing plant for the recovery of Li, Cs, Rb Maximum values: Geothermal fluids [362]
Au. Another technique for the recovery of PMs, which is still expensive 219 mg Li/lit
39 mg Cs/lit
in comparison with other techniques, is photocatalysis. The 170 mg Rb/lit

27
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

efficiency, however, not with combination with other processes. More­ Table 9
over, chemical precipitation, coagulation/flocculation and electro­ Presentation of essential patents developed in the area of PM recovery.
chemical processes can be investigated as pretreatment and/pre- Inventor(s) Publication Publication number Patent title
concentration steps to enhance the efficiency and affordability of date
membrane technologies for PM recovery. Koji Yamada 2010 US7815706B2 Method and apparatus
et al. for recovering platinum
4.2. Technology advancements group elements
Chen Xia 2010 US20100025259A1 Precious metal recovery
from solution
4.2.1. Opportunities and challenges Bryn Harris 2011 WO2011100821A1 Process for the recovery
In recent years, the continuous growth of population and world and Carl of gold from an ore in
economy increased the global demand for PMs such as Au, PGMs, and White chloride medium with a
noble earth elements. This requirement and the associated industrial- nitrogen species
Barun Gorain 2012 US8262768B2 Method to improve
based extraction of PMs have endangered the ecosystems and human
and Peter recovery of gold from
well-being [353]. PMs can be appropriately recovered from non- Kondos double refractory gold
economically beneficial wastewater streams by the abovementioned ores
techniques (Sections 3.1 to 3.5). For instance, municipal wastewaters Yu Haibin et al. 2013 CN102925713A Method for recovering
rhodium from rhodium-
include Pt particles originating from automotive catalysts and hospital
containing waste
wastewater (i.e., chemotherapeutic drugs containing Pt). The primary catalyst in
restriction for recovering PMs from these aquatic environments is their hydroformylation
significantly low PM concentrations. Thus, the development and utili­ through sulfur
zation of affordable, sustainable, and environmentally friendly tech­ David 2014 MX2013012774A Method for the recovery
Dreisinger of Indian, silver, gold
niques to recover PMs seem to be crucial [170]. Table 8 presents
et al. and other rare, precious
potential resources of PMs from different wastewater samples. Although and basic metals from
there has been an apparent improvement towards the development of complex oxide and
technologies for PM recovery, some bottlenecks still remain for future sulfured minerals
Yeonuk Choi 2015 US9051625B2 Method for recovering
promotion. Reaching a high efficient, eco-friendly, and sustainable re­
et al. precious metals and
covery of PMs, several other key points must be considered as follows copper from leach
[56]: solutions
Yuki Aoto and 2015 AU2013204872B2 Method for pretreating
(1) More developed techniques for commercialization in terms of Kazuhiro gold ore
Hatano
investment and cost
Chen Xia 2016 US9150942B2 Process of leaching
(2) Integration of the recovery techniques according to the physico­ precious metals
chemical properties of different PMs Marco DR. 2017 WO2017167553A1 Method for recovering
(3) The necessity of some pretreatment procedures to improve the stemmler rhenium and at least
efficiency and decline the environmental pollution et al. one platinum group
element from catalyst
particles
Numerous studies have confirmed that recycling PMs can save a David 2017 US9702024B2 Method for the
significant amount of energy and considerably reduce carbon emission Wohlgemuth hydrometallurgical
[354,355]. Au, Pt, Ag, and Pd are known as the most important PMs in et al. recovery of lithium,
nickel and cobalt from
various wastewater streams (i.e., industrial, hospital, and metallurgic
the lithium transition
effluent) produced from different anthropogenic activities (see Table 8) metal oxide-containing
[356]. Recently, investigators have made a countrywide report to fraction of used galvanic
evaluate the recovery opportunities of PMs from the American waste­ cells
water treatment plants (WWTPs). As an example, for a society of one Yeonuk Choi 2018 US10161016B2 Method for pre-
et al. treatment of gold-
million residents, the annual value of PMs in bio-solids/wastewater bearing oxide ores
streams was predicted up to US$ 13 million [356]. Harald Bauer 2019 DE102018208043A1 Method and apparatus
Hence, the recovery process of PMs from wastewater is considered as et al. for recovering gold,
a promising solution, which possesses the capability to mitigate the silver and platinum
metals
discrepancy between supply and demand [353]. The critical question is
Yeonuk Choi 2019 US10415116B2 Co-current and counter
that what will be occurred for the PM prices and how will demand for all and Samir current resin-in-leach in
PMs that support our technological-based sustainable lifestyles be met in Chefai gold leaching processes
the next years. Recovery and reuse can be the response. The recovery of Jakub 2019 WO2019178051A1 Precious metals
PMs from various wastewater streams is regarded as an economical, eco- Pedziwiatr recovery processes
and Ronald
friendly beneficial and productive route to facilitate the sustainable Todd Graves
application of PMs. Alexander 2021 WO2021089233A1 Method for obtaining
Eifert and platinum and/or
4.2.2. Influence of impurities on the PM recovery Claudio ruthenium
Baldizzone
In various industrial-based utilizations such as catalytic field, the
removal process of impurities (i.e., Fe, Cu and Zn) from solution of PMs
is of great importance due to their detrimental impacts on catalysts’ role on the PM recovery processes [365,366]. Currently, it has been
efficiency and their deactivation during processes. Thus, it is of great reported that some metallic impurities such as iron (Fe) and copper (Cu)
importance that PMs be free from or only include insignificant per­ possess significant influence on the PM recovery using some techniques
centages of impurities, because the existence of these impurities can such as IE, precipitation, and electrodeposition-redox replacement
poison the catalyst and deteriorate the catalytic reaction. Moreover, (EDRR). It is concluded that the existence of Fe declines the recovered
impurities can overcome the separation of PMs in a competitive way amount of PMs because of competition between PMs (Au, Ag, and PGMs)
[363,364]. Thus, it is well identified that impurities play very important

