1 s2.0 S0045653523007750 Main

Chemosphere 328 (2023) 138508
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Chemosphere
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Adsorption of heavy metals on natural zeolites: A review

Lisbania Velarde a, b, Mohammad Sadegh Nabavi b, Edwin Escalera a, Marta-Lena Antti b,
Farid Akhtar b, *
a
Department of Chemistry, Faculty of Science and Technology, San Simon University, UMSS, Cochabamba, Bolivia
b
Division of Materials Science, Department of Engineering Sciences and Mathematics, Luleå University of Technology, SE-971 87, Luleå, Sweden
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
• The accumulation of heavy metals in

water sources has increased.
• Natural zeolites are environmentally
friendly adsorbents for the removal of
heavy metals.
• The structure of natural zeolites can be
modified by acid/basis/salt reagent,
surfactants, and metallic reagents.
• The most applied natural zeolite for the
removal of heavy metals is clinoptilolite.
• Properties of natural zeolites are unique
in each region.
A R T I C L E I N F O A B S T R A C T
Handling Editor: Yongmei Li Water pollution has jeopardized human health, and a safe supply of drinking water has been recognized as a
worldwide issue. The increase in the accumulation of heavy metals in water from different sources has led to the
Keywords: search for efficient and environmentally friendly treatment methods and materials for their removal. Natural
Adsorption zeolites are promising materials for removing heavy metals from different sources contaminating the water. It is
Heavy metals
important to know the structure, chemistry, and performance of the removal of heavy metals from water, of the
Wastewater
natural zeolites to design water treatment processes. This review focuses on critical analyses of the application of
Natural zeolites
Clinoptilolite distinct natural zeolites for the adsorption of heavy metals from water, specifically, arsenic (As(III), As(V)),
cadmium (Cd(II)), chromium (Cr(III), Cr(VI)), lead (Pb(II)), mercury(Hg(II)) and nickel (Ni(II)). The reported
results of heavy-metal removal by natural zeolites are summarized, and the chemical modification of natural
zeolites by acid/base/salt reagent, surfactants, and metallic reagents has been analyzed, compared, and
described. Furthermore, the adsorption/desorption capacity, systems, operating parameters, isotherms, and ki
netics for natural zeolites were described and compared. According to the analysis, clinoptilolite is the most
applied natural zeolite to remove heavy metals. It is effective in removing As, Cd, Cr, Pb, Hg, and Ni. Addi
tionally, an interesting fact is a variation between the natural zeolites from different geological origins regarding
the sorption properties and capacities for heavy metals suggesting that natural zeolites from different regions of
the world are unique.
* Corresponding author.
E-mail address: farid.akhtar@ltu.se (F. Akhtar).
https://doi.org/10.1016/j.chemosphere.2023.138508
Received 25 October 2022; Received in revised form 20 February 2023; Accepted 24 March 2023
Available online 25 March 2023
0045-6535/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
L. Velarde et al. Chemosphere 328 (2023) 138508
1. Introduction purpose because of the low cost, easy operation, no additional operating
cost for sludge removal, short duration time, and applicability for many
In the last decade, access to clean water has become a challenge applications (Anderson et al., 2022; Barakat, 2011; Chakraborty et al.,
because of growing industrial activities and populations. In addition, the 2022).
increase in the demand for services and food production has led to It is crucial to find a suitable adsorbent to fulfill the requirements for
increasing waste, pollution, and degradation of natural water sources, both pilot and industrial scales (Carolin et al., 2017). A promising
which affect access to clean drinking water (Darabdhara and Ahmar adsorbent can be defined as a material to remove heavy metals with a
uzzaman, 2022; Manikandan et al., 2022). high adsorption capacity, selectivity and rapid kinetics of adsorption
The pollutants affecting natural water sources are heavy metals (Cu, and desorption, and low energy penalty for regeneration (Yahya et al.,
Ag, Zn, Cd, Hg, Pb, Cr, Mo, Mn, Co, Ni), inorganic pollutants (NO−3 , 2018). Moreover, it should be long-term durable, cheap, sustainable,
NH4+, PO2− 4 ), metalloids (B, Si, Te), organic pollutants (benzene, and environmentally friendly (Renu et al., 2017; Vardhan et al., 2019).
phenol, toluene, chloroaniline, pyrene, methylene blue), microorgan There are several kinds of adsorbents for removal of heavy metals, such
isms (Escherichia coli, Staphylococcus aureus) (Awad et al., 2019; Singh as activated carbon (Duan et al., 2020), carbon nanotubes (Bassyouni
et al., 2018). Among these pollutants, heavy metals are greatly con et al., 2020), graphene oxide (Wu et al., 2020), mesoporous silica, and
cerning because of the large and increasing number of industrial activ mesoporous carbon (Anbia and Davijani, 2013; Anbia and Dehghan,
ities that dispose of these heavy metals into wastewater discharge (Kaya 2014; Da’na, 2017; Gupta et al., 2019; Hamad et al., 2016; Song et al.,
et al., 2019a; Kaya et al., 2019b). Moreover, since they are toxic, they 2022), clays (Ozdes et al., 2011; De Pablo, Chávez, and Abatal, 2011),
cause illnesses and diseases such as lung cancer and cancers of other zeolites (Jiménez-Castañeda and Medina, 2017; Misaelides, 2011; Yuna,
respiratory organs, the kidney and bladder, damage to the brain and 2016), metal organic frameworks (Li et al., 2021), and adsorbents from
reproductive organs, and heart and immune system disorders (P. Ahmad industrial/agricultural by-product residues (Babel and Kurniawan,
et al., 2020; Ali et al., 2019; Bhat et al., 2021). Treatment to reduce or 2003; De Gisi et al., 2016; Mckay et al., 1989; Srivastava et al., 2008;
eliminate heavy metals in drinking water to permissible levels is critical Vardhan et al., 2019) . Among the adsorbents mentioned, naturally
for human health (Flora et al., 2008; Kumar and Puri, 2012; Qasem occurring clays like natural zeolites have attracted attention because of
et al., 2021). their worldwide presence in a variety of different structures, chemical
Several processes treat water containing heavy metals, such as compositions, and ab/adsorption properties, as well as their continuous
coagulation (Tang et al., 2014; Wang et al., 2021), chemical precipita exploitation (Ackley et al., 2003; Misaelides, 2011; Tran et al., 2015).
tion (Benalia et al., 2022; Fu and Wang, 2011), ion exchange process This review presents a summary of research on the removal of heavy
(Da;browski et al., 2004; Qasem et al., 2021), membrane separation metals in natural zeolite adsorbents (Fig. 1), and further promote the use
(Kamran et al., 2022), reverse osmosis (Azimi et al., 2017; Mohseni of natural, low-cost, and easily accessible adsorbents to contribute to
et al., 2021) and adsorption (Mao and Gao, 2021; Shahrokhi-Shahraki wards environmental care and minimize the use of synthetic adsorbents
et al., 2021). However, adsorption could be the best option for this that generate pollution through the synthesis process and use of
Fig. 1. An overview of the research on the removal of heavy metals with natural zeolites.
2
precursor materials. Furthermore, this review includes various modifi properties such as ion exchange, adsorption, dehydration (Akhtar et al.,
cation and treatment methods for natural zeolites to tailor the adsorp 2014; Nabavi et al., 2014; Wang and Peng, 2010). Natural zeolites
tive properties. The chemical composition of natural zeolites from originate from a process of alteration of volcanic glass under different
distinct countries is gathered and reported. The collected data includes geochemical conditions at different temperatures (Marantos, Ioannis
the textural properties of natural zeolites (pore diameter, surface area, and Christidis, George E and Ulmanu, 2012). The crystal structure of
and pore volume). An extensive data summary of previous in natural zeolite minerals is tetrahedral, consisting of either silicon or
vestigations of the removal of heavy metals on natural zeolites is aluminum surrounded by oxygen atoms. The internal structure of nat
detailed. The removal of heavy metals such as arsenic, cadmium, chro ural zeolites is composed of large channels and cages containing H2O
mium, lead, nickel, and mercury are discussed. These elements are the molecules and cations such as K+, Na+, Ca2+, and Mg2+. These molecules
most hazardous metallic elements according to ATSDR (Agency for toxic and cations can ionically exchange with other elements
substances and disease registry) ranking. A discussion about the regen (Jiménez-Castañeda and Medina, 2017; Yuna, 2016). Natural zeolites
eration process of natural zeolites is included. Furthermore, the are described with the following chemical formula (Coombs et al.,
modeling and simulation of adsorption and kinetic data are also 1998).
described. ( )[ ]
Mx+ , My2+ Al(x+2y) Sin− (x+2y) O2n × mH2 O (i)
2. Natural zeolites
2+
Where M+
x are monovalent values with stoichiometry x, My are divalent
Natural zeolites are porous hydrated aluminosilicate materials con values with stoichiometry y, [Al(x+2y) Sin− (x+2y) O2n ] is structural cations,
taining pores ranging from macropores to mesopores with suitable
Table 1
Chemical composition and cation exchange capacity (CEC) of natural zeolites in the world.
Zeolite Chemical Composition (wt %)
SiO2a TiO2b Al2O3c Fe2O3d MgOe CaOf MnOg Na2Oh K2Oi P2O5j LOIk Ref.
Iranian Clinoptilolite 66.50 0.21 11.81 – 0.72 3.11 0.04 2.01 3.12 0.01 11.17 Ghiaci et al. (2004)
Sardinian Clinoptilolite 61.86 0.253 12.50 2.95 0.66 1.38 0.040 3.65 3.72 – – Cincotti et al. (2006)
Australian Clinoptilolite 68.3 – 13.00 1.4 – 2.1 – – 4.1 – – (Wang et al., 2008)
Turkish Clinoptilolite 70.90 – 12.40 1.21 0.83 2.54 – 0.28 4.46 – 7.20 Oter and Akcay (2007)
Kazakh Clinoptilolite 65.28 – 10.81 0.16 0.93 2.32 – 0.95 1.38 – 18.50 Sultanbayeva et al. (2013)
Turkish Clinoptilolite 75.28 0.06 12.04 1.11 1.21 4.43 – – 4.49 – –
Korean Clinoptilolite 66.5 0.25 12.93 1.50 0.68 1.75 0.04 2.93 2.55 0.05 11.27 Zeng et al. (2010)
Japanese Chabazite-Ca 45.26 1.31 21.84 5.21 1.52 7.58 0.11 3.65 0.77 0.26 12.41 Zeng et al. (2010)
Bulgarian Clinoptilolite 70.10 0.13 11.40 0.78 0.37 2.95 – 0.70 3.30 – – Shaheen et al. (2012)
Serbian Clinoptilolite 66.57 – 13.13 2.30 0.56 3.85 – 1.27 1.17 – 11.05 Kragović et al. (2013)
Jordanian Clinoptilolite 35.63 1.73 9.71 11.71 11.27 6.65 0.12 1.42 1.29 0.53 – Al-Haj Ali and El-Bishtawi (1997)