28
A. Taghvaie Nakhjiri et al.
Fig. 26. Detailed information about the fluctuation of PM prices in U.S. Dollars per troy ounce from 1969 to 2021 (Pt: platinum, Pd: palladium, Au: gold, and Ag:
silver). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Data have been provided from [161].
and Fe3+ for reduction at the cathode surface. Albeit, this phenomenon
can be advantageous for increasing the purity of PMs because the base
metal (Zn or Cu) can be selectively oxidized by Fe3+ and therefore the
cathode surface enriches with the PMs [365,366]. In the PM recovery
process, Fe can be an important challenge. In aqueous solutions,
oxidized Fe species present in two forms including ferrous (Fe2+) and
ferric (Fe3+) ions. In an electrochemical cell, iron can be problematic
owing to the ferrous/ferric redox couple. At the anode surface, Fe2+ is
oxidized to Fe3+ by losing an electron as follows:
Fe2+ →Fe3+ + e−
3+
Meanwhile, at the cathode surface, Fe ion is reduced to Fe
obtaining an electron as the follows:
Fe3+ + e− →Fe2+
Despite the fact that these reactions balance each other, they actually
use electricity and possess a harmful influence on current efficiency
(CE). Based on Faraday’s Law, CE is defined as the real rate of recovered
metal to its theoretical amount [367].
4.2.3. Patents
Table 9 presents developed patents in recovering important PMs
from different sources in the recent 10 years. This table can provide a
good opportunity for researchers worldwide to be familiar with state-of-
the-art patents focusing on PM recovery using a variety of methods. As
could be observed, Au is the most patented PM to be recovered from
wastewater streams.
4.3. Market issues
4.3.1. Trend for price
PMs are believed to be an appropriate portfolio hedge against
inflation. Fig. 26 represent the comprehensive information about the
price fluctuation of PMs in US$ per troy ounce from 1969 to 2021.
Reviewing the PM prices’ history and their associated fluctuations may
assist investors in recognizing the trends that result in helping them to
make accurate decisions about buying and selling PMs. It can also
encourage researchers and R&D companies to scale up the recovery
processes for PMs from wastewater, even if they exist in a trace amount.
As could be observed, Pd and Au have showed the sharpest growth
among other items since 2016.
Desalination 527 (2022) 115510
4.3.2. Demand and future trend
Nowadays, PMs have become an indisputable part of human life. The
existence of brilliant characteristics such as excellent resistance to
corrosion and appropriate malleability has made PMs beneficial for an
extensive variety of industries [56,81]. Au is not just regarded as a
luxurious metal, but it also has excellent electrical conductivity, which
has led to its widespread use in almost all high-tech electronic devices
such as smartphones and computers. Indeed, the potential capability of
Au to reflect sunlight has made it necessary to protect spacecraft from
the absorption of a significant amount of ultraviolet radiation, as well as
(10)
making it an essential substance in solar panels [84,368].
2+ Ag is a versatile PM, which has various industrial applications such
by
as electronic devices, medical devices, and photovoltaic cells in solar
panels [369–371]. Pt and Pd are known as rare PMs that can be safely
(11) grouped together when the purpose is to interpret their industrial ap­
plications. Both Pt and Pd are applied to make catalytic converters in
gas-powered cars. This critical application has made them meaningful
for the present-time automotive industry (see Fig. 26 for Pd). Even
though both abovementioned PMs have various applications in the
manufacturing of medical equipment, the automotive industry can be
taken into account as the most prominent demand for both Pt and Pd
[372]. Detailed information about the important natural sources, utili­
zation, and demand outlooks of all prevalent PMs is represented in
Table 10.
Fig. 27 schematically demonstrates the overall production trend of
four common PMs (Au, Ag, Pt, and Pd) worldwide. One can see at a
glance that after 2012, the overall production of these four PMs has not
dramatically fluctuated, and their production has been an almost con­
stant while their global demand is growing every year, as mentioned
earlier. Therefore, developing novel and promising technologies to
recover PMs from various types of aquatic and non-aquatic environ­
ments seems crucial.
5. Conclusions
This review paper aims to outline the state-of-the-art breakthroughs
and recent developments in recovery of PMs from wastewater streams.
Physical techniques (i.e., adsorption, coagulation/flocculation), chemi­
cal techniques (i.e., ion-exchange, photocatalysis, electrochemical, and
precipitation), biological processes (i.e., biosorption, bioleaching),
membrane technology, ionic liquids, and hybrid technologies are the
main methods, which their efficiencies and characteristics on the
29
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