Iranian Clinoptilolite 65 0.03 12.02 1.50 0.1 2.30 0.04 1.8 3 0.01 12 Olad et al. (2012)
Greek Clinoptilolite 70.1 0.113 12.0 0.727 0.765 3.04 – 0.304 3.31 – 9.45 ( Inglezakis et al., 2015)
Turkish Clinoptilolitel 80.20 – 11.20 – 0.79 3.46 – 0.20 2.36 – – Bektaş and Kara (2004)
Chilean Clinoptilolite 67.00 0.20 13.00 2.00 0.69 3.20 0.04 2.60 0.45 0.05 Englert and Rubio (2005)
Bosnian-Herzegovinian 65.7 – 13.0 1.48 1.41 3.08 – 0.95 1.33 – 12.9 Rakić et al. (2013)
Clinoptilolite
Chinese Clinoptilolite 65.52 0.21 9.89 1.04 0.61 3.17 0.06 2.31 0.88- 10.02 (Wang et al., 2007) (Fei et al.,
2010)
Romanian Clinoptilolite 66.72 0.33 12.28 1.54 9.68 4.37 – 0.59 3.07 – 10.38 Stanić et al. (2009)
Mexican Clinoptilolite 77.9 – 9.58 0.93 0.39 2.00 – 0.30 5.93 – – Berber-Mendoza et al. (2006)
Japanese Clinoptilolite 69.4 – 11.0 0.8 0.7 1.4 – 3.3 3.2 – – Chutia et al. (2009)
Japanese Mordenite 72.1 – 12.9 1.5 – 2.6 – 1.8 2.1 – – Chutia et al. (2009)
Spanish Clinoptilolite 68.15 0.20 12.30 1.30 0.90 3.95 – 0.75 2.80 – – Rodríguez-Iznaga et al. (2018)
Iranian Clinoptilolite 68.61 . 9.85 1.026 0.507 1.3 – 3.727 3.618 0.023 12.83 Ouki and Kavannagh (1999)
Serbian Clinoptilolite 64.88 0.37 12.99 2.00 1.07 3.26 – 0.95 0.89 – 13.59 Minceva et al. (2008)
Greek Clinoptilolite 77.08 0.11 13.08 0.97 0.76 3.68 – 0.34 4.00 – – Katsou et al. (2011)
Italian Clinoptilolite 63.36 – 12.90 – 1.29 3.0 1.39 2.16 – – – Langella et al. (2000)
Turkish Clinoptilolite 74.36 0.07 11.87 1.03 0.85 1.95 0.02 0.59 4.07 0.01 – (Gedik and Imamoglu, 2008)
Iranian Clinoptilolite 68.61 – 9.85 1.026 0.507 1.3 – 3.727 3.618 0.023 12.83 Asgari et al. (2013)
Turkish Clinoptilolite 70.0 0.07 12.8 0.75 1.65 2.6 0.03 0.9 4.3 0.16 – Kocaoba et al. (2007)
Cuban Clinoptilolite 62.36 – 13.14 1.63 1.22 2.72 – 3.99 1.20 – 13.15 Marzal et al. (2005)
Turkish Clinoptilolite 71.0 0.10 11.80 1.70 1.40 3.40 – 0.40 2.40 6.87 – Çoruh and Ergun (2009)
Turkish Clinoptilolite 68.96 – 12.45 0.82 1.40 2.53 – 1.34 3.52 – 8.98 Argun (2008)
Slovakian Clinoptilolite 70.90 0.12 10.49 1.35 0.92 2.82 0.004 <0.2 3.58 0.004 – Wingenfelder et al. (2005)
Mexican Clinoptilolite 64.4 – 12.2 1.13 0.5 2.6 – 0.54 3.07 – – Saucedo-Delgado et al. (2017)
a
SiO2: silicon oxide (II).
b
TiO2: titanium oxide (IV).
c
Al2O3: alumina.
d
Fe2O3: iron (III) oxide.
e
MgO: magnesium oxide.
f
CaO: calcium oxide.
g
MnO: manganese oxide
h
Na2O: sodium oxide.
i
K2O: potassium oxide.
j
P2O5: phosphorus oxide (III).
k
LOI: loss of ignition.
l
Turkish natural zeolite contains in its composition 1.79 wt % of FeO.
3
and m is the number of water molecules in the structure (Čejka and van improve the structural properties, and increase the affinity towards the
Bekkum, 2005). cations. Currently, the principal modifications reported in the literature
Natural zeolites occur in different environments, mostly in alkali are through i) acid treatment, ii) base treatment, iii) salt treatment, iv)
media, i.e., saline/alkaline lakes, alkaline soils and land surfaces, deep- cationic surfactant modification, and v) metallic functionalization.
sea sediments, open hydrologic systems, products of the hydrothermal Treatments with either acids and bases or salts modify the structure
alteration as well as burial diagenetic or low-metamorphic rocks (Čejka (increase in surface area, microporosity, and pore size). Modification
and van Bekkum, 2005). More than eighty types of natural zeolites have with cationic surfactants and/or metallic reagents modifies the surface
been found and reported in the literature (Bish and Carey, 2001). The of the zeolite to improve the affinity towards anionic contaminants (Liu
most common natural zeolites-analcime, chabazite, clinoptilolite, et al., 2017; Taneva, 2012). Some typical reagents and textural prop
erionite, faujasite, ferrierite, laumontite, mordenite, and phillipsite-are erties for modification of natural zeolites are shown in Table 3.
found in volcaniclastic rock (Čejka and van Bekkum, 2005). The pri
mary sources of these natural zeolites are located in Slovakia, Greece, 3.1. Acid/base/salt pretreatment
the United States, Bulgaria, and Italy (Cappelletti et al., 2017). The
details on the occurrence and chemical composition of natural zeolites Natural zeolites treated in acid, base, or salt have higher cation
are included in Table 1. adsorption and heavy metal removal efficiency. The treatment process is
Natural zeolites can be classified based on three conditions. Each one simple and easy to perform. However, consider that an excess amount of
has a sub-classification; structural variations (chains, sheets, and struc acid, base, or salt can affect crystallinity and consequently, lower the
tures). The crystals are more equitable in dimensions, guest molecules adsorption capacity. Hence, the quantity of the acid, base or salt must be
migration (1-D diffusion, 2-D diffusion, and 3-D diffusion), and frame controlled (Margeta et al., 2013; Wang and Peng, 2010). The acid
work topology (singly connected 4-ring chains, double connected 4-ring treatment eliminates the impurities of the zeolite through the replace
chains, frameworks with 6 rings) (Bish and Carey, 2001; Ulmanu, 2012). ment of natural zeolite cations with H+ cations (Öztaş et al., 2008). Acid
The characteristics and properties of natural zeolites have attracted treatment generates more available adsorption sites in the zeolites and
attention for their efficiency in adsorbing heavy metals. Their adsorp raises the surface area and microporosity (Castaldi et al., 2008). More
tion properties are unique since natural zeolites behave as molecular over, it increases the Si/Al ratio because of the dealumination process
sieves, in which small molecules can pass through the inlet channels and (Shi et al., 2018; Wang and Peng, 2010).
get adsorbed in the dehydrated channels and central cavities, while HCl is the most commonly used acid for treatment. A significant
large molecules cannot pass through (Ulmanu, 2012). In addition, nat increase in the surface area of natural clinoptilolite from 13 m2/g to 78
ural zeolites ion exchange property allows cation exchange with other m2/g was reported after treatment with 2M HCl (Sprynskyy et al., 2006).
ions like heavy metals (Ulmanu and Ildiko, 2012). According to the The acid treatment was found to be more effective than other methods
literature, natural zeolites typical range of cation exchange capacity is for the treatment (Bektaş and Kara, 2004; Gedik and Imamoglu, 2008).
2–4 milliequivalents per gram (meq/g) (Dionisiou and Matsi, 2016; Base and salt mediums for the treatment of natural zeolites have been
Ulmanu, 2012). Consider that the behavior of cation exchange and the mostly investigated and are reported by several authors (Al-Haj-Ali &
selectivity depends on other parameters such as the environment tem Al-Hunaidi, 2010; Bektaş and Kara, 2004; Gedik and Imamoglu, 2008;
perature, ion valence, charge density on the anionic framework, elec Günay et al., 2007; Mihaly-Cozmuta et al., 2014). Treatments with bases
trolyte concentration, cation framework topology, and ion size and can dissolve the Si in zeolite and decrease the Si/Al ratio against acid
shape (Čejka and van Bekkum, 2005; Ulmanu, 2012). These parameters treatment. In addition, the higher pH in the treatment with base can
and the chemistries of natural zeolites influence their cation exchange eliminate the crystal structure of zeolite (Jovanovic et al., 2012; Shi
property, especially their selectivity, whereby natural zeolites show a et al., 2018). The treatments with salts can remove water or inorganic
higher affinity for certain heavy metals (Oter and Akcay, 2007; Wang impurities by exchanging metal ions within the structure. Thus, the main
and Peng, 2010). The selectivity for different natural zeolites in the disadvantage of salt treatment is the high cost of salt reagents (Liu et al.,
adsorption of heavy metals is provided in Table 2. 2017; Shi et al., 2018).
The most common reagents used for base and salt treatments are
3. Modification of natural zeolites NaCl, Na2CO3, and NaOH. They convert natural zeolites to sodium
exchanged form (Na-zeolite). Sultanbayeva et al. (2013) activated and
Modifying natural zeolites by treatment with different reagents has converted natural heulandite-clinoptilolite to sodium form using sodium
recently gained considerable interest (Dionisiou and Matsi, 2016; Iran carbonate, which showed an increase in the active sorption centers.
najad and Kamran Haghighi, 2020; Reeve and Fallowfield, 2018; Shi Likewise, Lin et al. (2015) reported an increase in the surface area and
et al., 2018; Yuna, 2016). The treatments remove the impurities, ion exchange capacity of natural clinoptilolite by using NaOH (1.5 ML).
Besides, Gedik and Imamoglu (2008) reported higher Cd adsorption
capacity on natural clinoptilolite through the treatment with NaCl in
Table 2 comparison with the treatment with KCl, CaCl2, and HCl. Moreover, a
The cation exchange selectivity of heavy metals on natural zeolites.
considerable increase in Ni adsorption capacity was reported by treating
Zeolite Selectivity Ref. the natural clinoptilolite in a mixed solution of HCl and NaCl, compared
Clinoptilolite Pb > Cu > Zn > Cd > Ni Shaheen et al. (2012) to treating the natural zeolite only with either HCl or NaCl (Çoruh and
Heulandite Pb > Cu > Cd > Cr > Zn Nguyen et al. (2015) Ergun, 2009).
Clinoptilolite Pb > Cu > Cd > Ni Sprynskyy et al. (2006)
Scolecite Cr > Mn > Cd > Ni Dal Bosco et al. (2005)
Clinoptilolite Pb > Cu (Wang et al., 2008)
3.2. Modification with cationic surfactant
Na- Pb > Cu > Cd Fei et al. (2010)
Clinoptilolite Natural zeolites can be modified by cationic surfactants (SMZ) which
Clinoptilolite Pb > Cu > Cd > Zn > Cr > Co > Ouki and Kavannagh (1999) convert natural zeolites into multifunctional adsorbents suitable for
Ni
cations, anions, and molecular species uptake from different polluted
Chabazite Pb > Cd > Zn > Co > Cu > Ni > Ouki and Kavannagh (1999)
Cr sources (Dionisiou and Matsi, 2016). The large surfactant molecules
Clinoptilolite Pb > Cd > Zn Minceva et al. (2008) cannot enter the channels and cavities of the natural zeolites. Therefore,
Clinoptilolite Pb > Cu > Cd > Ni Merrikhpour and Jalali the modification process only occurs on the outer surface of the natural
(2013) zeolites (De Gisi et al., 2016). The interaction between natural zeolites
Clinoptilolite Pb > Zn > Cu > Ni Oter and Akcay (2007)
and cationic surfactants occurs through the exchange of organic cations
4
L. Velarde et al.
Table 3
Zeolite textural properties, pretreatment and modification reagents.
Zeolite Composition Pore Diameter Surface area (m2/g) Pore volume Pretreatment Surfactant or Metallic Ref.
(nm) (cm3/g) solution Modification Reagent
American Clinoptilolite – – 15 – – HDTMA (Li et al., 2007)

(Winston, New Mexico)
Turkish Clinoptilolite – – Natural zeolite: 0.1 N NaCl 0.1 M FeCl3*6H2O Bilici Baskan and Pala (2011)
34.11,
Na modified
zeolite: 33.11
Fe modified zeolite:
79.27
Ukrainian Clinoptilolite 75% Clinoptilolite 3.7,12,23 Natural zeolite:13.2 – – – Sprynskyy et al. (2006)
Quartz, Calcite, Brotite, Muscovite, Chlorite, Modified – 2 M HCl –
Montmorillonite clinoptilolite: 78.9
Mordenite 96% mordenite – 14.6 – – 28.4 g/Kgzeolite EHDDMA- Campos et al. (2007)
HDTMA
Australian Clinoptilolite Clinoptilolite, Mordenite, Quartz, Smectite and 4 16 – 0.5 M NaCl – (Wang et al., 2008)
Mica
Turkish Clinoptilolite Clinoptilolite, Heulondite, Quartz, Biotite and – – – NH4Cl – Oter and Akcay (2007)
Micrecline
Iranian Clinoptilolite NCP: 2.74 NCP: 23.19 NCP: 0.12 – HDTMA-Br Shirzadi and
NSMZ: 4.60 NSMZ: 29.72 NSMZ: 0.13 DT Nezamzadeh-Ejhieh (2017)
NSMZ-DT: 2.17 NSMZ-DT: NSMZ-DT:
34.33 0.208
Iranian Clinoptilolite 90% Clinoptilolite – 107 – – HDTMA Ghiaci et al. (2004)
10% Mordenite CPB
Korean Natural – – Natural zeolite: – – – Zeng et al. (2010)
Clinoptilolite 27.0
5
Modified – – Modified – – HDPB