Table 10 holds promise for the development of PMs recovery from wastewater in
Summarization of various PM applications and their demand outlook the future. It is highlighted (Table 3) that some ILs such as [C8mim]
[87,150,373,374]. [BF4], [3MOPYR][BF4], [4MOPYR][TfO], [OMIM][Cl], [OPYR][Cl] and
PMs Top natural Application Demand outlook [OPYR][Tf2N] have shown excellent efficiency for recovery of PMs in
source various industrial operations like LLE, precipitation, and hollow fiber
(mining) supported liquid membrane.
Gold (Au) • China (13%) • Jewelry • Demand cycles According to the reviewed literature, it has been perceived that
• Australia • Investment • Investment driven biological techniques are simple, effective, and economical procedures
(10%) Electronics
•
to recover PMs, which have excellent ability to be applied in industrial-
• Russia (9%) • Dental
• USA (7%) • Colors scale operations. Moreover, it has also shown a need for more in­
All others • Decoration vestigations in PM recovery from wastewater (particularly Au, Ag, Pt,
(61%) • Bonding wire and Pd) to be crucial, which could be due to high prices and widespread
Silver (Ag) • Mexico • Solar panels • Increasing applications in use of these PMs. Bacteria, algae, and fungi have been of greater interest
(23%) Electronics electronics, automotive,
than other biomass materials used for PMs biosorption. Due to the low
•
• Peru (16%) • Investment and solar photovoltaic
• China (13%) • Catalysts system efficiency of most microorganisms (particularly the live microorgan­
• Poland (5%) • Jewelry isms), it is essential to develop novel modification methods to modify
All others • Chemistry some drawbacks such as the powder-shaped structure, low structural
(43%)
strength, and low selectivity for the recovery of PMs. Chemical modifi­
Platinum • South Africa • Automotive • Long term demand in
(Pt) (≈73%) • Glass proton-exchange membrane cation and immobilization are the fundamental modification methods
• Russia • Glass fiber (PEM) fuel cell applied on biomasses for recovery of PMs. Recently, different modifi­
(≈11%) • Catalyst cation techniques, including culture optimization and genetic engi­
• Zimbabwe • Jewelry neering, have been widely presented to enhance the specifications of
(≈7%) Chemotherapy
biological cells during the growth. It may be understood from this re­
•
• North
America (6%) view paper that chemical components consisting of sulfur groups play a
All others crucial role in enhancing the sorption capacity and biosorbent selec­
(3%) tivity for recovery of PMs. It must be mentioned that further studies on
Palladium • Russia Automotive • Application in Li-O2
•
finding novel solvents to eliminate adsorbed PMs without destructive
(Pd) (≈38%) • Electronic battery material
• South Africa • Dental/alloys influences on the properties and sorption capacities must be carried out.
(≈36%) • Catalysts The processes applying physical techniques for PM recovery from the
• North • Jewelry aquatic environment are other promising techniques, which have been
America • Investment thoroughly investigated in this work. It was found that the design of
(15%)
efficient physical recovery methods enhances the capacity of PM re­
• Zimbabwe
(5%) covery and decreases the environmental toxicity due to declining the
All others reagents and, thus feed consumption. It is known that the inadequate
(6%) release of PMs and production of fine particles (<53 μm) during size
Rhodium • South Africa • Catalyst • Long term demand in
reduction, are resulted in increasing the PM loss during physical sepa­
(Rh) (≈81%) • Glass manufacturing various auto
• Russia production catalysts
ration. Therefore, the recovery of the PMs’ fine fractions in a fluid is a
(≈9%) significant challenge. Based on current findings, the development of
• Zimbabwe alternative processes (i.e., floatation) can be offered as a future
(5%) perspective in PM recovery from waste streams.
• North
Membrane technology, including LMPs, FO, RO, and MD, is another
America (3%)
All others promising technique for efficient recovery of PMs from waste streams.
(2%) FO process has illustrated excellent capability in the recovery of
Iridium (Ir) • South Africa • Crucibles • Growing steady demands different PMs and heavy metals from industrial wastewater. RO is an
(≈96%) • Electronic
important pressure-driven membrane technology, in which the need for
• Zimbabwe devices
(3%)
small space, low pressure, acceptable selectivity, and high separation
All others performance can be determined as its advantages. In contrast, the ex­
(1%) istence of critical negative points like moderate to high capital and
Ruthenium • South Africa • Chemical • Growing steady demands operational cost, fouling, and low permeate flux have restricted the
(Rh) (≈96%) materials
broad application of RO technique for PM recovery. Compared to FO and
• Zimbabwe • Chlor-alkali
(3%) RO, the MD process has special privileges, including negligible operating
All others pressure, high water recovery, excellent recovery efficiency, and small
(1%) footprint. However, the energy-intensiveness of this technique has
Osmium • South Africa • Corrosion- • Unique small applications decreased its popularity for possible application in PM recovery. LMPs
(OS) (≈96%) resistant
• Zimbabwe substances
have emerged as promising options to overcome the operational chal­
(3%) • Alloys lenges of the above-mentioned technologies. LM has some substantial
All others production advantages, such as high recovery performance and large interfacial
(1%) area. However, LMs faced severe challenges, such as destruction or
leakage of emulsion globules in emulsion liquid membranes (ELMs) or
recovery process of PMs are discussed in detail. liquid stability in the porous support in supported liquid membranes
Ionic liquids are important organics with great capability for re­ (SLMs), which prevented them from growing and becoming
covery of PMs. As mentioned earlier, anionic exchange and ionic pairing industrialized.
are prominent mechanisms of PM recovery. In this study, noteworthy In recent decades, hybrid techniques have been considered an effi­
physical, chemical, and thermodynamic parameters that affected the cient approach to integrating chemical and biological processes to
recovery efficiency/mechanism of PMs have been evaluated. This work achieve the advantages of both methods. In hybrid techniques, a
sequence takes place that the ore is treated biologically, accompanying