zeolite:10.5
Japanese Natural – – Natural zeolite:48.2 – – –
Chabazite-Ca Modified – Modified – – HDPB
zeolite:5.0
Iranian Clinoptilolite Nanocrystalline natural zeolite 99.6% NaNPs – 323.4 – – BF Noroozifar et al. (2014)
9.51% H2O
Iranian Clinoptilolite 88.7% Clinoptilolite, 3.5% quartz and 7.8% MCP: 0.21 MCP: 68 MCP: 1700 – DMG Nezamzadeh-Ejhieh and
cristobalite NCP: 0.13 NCP: 97 NCP: 38 Kabiri-Samani (2013)
MCP-DMG: 0.18 MCP-DMG: 54 MCP-DMG: 1900
NCP-DMG: 0.11 NCP-DMG: 71 NCP-DMG: 62
Turkish Clinoptilolite 80% Clinoptilolite Natural Natural Natural NaCl 2 M – Bektaş and Kara (2004)
10% Quartz, 4% feldspar, 3% Quartz-opal, and zeolite:17 zeolite:15.36 zeolite:0.23
13% other traces of clays minerals Modified Modified Modified
zeolite:16.7 zeolite:16.41 zeolite:0.017
Mexican Clinoptilolite Estilbite, cristobalite, clinoptilolite, modernite, – – – NaCl 1 M HDTMA Cortés-Martínez et al. (2004)
analcime, quartz, calcite, and monocyclic
symmetry
Chilean Clinoptilolite 48% Clinoptilolite, 30% mordenite, 5% albite, – – – NaCl 1 M – Englert and Rubio (2005)
15% quartz
Chemosphere 328 (2023) 138508

Bosnian-Herzegovinian 72.6% Clinoptilolite, 14.6% feldspar plagioclase – – – NaCl 2 M – Rakić et al. (2013)
Clinoptilolite and 12.8% quartza
Chinese Clinoptilolite 50% zeolite minerals, quartz and feldspar 0.4 28.12 0.11 NaCl – Yuan et al. (2018)
Serbian Clinoptilolite Natural zeolite: 69% Clinoptilolite, 18% – – – – – Kragović et al. (2013)
plagioclase and 12% quartz
Fe (III) modified zeolite: 75% Clinoptilolite, 12% – – – – FeCl3*6H2OKOH
plagioclase and 13% quartz
Australian Heulandite Natural zeolite: Heulandite and quartz – 15.4 – – – Nguyen et al. (2015)
(continued on next page)
L. Velarde et al.
Table 3 (continued )
Zeolite Composition Pore Diameter Surface area (m2/g) Pore volume Pretreatment Surfactant or Metallic Ref.
(nm) (cm3/g) solution Modification Reagent
Fe (III) zeolite: Iron-coated zeolite heulandite, – 7.51 – – Fe (NO3)3*KOH

quartz, Fe oxidir, or oxo- hydroxidic
Jordanian Phillipsite Phillipsite, some non-zeolite materials such as – – – NaCl – Al-Haj-Ali and Al-Hunaidi
calcite and clays (2010)
Iranian Clinoptilolite – – – – HCl Polyaniline Olad et al. (2012)
Greek Clinoptilolite – – 28.64 – – – (Inglezakis et al., 2015)
Clinoptilolite Clinoptilolite, heulandite, mordenite, quartz, – 17.83 0.015 – – Minceva et al. (2008)
sanidine and biotite
Turkish Natural – 1.75 36.7 – 1 M NaCl – (Gedik and Imamoglu, 2008)
Clinoptilolite Na- 40.4 1 M KCl
Modified 1 M CaCl2
1 M HCl
Iranian Natural – 26.66 13.7 0.051 – – Asgari et al. (2013)
Clinoptilolite SMZ – 27.8 3.5 0.032
Turkish Clinoptilolite – 9.88 18.20 0.32 – – Kocaoba et al. (2007)
Turkish Clinoptilolite – 0.40 12 – – – Argun (2008)
Cuban Clinoptilolite Clinoptilolite >53%, 10.11 27.08 0.006402 – – Marzal et al. (2005)
6
Mordenite >17%, Feldspar, Quartz, Calcite

Turkish Clinoptilolite 45% Clinoptilolite – 95 – 2 M NaCl – Çoruh and Ergun (2009)
5% Heulandite 0.1 HCl
Iranian Clinoptilolite – 18.84 13.8 – – – Merrikhpour and Jalali (2013)
Iranian Clinoptilolite – 1000–10,000 28.24 – – FeCl2*4H20 (Javanbakht et al., 2019)
FeCl3*6H20
Chitosan
Iranian Natural – 31,46 14.85 0.11 – HDTMA-Br Zekavat et al. (2020)
Clinoptilolite HMNZ 38,19 9.55 0.09
Mexican Natural – 28.98 7.72 0.072 2 M NaCl HDTMA Wen et al. (2021)
Clinoptilolite Na- 27.57 5.41 0.051
Modified
Mexican Natural – – 11.67 – 0.3 M NaCl HDTMA-Br Salgado-Gómez et al. (2014)
Clinoptilolite Na- 11.93
Modified
SMZ 5.29
a
NaCl: sodium chloride; HCl: hydrochloric acid; NH4Cl: ammonium chloride; NaNPs: purified natrolite nanoparticles modified; e HDTMABr: Hexadecyltrimethylammnium bromide; f EHDDMA: ethylhexadecyldime-
b c d
thylammonium; g HDTMA: hexadecyltrimethylammonium; h BF: Baloform; i DMG: dimethylglyoxim; j DT: Dithizone; k HDPB: hexadecylpyridinium bromide; l KOH: Potassium hydroxide; m FeCl3*6H2O: Iron (III) chloride
hexahydrate; n Fe (NO3)3: iron nitrate, o CPB: N-cetylpyridium bromide, p HMNZ: HDTMA-modified natural zeolite.
Chemosphere 328 (2023) 138508

of the surfactant and the inorganic cations of the zeolite, thus forming a 4.1. Arsenic
positive surface on the zeolite (Noroozifar et al., 2014).
The most commonly used surfactants in the modification of natural Arsenic is found in water resources mainly in inorganic forms like
zeolites are benzyltetradecyl ammonium chloride (BDTDA) (Kuleyin, trivalent As(III) and pentavalent As(V), as well as in organic forms like
2007), N-cetylpyridium bromide (CPB) (Kuleyin, 2007), cetylpyr monomethylarsonate (MMA) and dimethylarsinate (DMA) in some cases
idinium chloride (CPC) (Mendoza-Barrón et al., 2010; Ren et al., 2016), (Chang et al., 2008; Thirunavukkarasu et al., 2002). It has been reported
cetyltrimethylammonium bromide (CTAB) (Karadag et al., 2007) N,N,- that raw natural zeolites have no affinity for As capture because of their
dimethyldehydroabietylamine (DAAO) (Karadag et al., 2007), negative surface (Li et al., 2007). Hence, it is necessary to modify the
ethylhexadecyldime-thylammonium (EHDDMA), hexadecylpyridinium surface of natural zeolites with cationic surfactants or metallic reagents
bromide (HDPB) (Zeng et al., 2010), hexadecyltrimethylammonium to enhance the uptake capacity of As.
(HDTMA) (Anari-Anaraki and Nezamzadeh-Ejhieh, 2015; Torabian Mendoza-Barrón et al. (2010) reported 12.5 times greater adsorption
et al., 2010; Wen et al., 2021), hexadecyltrimethylammonium bromide for HDTMA modified natural clinoptilolite than unmodified natural
(HDTMA-Br) (Asgari et al., 2013; Mirzaei et al., 2016; Salgado-Gómez clinoptilolite. Li et al. (2007) reported no affinity of clinoptilolite for As
et al., 2014; Zekavat et al., 2020) and hexadecyltrimethylammonium (V) and As(III), but adsorption of 0.54 mg/g for As(V) and 0.12 mg/g for
chloride (HDTMA-Cl) (Torabian et al., 2010). As(III) was achieved after the modification by HDTMA. In another study,
Various authors have reported a negligible affinity of natural zeolite Macedo-Miranda and Olguín (2007) verified the adsorption of 0.004
towards heavy metal cations such as Cr and As (Campos et al., 2007; Li mg/g for As(V) after HDTMA modification of clinoptilolite–heulandite.
et al., 2007; Song et al., 2015; Zeng et al., 2010). However, a significant However, they did not report the adsorption of As(V) (III) in natural
increase in the adsorption capacity of Cr and As was reported after the clinoptilolite-heulandite. It is expected to be negligible.
modification of natural zeolites with cationic surfactant (Asgari et al., As another alternative, the modification of natural zeolites by
2013; Chutia et al., 2009; Ghiaci et al., 2004; Li et al., 2007; Ren et al., metallic elements for arsenic removal has been vastly reported in the
2016; Song et al., 2015b; Zeng et al., 2010). It has been reported literature (Asere et al., 2019; Bilici Baskan and Pala, 2011; Jeon et al.,
(Mendoza-Barrón et al., 2010; Ren et al., 2016) that the adsorption ca 2009; Li et al., 2011; Stanić et al., 2009). Jeon et al. (2009) reported a
pacity of a modified clinoptilolite by surfactant increased 5 and 12.5 null affinity of As(V) by natural clinoptilolite and adsorption of 0.6 mg/g
times for Cr(VI) and As(V), respectively. by iron-coated zeolite (ICZ). Also, Stanić et al. (2009) reported an As(V)
Cationic surfactants can also alter the pore volume, pore diameter removal of 1.5 mg/g (96%) onto iron (III)-modified zeolitic tuff. Li et al.
(increase), and surface area (decrease) of the natural zeolites. The (2011) reported As(III) and As(V) adsorption of 0.1 mg/g and 0.05 mg/g
reduction in the surface area and pore volume could be because of the on Fe-exchanged zeolite (Fe-eZ), respectively (no reference values for As
blocking of pore channels of natural zeolites with surfactant (III) (V) adsorption on unmodified natural zeolite were reported). The
(Mendoza-Barrón et al., 2010; Zekavat et al., 2020; Zeng et al., 2010). adsorbent types and adsorption capacities with the experimental con
ditions of As(V) and As(III) adsorption are summarized in Table S1 of
3.3. Modification with metallic reagent supplementary material.
Magnetically modified zeolite (MMZ) suitably combines the prop 4.2. Cadmium
erties of zeolites and magnetic compounds (Maharana and Sen, 2021).
The characterization of the magnetically modified zeolites shows that Cadmium is a toxic element present in several industrial wastewa
the presence of magnetic compound does not inhibit the natural zeolites ters, such as the production of cadmium batteries, cadmium smelting,
frameworks and channels (Kragović et al., 2013b; Liang et al., 2011; and the manufacture of cadmium pigments (Friberg et al., 2018). The
Yuan et al., 2018b). Iron, and copper are the metallic compounds used in adsorption percentage of cadmium removal by natural zeolites could be
magnetically modified natural zeolites (Ates et al., 2011; Guaya et al., 100% based on the literature (Dal Bosco et al., 2005). Vaca Mier et al.
2015; Heredia et al., 2019; Li et al., 2011; Neolaka et al., 2022; Vakili (2001) reported Cd adsorption of 99% and higher than 90% for batch
et al., 2019). Several authors reported higher pollutant adsorption ca and fixed-bed column systems, respectively. A similar study for Cd
pacity by magnetically modified natural zeolites because more adsorp adsorption in mine water achieved about 86% for strong acidic and 21%
tion sites are present (Liang et al., 2011; Lv et al., 2014; Simsek et al., for weak acidic mine water. The low cadmium adsorption in weak acidic
2013; Yuan et al., 2018), They reported Pb adsorption capacity of 84.00 water was possibly because of Ca, Mg, and Mn elements which can
mg/g and 66.96 mg/g for MMZ and Na-zeolite, respectively. Likewise, reduce the metal adsorption capacity (Wingenfelder et al., 2005).
the modification of natural clinoptilolite with Fe(II) resulted in Even though most of the studies on cadmium adsorption are reported
achieving a Cr(VI) adsorption capacity of 6 mmol/kg (Lv et al., 2014b). only with the application of natural zeolites, some authors studied
Another study of MMZ achieved adsorption capacities of 83.41 mg/g, cadmium adsorption by modified natural zeolites (Cortés-Martínez
31.27 mg/g, and 16.53 mg/g for Pb, Cd, and Cu respectively (Liu et al., et al., 2004; Nguyen et al., 2015). Cortés-Martínez et al. (2004) reported
2022). a slight decrease in Cd adsorption after the surfactant modification of
about 3% for SMZ. In contrast, Nguyen et al. (2015) reported an increase
4. Hazardous heavy metals; adsorption using natural zeolites in Cd adsorption after another type of modification, an iron-coated
modification for both batch and fixed-bed systems. They reported Cd
Different factors affect the adsorption of heavy metals by natural adsorption on ICZ of 7% and 46% higher than the natural zeolite for the
zeolites such as metal and zeolite properties and adsorption conditions batch and fixed-bed system, respectively. Further details of the cadmium
(pH, temperature, stirring speed, and initial metal concentration) adsorption conditions from the above-mentioned research and other
(Misaelides, 2011). Therefore, optimizing all these parameters is crucial research are shown in Table S2 of the supplementary material.
for better performance. A summary of several previous investigations on
heavy metal adsorption by natural zeolites is presented in Tables S1–S6 4.3. Chromium
in the supplementary material. The heavy metals studied are the most
hazardous according to the ATSDR (Agency for toxic substances and Chromium can be found in trivalent (Cr(III)) and hexavalent (Cr(VI))
disease registry) ranking, i.e., As, Cd, Cr, Pb, Hg, and Ni. forms, while the latter is more toxic. Therefore, the chemical reduction
of Cr(VI) to Cr(III) is the most common method to remove the element.
Cr(III) and Cr(VI) are present in the form of anions such as H2CrO4,
HCrO4-, CrO2− 2−
4 , and Cr2O7 (Guertin, Jacques and Jacobs, James A and
7
Avakian, 2004). Hence, natural zeolites adsorption could be negligible 84.0 mg/g for MMZ and 66.9 mg/g for Na-Z. The summarized data of the