30
A. Taghvaie Nakhjiri et al. Desalination 527 (2022) 115510

Fig. 27. Total production of four well-known PMs (Au: gold, Ag: silver, Pt: platinum, and Pd: palladium) worldwide. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
Data have been adopted from [136,137].

by a chemical process or vice versa, which eventuates in decreasing the MW Mining waste
consumption of chemical reagents and modifying the environmental NF Nanofiltration
profile. Indeed, the development of novel hybrid technologies to inter­ PAC Poly‑aluminum chloride
connect chemical and biological processes to enhance the PM recovery PCB Printed circuit board
efficiencies from different aquatic/non-aquatic environments can be PGMs Platinum group metals
identified as an essential outlook towards the sustainable supplement PMAs Precious metal alloys
and application of PMs. PMs Precious metals
Understanding the advantages and disadvantages of all practical POU Point-of-use
approaches to PM recovery can open new horizons for the proper se­ PVPy Poly(vinylpyridine)
lection of the most efficient technique to increase recovery efficiency. RE Reference electrode
Table 7 outlines the advantages and disadvantages of all techniques used RIE Reductive ion exchange
to recover PMs. RO Reverse osmosis
SLM Supported liquid membrane
Abbreviations UM Urban mining
VRFB Vanadium redox flow battery
AE Anionic exchange WE Working electrode
AER Anionic exchange reaction WEEE Waste electronical and electronics equipment
ASSs Aquatic system sediments WWTPs Wastewater treatment plants
CE Counter electrode ZIF Zeolitic imidazolate framework
CE Current effciency
CIMS Cationic inorganic metal salts CRediT authorship contribution statement
CN Cyanide
DCMD Direct contact membrane distillation Ali Taghvaie Nakhjiri: Writing - Original Draft, Writing - Review &
ELM Emulsion liquid membrane Editing
ELVs End of life vehicles Hamidreza Sanaeepur: Conceptualization, Supervision, Methodol­
EPRP E-waste PM recovery plant ogy, Project administration, Investigation, Writing - Review & Editing
EV Electric vehicle Abtin Ebadi Amooghin: Writing - Review & Editing, Investigation
FO Forward osmosis Mohammad Mahdi A. Shirazi: Supervision, Project administration,
FSW Floor sweeping waste Investigation, Writing - Review & Editing
HWW Hand-washing waste
IE Ion exchange
Declaration of competing interest
IER Ion exchange resins
ILs Ionic liquids
We would like to confirm that there is no conflict of interests among
IP Ion pairing
authors and all of us completely agree that this manuscript should be
IPR Ionic pairing reaction
submitted to this journal and the "VSI: Desalination of Saline Waste­
LLE Liquid-liquid extraction
water" special issue.
LMP Liquid membrane process
LMs Liquid membranes
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