because of the negative charge and a modification by a cationic sur studies mentioned on the adsorption of Pb by natural zeolites is detailed
factant or metallic reagent is needed (Campos et al., 2007) to increase in Table S4 in the supplementary material.
zeolite affinity (Asgari et al., 2013; Dionisiou and Matsi, 2016; Ley
va-Ramos et al., 2008; Lv et al., 2014; Olad et al., 2012; Salgado-Gómez 4.5. Mercury
et al., 2014; Zekavat et al., 2020). Campos et al. (2007) reported an
adsorption percentage of 93% of Cr(VI) adsorption for mordenite Another toxic heavy metal is mercury, which is found in the envi
modified by HDTMA-HSO4 and 67% for natural zeolite modified by ronment because of contamination caused by mining activities, the
EHDDMA. Olad et al. (2012) reported adsorption of 98% for Cr(VI) on manufacture of dyes, electrolytic catalysis, etc. (Langford and Ferner,
clinoptilolite modified with polyaniline. Additionally, Zeng et al. (2010) 1999). Table S5 provides the studies of the adsorption of Hg by natural
reported a significant enhancement of Cr(VI) adsorption, 9.5 times zeolites. Chojnacki et al. (2004) demonstrated the adsorption of Hg on
higher after modification of chabazite-Ca (HZ) by HDPB. Modifying natural clinoptilolite. Their research showed the feasibility of natural
natural zeolites by metallic reagent is another approach based on the clinoptilolite to remove Hg from copper smelting and refining effluents.
literature (Lv et al., 2014; Mthombeni et al., 2018; Nguyen et al., 2015b; Also, Shirzadi and Nezamzadeh-Ejhieh (2017) reported considerable
Olad et al., 2012; Sharma et al., 2009). Lv et al. (2014) reported an in adsorption of Hg by surfactant modified natural zeolite than raw cli
crease in Cr(VI) adsorption to 0.3 mg/g after modification of natural noptilolite. They showed a Hg adsorption of 170.5 mg/g for natural
clinoptilolite by Fe(II). Nguyen et al. (2015) showed an increment of clinoptilolite modified with HDTMA-Br and dithizone. The result was
chromium adsorption after heulandite modification by iron coating. 84.2 mg/g for raw clinoptilolite.
They reported an adsorption increase of 10% for ICZ. Table S3 of sup In addition to the studies mentioned, an adsorption capacity of Hg in
plementary material summarizes the chromium adsorption conditions of the range of 9–26 mg/g for Na and Ag modified natural clinoptilolite
some studies. was reported (Inglezakis et al., 2023).
4.4. Lead 4.6. Nickel
Lead (Pb) is one of the most dangerous heavy metals. The contami Nickel is present in the wastewater of nickel refining operations,
nation comes mainly from the production of batteries and metallurgical roasting, smelting, and electrolysis industries (Moore et al., 2012). A
alloys (Wani et al., 2015). The affinity of natural zeolites for Pb, either in study of Brazilian scolecite showed a high percentage of nickel adsorp
single or mixed solutions has been investigated intensively (Merrikh tion (96%) at low initial concentrations (10–100 mg/L). However, the
pour and Jalali, 2013; Nguyen et al., 2015; Shaheen et al., 2012; adsorption was 40% at the high initial concentrations of Ni (100–5000
Sprynskyy et al., 2006). Mixed solutions are investigated to study the mg/L), showing a destructive effect on adsorption quality by increasing
behavior of adsorption of one metal in the presence of other elements to the initial concentrations (Dal Bosco et al., 2005). This was in agreement
apply to a real wastewater system (Dal Bosco et al., 2005; Hernández- with the results of (Sprynskyy et al., 2006), stating that the removal of
Montoya et al., 2013; Inglezakis et al., 2007). nickel is inversely proportional to the metal concentration. In contrast,
Wingenfelder et al. (2001) reported the adsorption of Pb by Slova Serbian clinoptilolite achieved higher adsorption capacity when both
kian natural zeolite in mine water with about 100% in acidic solutions. initial concentration and temperature were higher (Rajic et al., 2010).
Moreover, they investigated the effect of the zeolite particle size by Likewise, Rodríguez-Iznaga et al. (2018) reported higher capacity
having two categories; small particles (0.3–1.0 mm) and thick particles adsorption of Ni by increasing the temperature. Therefore, it can be
(1.0–2.5 mm). Small particles showed slightly higher binding to Pb inferred that different natural zeolites act differently by nature.
compared to big particles. Equally, Bektaş and Kara (2004) reported a Some authors studied the adsorption of Ni in the surfactant-modified
slight increase in Pb adsorption with a small particle size clinoptilolite. natural zeolite. For example, Shirzadi and Nezamzadeh-Ejhieh (2017)
Inglezakis et al. (2007) concluded that clinoptilolite dust is more effi reported an increase in Ni adsorption (3 times more) after DMG modi
cient than granular clinoptilolite (2.5–5.0 mm) in Pb uptake. fication. In addition, the authors studied the adsorption of Ni in both
Another parameter studied in the adsorption of Pb in natural zeolite single and mixed solutions, for example, a low adsorption percentage of
is the initial concentration. Günay et al. (2007) studied the proportional Ni (20%) in the presence of Cu, Pb, and Zn was reported by Oter and
adsorption increase and the initial concentration for Pb from 50 to 400 Akcay (2007). This result agreed with the Shaheen et al. (2012) and
mg/l. They reported a higher Pb adsorption for 400 mg/g than for a Al-Haj Ali and El-Bishtawi (1997) studies. The low Ni adsorption values
concentration of 50 mg/g. The increase was 4 and 6 times more for raw in mixed solutions could be because of the differences in the chemical
and pretreated clinoptilolite. In contrast, Shaheen et al. (2012) reported characteristics (ionic radius, electronegativity, dehydration energy)
a decrease in Pb adsorption by increasing the initial concentration in the between the other existing heavy metals in the mixed solutions, i.e., Zn,
range of 50–300 mg/l. They reported a maximum Pb adsorption of 99% Cu, Cd, Pb, Cr, Mn. However, Pb limits the adsorption of Ni more in
for an initial concentration of 50 mg/g. Thus, we can conclude that the mixed solution, since it possesses a small hydrated cationic radius,
effect of the initial concentration affects the adsorption of heavy metals which facilitates its adsorption into natural zeolite channels (Mihaly-
according to the characteristics of each natural zeolite. Furthermore, Cozmuta et al., 2014; Shaheen et al., 2012). Table S6 in the supple
several studies have dealt with the modification of natural zeolite mentary material summarizes the nickel adsorption studies with natural
(Al-Haj-Ali & Al-Hunaidi, 2010; Bektaş and Kara, 2004; Kragović et al., zeolites.
2013; Minceva et al., 2008; Nguyen et al., 2015; Oter and Akcay, 2007;
Shirzadi and Nezamzadeh-Ejhieh, 2017; Sprynskyy et al., 2006; Yuan 5. Mechanism of adsorption of heavy metals on natural zeolites
et al., 2018). Cincotti et al. (2006) found Pb adsorption on
sodium-modified natural zeolite 1.3 times greater than unmodified Because of their chemical nature, the dominant adsorption mecha
natural zeolite. Shirzadi and Nezamzadeh-Ejhieh (2017) reported a nism for natural zeolites is ion exchange since zeolite cations are able to
higher Pb adsorption on HDTMABr-dithizone modified clinoptilolite exchange with others cations in liquid solutions (Jiménez-Reyes et al.,
(145.0 mg/g) than on raw clinoptilolite (74.6 mg/g) showing higher 2021). In addition, the authors reported different mechanisms for the
adsorption by surfactant modified natural zeolites. Kragović et al. adsorption of heavy metals with natural zeolites, such as ion exchange,
(2013) reported higher Pb adsorption for Fe(III)-modified zeolite electrostatic attraction, intrapore adsorption, surface complexation, and
compared with the natural zeolite, with values of 133 mg/g and 66 surface precipitation (Günay and Ertan Arslankaya, 2007; Asgari et al.,
mg/g, respectively. Also, Yuan et al. (2018) showed Pb adsorption of 2013; Haggerty and Bowman, 1994a; Jeon et al., 2009; Ren et al.,
8
2016c). Ion exchange and electrostatic attraction mechanisms are the

most investigated mechanisms (Fig. 2) (Anari-Anaraki and Fe − OH + H2 AsO4 2− → Fe − O2 AsO2 H− + OH− (4)
Nezamzadeh-Ejhieh, 2015; Asgari et al., 2013; Gedik and Imamoglu,
2008; Ren et al., 2016). 2FeOH + HAsO4 2− → 2FeO − AsO2 H + 2OH− (5)
The pH influences the adsorption mechanism of heavy metals with For chromium, anion exchange and electrostatic attraction were
natural zeolites since it affects the surface charge and consequently the reported as the main mechanisms in the anionic species of Cr ((CrO2− 4 ;
cations adsorption (Al-Haj-Ali & Al-Hunaidi, 2010; Al-Haj Ali and H2 CrO4 ); Cr2 O2− ) in the pH ranges of 1–6 and greater than 6, respec
7
El-Bishtawi, 1997; Inglezakis et al., 2010; Lihareva et al., 2010; Lla tively (Haggerty and Bowman, 1994a; Ren et al., 2016; Zeng et al.,
nes-Monter et al., 2006; Vaca Mier et al., 2001). Gedik and Imamoglu
2010). Asgari et al. (2013) described the Cr(VI) adsorption on SMZ by
(2008) reported that the principal mechanisms of cadmium adsorption electrostatic attraction, which can be represented as the following:
with natural zeolites are ion exchange and physical adsorption for pH
values greater and smaller than 4, respectively. With nickel, the authors 2SMZ+ + HCrO−4 + Cr2 O2−7 → SMZ+ HCrO−4 + SMZ+ Cr2 O2−7 (6)
reported ion exchange as the predominant mechanism for pH lower than
8 (Argun, 2008; Merrikhpour and Jalali, 2013). In that pH range, 6. Technology in the application of natural zeolites
hydrogen ions are reduced, and a greater amount of Ni can be
exchangeable with the exchangeable cations characteristic of natural The adsorption process is a surface phenomenon where atoms, ions,
zeolites (Çoruh and Ergun, 2009). Equally, for lead and mercury, the or molecules are trapped on the surface of a solid materia. The adsorbate
most reported mechanism is ion-exchange through the exchange with is the substance being adsorbed, and the adsorbent is the adsorbing
exchangeable cations of zeolites (Ca2+, Na2+, K2+, Mg2+) (Kragović material. The interaction of the adsorbate components can be through
et al., 2013; Shirzadi and Nezamzadeh-Ejhieh, 2017). physical adsorption (physisorption), which occurs through intermolec
With arsenic, the authors reported suitable adsorption in the pH ular forces (van der waals, dispersion interactions, hydrogen bonding),
range of 3–14 where their anionic species (H2AsO−4 and HAsO4) interact or through chemical adsorption (chemisorption). It occurs through the
with SMZ through the anion exchange mechanism (Chutia et al., 2009; formation of chemical bonds (covalent and ionic bonds) (Crini et al.,
Li et al., 2007; Mendoza-Barrón et al., 2010; Stanić et al., 2009). Chutia 2019; Klein, 1985; Saleh, 2022). The adsorption process can be carried
et al. (2009) reported the following conceptual equations to express the out with various contact methods such as batch systems, fixed bed
interaction between the arsenate and HDTMA bromide by anion processes, pulsed beds, fluidized beds, and moving mat filters (Crini
exchange: et al., 2019; Patel, 2019). However, the batch system and fixed-bed
process are the most used. A scheme with the types of adsorption pro
SMZ − Br + H2 AsO4 − → SMZ − H2 AsO4 + Br− (1)
cesses and different parameters that influence it iss shown in Fig. 3.
There are two main hypotheses regarding the adsorption of heavy
2SMZ − Br + HAsO4 2− → SMZ2 − HAsO4 + 2Br− (2)
metals by natural zeolites in batch and fixed-bed systems. The first hy
In addition, Jeon et al. (2009) reported an As(V) adsorption on ICZ pothesis assigns a similar adsorption capacity to both systems (Baker
through a ligand exchange reactions mechanism expressed by the et al., 2008; Jeon et al., 2009). Thee second hypothesis claims a higher
following equations: adsorption capacity for batch systems (Inglezakis et al., 2015; Nguyen
et al., 2015). The advantages of the fix-bed process are its higher
Fe − OH + H2 AsO4 − → Fe − OAsO3 H + OH− (3) adsorption time and better heat/mass transfer than a batch system. On
the other hand, it is easier for a batch system to control the adsorption
Fig. 2. A scheme for principal mechanisms of adsorption of heavy metals with natural zeolites: a) Ion Exchange, b) Electrostatic Interaction.
9
Fig. 3. Factors influencing the adsorption process.
parameters mentioned (Crini et al., 2019). Both batch systems and H2SO4, HNO3, HCOOH, CH3COOH), and alkalis (NaCl, KCl, NH4Cl,
fixed-bed processes have low costs and are easy to operate. NaOH, NaHCO3, Na2CO3, KOH, K2CO3 Ca (NO3)2).
Katsou et al. (2011) reported the effect of different desorbing re
7. Regeneration/desorption process of natural zeolites agents (HNO3 (5% and 10%), NaCl, KCl (0.1 M, 0.5 M, 1 M, 3 M, and 5
M), and NH4Cl) for Pb desorption from natural clinoptilolite. They found
An important feature of the adsorbents is their regeneration capacity that 3 M KCl has many cycles while the first desorption capacity was
to recover the adsorbed heavy metals and reuse the natural zeolites in as greater than 98.5%. Likewise, the desorption capacity of Cd from
many cycles as possible. The regeneration cycles make use of the acid-modified clinoptilolite with different desorbing agents (NaCl (0.5
adsorbent more effectively and, consequently, provide lower costs M, 1 M, 2 M), HNO3, HCl, NH3, KNO3 (0.05 M, 1 M), KClO3 (0.05 M, 0.1
(Upadhyay et al., 2021; Vakili et al., 2019). The desorption process M)) was reported. In the study mentioned, 88–92% of Cd was recovered
depends on different parameters, such as the desorption operating pa using 1 M of KNO3 as a desorbent agent (Vasylechko et al., 2003).
rameters, selectivity, and the solution concentration (Katsou et al., Furthermore, the desorption process of surfactant and metallic-
2011; Lata et al., 2015). In contrast to the adsorption of heavy metals modified natural zeolites was reported (Chutia et al., 2009; Nguyen
with natural zeolites, fewer studies have investigated the desorption of et al., 2015). The regeneration of chromate-saturated HDPB-zeolite with
heavy metals from natural zeolites. Na2CO3/NaOH extraction and HCl solution achieved an efficiency of
According to the literature (Chutia et al., 2009; Dal Bosco et al., more than 90% (Zeng et al., 2010). A desorption process of single and
2005; Gedik and Imamoglu, 2008; Lata et al., 2015; Nguyen et al., 2015; mixed solutions of Pb, Cd, Cu, Cr, and Zn from ICZ was reported. The ICZ
Öztaş et al., 2008), there are two main categories of reagents to wash was regenerated using 0.1 M HCl, and two cycles of regeneration were
and recover natural zeolites by removing heavy metals i.e., acids (HCl, successfully achieved. After the second regeneration cycle, they
10
observed a considerable decrease in the desorption percentage because equal affinity to the adsorbate and most of the adsorption sites have a
of the possible damage of the ICZ structure by contact with an acidic similar affinity towards the adsorbate (Al-Abbad and Al Dwairi, 2021;
medium (Nguyen et al., 2015). Chen et al., 2022; Cincotti et al., 2006; Pomazkina et al., 2014; Rakhym
The amount of each metal desorbed from zeolite into the solution per et al., 2020; Ratios, 2019; Shirzadi and Nezamzadeh-Ejhieh, 2017; Yuan
unit mass of desorbing (qd (mg/g)) at equilibrium is: et al., 2018). The Freundlich model has also been widely applied to the
adsorption data for heavy metal adsorption with zeolites (Kragović
(Cdesorded )
qd = ∗V (7) et al., 2013; Merrikhpour and Jalali, 2013; Salgado-Gómez et al., 2014;
m
Song et al., 2015). Freundlich model predicts that heavy metal adsorp
where Cdesorbed is the liquid phase metal concentration detected in the tion is multilayer adsorption with a heterogeneous surface of natural
desorption solution at the end of the desorption experiment (in the zeolites, indicating infinite surface coverage and not adsorbent satura
equilibrium conditions) (mg/L) and V is the volume of the desorbing tion (Chen et al., 2022). Other isotherm models that have also been
solution (L) (Katsou et al., 2011). applied to study the relationship between the heavy metal adsorption
The amount of pollutant adsorbed on the natural zeolites and the and natural zeolites are Dubinin-Radushkevich (Asgari et al., 2013;
final pollutant concentration can be calculated through the desorption Inglezakis et al., 2010; Li et al., 2007), Temkin (Günay et al., 2007), and
ratio equation (8) (Öztaş et al., 2008). Redlich-Peterson isotherm (Mehdi et al., 2022). Therefore, the appli
[ ] cability of mathematical models to model the adsorption/desorption
q process will be according to the analysis of the characteristics of heavy
Desorption Ratio = d × 100% (8)
qt metals, natural zeolites, and operating parameters.
where qd is the amount of metal desorbed per unit mass of desorbing 8.2. Adsorption/desorption kinetics
(mg/g), and qt is the amount of metal adsorbed onto the mineral per unit
mass of adsorbent at equilibrium (mg/g). Different mathematical models could describe the rate of adsorp
According to the literature (Lata et al., 2015; Lihareva et al., 2010; tion/desorption and diffusion of heavy metals on natural zeolites. This
Vasylechko et al., 2003), the desorption process could be the inverse of data provides insight into the adsorption stages, including internal mass
the adsorption process for modified zeolites in acidic or basic media. In transfer, external mass transfer, and adsorption (Sikiru et al., 2022). The
other words, if the natural zeolite was treated in an acidic medium, the models applied are pseudo-first-order models which assume a
desorption process should be carried out in a basic solution. In contrast, non-reversible reaction (Merrikhpour and Jalali, 2013; Shaheen et al.,
if the natural zeolite was treated in a base medium the desorption pro 2012; Zanin et al., 2017),and pseudo-second-order kinetic models,
cess should be carried out in an acidic solution. In addition, the which indicate that the rate-limiting step is chemisorption. The Elovich
adsorption process is faster than the desorption process, and the metal model expresses rate-limiting step in chemisorption on an energetically
ions that were adsorbed readily were more difficult to desorb (Katsou heterogeneous surface (Noroozifar et al., 2014), and the intra-particle
et al., 2011). diffusion model contributes to determine whether adsorption occurs in
The desorption process could be used to determine the adsorption three stages (i) film diffusion (ii) intraparticle or pore diffusion (iii)
mechanisms. It shows if the adsorption process can be reversible or not sorption onto interior sites (Katsou et al., 2011; Ozdes et al., 2011).
by comparing the rate of adsorption and desorption process at equilib Among these kinetic models, the pseudo-second order kinetic model has
rium (Fu and Wang, 2011). For example, (Mendoza-Barrón et al., 2010), been the best fit for the adsorption of heavy metals with natural zeolites.
reported that the adsorption of As(V) on SMZ was not reversible in This result indicates that a large part of heavy metals such as As (Bilici
different pH values since the equilibrium in the desorption step differs Baskan and Pala, 2011), Cd (Merrikhpour and Jalali, 2013), Cr (Dimas
from the adsorption isotherms. Rivera et al., 2021; Lv et al., 2014a; Taamneh and Al Dwairi, 2013), Pb
A summary of previous investigations on the desorption of heavy (Fei et al., 2010; Ratios, 2019), Hg (Shirzadi and Nezamzadeh-Ejhieh,
metals on natural zeolites is presented in Table S7 of supplementary 2017), and Ni (Al-Abbad and Al Dwairi, 2021; Rajic et al., 2010) are
material. adsorbed with natural zeolites by chemisorption via intraparticle
diffusion and inner-pore (Boparai et al., 2011; Chen et al., 2022; Pah
8. Modeling of adsorption/desorption of heavy metals on lavanzadeh and Motamedi, 2020).It can also be indicated that the
natural zeolites adsorption process of heavy metals on zeolites is typically carried out in
two stages, a fast stage in which the equilibrium is reached quickly and
Mathematical models complement experimental studies for the following one which is slower and therefore takes longer to reach the
designing adsorption systems and optimizing the dynamic behavior of equilibrium (S. Z. N. Ahmad et al., 2020). Furthermore, a good corre
adsorption/desorption processes (Taamneh and Al Dwairi, 2013). For lation of three kinetic models (pseudo-first-order, pseudo-second-order,
mathematical modeling, it is crucial to determine the operation pa and intra-particle diffusion) for the adsorption of heavy metals like Cr
rameters such as contact time, stirring speed, pH, initial concentration, (VI) (Asgari et al., 2013; Sparks, 2003) as well as a mixed solution of Pb,
adsorbent dosage, temperature, particle size, flow rate, dimensions of Cu, Cd, Cr(III) and Zn are reported (Nguyen et al., 2015).
sorbent bed, etc. (Batool et al., 2018; Patel, 2021). Moreover, it is
necessary to analyze the properties of the adsorbent and adsorbate 9. Adsorption of heavy metals from wastewater
(here, natural zeolite and heavy metals, respectively) (Hong et al., 2019;
Mehdi et al., 2022). A summary of different isotherms and mathematical Despite numerous investigations on the kinetics and equilibrium
equations were reported in previous studies (Chen et al., 2022; Patel, behavior of natural zeolites in the adsorption of heavy metals, no out
2019). comes on the performance of natural zeolites in wastewater have been
reported. However, a few studies reported the effectiveness of natural
8.1. Adsorption/desorption isotherms zeolites in reducing the concentration of heavy metals after the
adsorption process. Halimoon and Yin (2010) studied the removal of
Different isotherm models have modeled the equilibrium adsorption heavy metals from textile wastewater for different adsorbent dosages
of different heavy metals with natural zeolites. According to the litera (10 mg/L- 40 mg/L), in their study they reported decrease in the con
ture, the Langmuir model is the best-fitting model for the adsorption of centration with percentages above 50%. The initial concentration of Pb,
heavy metals in zeolites. The Langmuir model describes monolayer Cu, Cd, Cr decreased from 0.64, 0.19, 0.41, 0.06 mg/L to 0.2507,
adsorption of heavy metal ions, where most of the active sites have an 0.0218, 0.0240, and 0.0247 mg/L, respectively. In other study a
11
decrease in the concentration of Cu, Fe, and Cr from printing industry administration, Funding acquisition, Resources, Writing - Review &
wastewater from 0.1220, 0.5598, 0.0935 mg/L to 0.018, 0,111, 0.031 Editing.
mg/L was reported by Zanin et al. (2017). Additionally, using the
Box-Behnken experimental design, considerable adsorption of Cd (96%) Funding
and Pb (99%) from Kermanshah oil refinery wastewater was reported
(Aghel et al., 2020). Swedish International Development Cooperation Agency (SIDA),
These few studies confirm that the optimization and mechanism of contribution No. 13486.
heavy metal adsorption on natural zeolites remains a challenge, mainly
because of the complex composition and chemistry of wastewater,
which can vary according to the effect of different parameters on the Declaration of competing interest
interaction of different components of the wastewater composition
(Martín-Lara et al., 2014; Mosivand et al., 2019). The authors declare that they have no known competing financial
Some alternatives to solve this challenge and model the isotherm and interests or personal relationships that could have appeared to influence
kinetic could be through the application of real-time concentration the work reported in this paper.
sensors. Also, the application of computational fluid dynamics (CFD)
(Baši’c et al., 2023; Esfandian et al., 2017) would facilitate to analyze Data availability
the phenomena underlying the interaction mechanisms between heavy
metals in wastewater and natural zeolites. Data will be made available on request.
10. Conclusions and outlook Acknowledgments
We summarize that natural zeolites are excellent adsorbents for This work was supported by Swedish International Development
heavy metals. Natural zeolite properties like ease of ion exchange, Cooperation Agency(SIDA), contribution No. 13486, Farid Akhtar ac
adsorption, dehydration, and rehydration, as well as being eco-friendly, knowledges the financial support from the National Natural Science
low cost, regenerative, easily accessible, and available, make natural Foundation of China (No. 52020105011).
zeolite an excellent choice as an adsorbent. The properties mentioned
will benefit people of those countries with natural zeolite resources, Appendix A. Supplementary data
helping to reduce costs and pollution using natural resources instead of
applying other kinds of toxic and/or synthetic adsorbents which Supplementary data to this article can be found online at https://doi.
generate different types of pollutants. org/10.1016/j.chemosphere.2023.138508.
In addition, to obtain greater adsorption capacity for heavy metals,
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Chemosphere 328 (2023) 138508

Contents lists available at ScienceDirect

Adsorption of heavy metals on natural zeolites: A review

• The accumulation of heavy metals in

American Clinoptilolite – – 15 – – HDTMA (Li et al., 2007)

Modified – – Modified – – HDPB

Chemosphere 328 (2023) 138508

Fe (III) zeolite: Iron-coated zeolite heulandite, – 7.51 – – Fe (NO3)3*KOH

Mordenite >17%, Feldspar, Quartz, Calcite

Chemosphere 328 (2023) 138508

4.4. Lead 4.6. Nickel

2016c). Ion exchange and electrostatic attraction mechanisms are the

Fig. 3. Factors influencing the adsorption process.

10. Conclusions and outlook Acknowledgments

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